Polymerization catalysts for producing polymers with low levels of long chain branching
18 claims: 2 independent, 16 dependent
- 1式:[式中、M 2 は、ジルコニウム又はハフニウムであり;R 5A 及びR 5B は、独立に、ヒドロカルビル基若しくはトリヒドロカルビルシリル基(それらのいずれも20個までの炭素原子を有する)、又は水素であり;nは、0から10(両端を含む)の整数であり;X 3A 及びX 4A は、独立に、1)F、Cl、Br、若しくはI;2)20個までの炭素原子を有するヒドロカルビル基、H、若しくはBH 4 ;3)ヒドロカルビルオキシド基、ヒドロカルビルアミノ基、若しくはトリヒドロカルビルシリル基(それらのいずれも20個までの炭素原子を有する);又は、4)OBR A 2 若しくはSO 3 R A (ここで、R A は、アルキル基若しくはアリール基であり、それらのいずれも12個までの炭素原子を有する)である。] を有する化合物 。
- 2X 3A 及びX 4A が、独立に、F、Cl、Br、若しくはIである、請求項1に記載の化合物。
- 3X 3A 及びX 4A がClである、請求項1に記載の化合物。
- 4X 3A 及びX 4A が、独立に、H、BH 4 、メチル、フェニル、ベンジル、ネオペンチル、トリメチルシリルメチル、CH 2 CMe 2 Ph;CH 2 SiMe 2 Ph;CH 2 CMe 2 CH 2 Ph;又はCH 2 SiMe 2 CH 2 Phである、請求項1に記載の化合物。
- 5X 3A 及びX 4A が、独立に、メチル、フェニル又はベンジルである、請求項1に記載の化合物。
- 6R 5A 及びR 5B が、独立に、H、メチル、アリル、ベンジル、ブチル、ペンチル、ヘキシル、又はトリメチルシリルである、請求項1に記載の化合物。
- 7R 5A 及びR 5B が、独立に、H又はメチルである、請求項1に記載の化合物。
- 8R 5A 及びR 5B がHである、請求項1に記載の化合物。
- 9nが1から6(両端を含む)の整数である、請求項1に記載の化合物。
- 10nが1又は2である、請求項1に記載の化合物。
- 11R 5A 及びR 5B が、独立に、H又はメチルであり;nが1から6(両端を含む)の整数であり;X 3A 及びX 4A が、独立に、Cl、メチル、フェニル又はベンジルである、請求項1に記載の化合物。
- 12以下の式のいずれかを有する化合物である、請求項1に記載の化合物。
- 13以下から選択される式を有する化合物。
- 14以下の式を有する化合物である、請求項13に記載の化合物。
- 15以下の式を有する化合物である、請求項13に記載の化合物。
- 16以下の式を有する化合物である、請求項13に記載の化合物。
- 17以下の式を有する化合物である、請求項13に記載の化合物。
- 18以下の式を有する化合物である、請求項13に記載の化合物。
Independent claims18
225 paragraphs, as filed
The present invention relates to an organic metal composition, an olefin polymerization catalyst composition, an olefin polymerization and copolymerization method using the catalyst composition, and a technical field of polyolefin.
Mono-1-olefins containing ethylene (α-olefins) are often combined with solid oxides and in the presence of cocatalysts using catalytic compositions using titanium, zirconium, vanadium, chromium, or other metals. It is known that it can be polymerized. These catalyst compositions may be useful for both homopolymerization of ethylene and copolymerization of ethylene with commonomers such as propylene, 1-butene, 1-hexene, or other higher α-olefins. Therefore, constant exploration is underway to develop new olefin polymerization catalysts, catalytic activation methods, and methods of making and using catalysts that provide enhanced catalytic activity and polymeric materials made for specific end applications. It has been damaged.
<p num="0003"> Polyethylene (PE) produced by a number of methods generally contains a small amount of long chain branched molecules to be adjusted. In some cases, long chain branching (LCB) is desirable to improve foam stability during film blow molding or to increase the processability of metallocene-catalyzed resins. However, in many applications, the presence of LCB is usually considered undesirable due to the increased elasticity given to the resin. Therefore, the ability to control LCB levels in polyethylene using metallocene-based catalysts is a desirable goal.</p><p num="0004"> An example of this need is found in the use of cross-linking or ansa-metallocene catalysts, which are desirable catalysts for some purposes but may tend to produce polymers with LCB levels that are detrimental to film performance. Therefore, novel catalyst compositions and methods that allow better control of LCB levels within the desired specification range are desirable goals.</p>
<p num="0005"> The present invention includes catalyst compositions, methods of preparing catalytic compositions, methods of polymerizing olefins, and ethylene polymers and copolymers. In the process of investigating metallocene-based olefin polymerization catalysts, the long-chain branched (LCB) content of PE resins produced using such catalysts is, among other things, related to the type of metallocene catalyst used and the catalyst composition. It has also been found to be involved in certain solid oxide activators that may constitute one of the components of the.</p><p num="0006"> For example, in one embodiment of the invention, it has been discovered that certain metallocene-based catalyst systems can produce high molecular weight polyethylene with low levels of LCB, even under relatively high temperature conditions. Metallocenes useful in preparing the catalytic compositions of the present invention include, but are not limited to, pendant alkenyl (olefin-containing) groups attached to at least a portion of the cyclopentadienyl form of the strongly crosslinked ligand. Includes strongly crosslinked ansa-metallocenes, including one or two aryl groups attached to the crosslinked atoms of the strongly crosslinked ligand, particularly one or two phenyl groups.</p><p num="0007"> Thus, in one embodiment, the invention is strongly cross-linked containing a pendant olefin-containing moiety attached to at least a portion of the cyclopentadienyl-type ligand and one or two aryl groups attached to the cross-linked atom of the cross-linked ligand. Includes a catalytic composition comprising at least one ansa-metallocene compound; optionally at least one organoaluminum compound; and at least one activator. In one embodiment, the at least one activator is a solid oxide treated with an electron-attracting anion; layered minerals; ion-exchangeable activators-carriers; organic aluminoxane compounds; organoboron compounds; organic borates. It can be a salt compound; or an activator-carrier containing any combination of any of these activators. In another embodiment, the invention, as provided herein, is one or two attached to a pendant olefin-containing moiety attached to at least a portion of a cyclopentadienyl-type ligand and a cross-linked atom of the cross-linked ligand. It comprises at least one strongly crosslinked ansa-metallocene compound containing an aryl group; optionally at least one organoaluminum compound; and at least one activator contact product. In this embodiment, the present invention includes a composition of a substance, a catalyst composition for polymerizing an olefin, a method for preparing a catalyst composition, a method for polymerizing an olefin, a novel polymer and a copolymer of ethylene, and the like, respectively. In the case of, at least one strongly crosslinked ansa- containing a pendant olefin-containing moiety attached to at least a part of the cyclopentadienyl type ligand and one or two aryl groups bonded to the crosslinked atom of the crosslinked ligand. Includes metallocene compounds; optionally at least one organic aluminum compound; as well as at least one activator. In another embodiment, the at least one activator can be a solid oxide activator-carrier, i.e., an activator-carrier containing a solid oxide treated with an electron-attracting anion.</p><p num="0008"> In one embodiment, the catalytic compositions of the invention are 1) at least one ansa-metallocene; 2) optionally at least one organoaluminum compound; and 3) contact with at least one activator. Can include products, where a) At least one ansa-metallocene has the formula: (X<sup>1</sup>) (X<sup>2</sup>) (X<sup>3</sup>) (X<sup>4</sup>) M<sup>1</sup>[During the ceremony, M<sup>1</sup>Is titanium, zirconium, or hafnium; (X<sup>1</sup>) And (X<sup>2</sup>) Are independently substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl; (X<sup>1</sup>) And (X<sup>2</sup>The one substituent on) is given by the formula ER<sup>1</sup>R<sup>2</sup>In the formula, E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is (X).<sup>1</sup>) And (X<sup>2</sup>), And R<sup>1</sup>And R<sup>2</sup>Are independently alkyl or aryl groups (each of which has up to 12 carbon atoms) or hydrogen, where R<sup>1</sup>And R<sup>2</sup>At least one of them is an aryl group; (X<sup>1</sup>) Or (X<sup>2</sup>) At least one substituent is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms; (X<sup>3</sup>) And (X<sup>4</sup>) Are independently 1) F, Cl, Br, or I; 2) a hydrocarbyl group with up to 20 carbon atoms, H, or BH.<sub>4</sub>3) Hydrocarbyl oxide group, hydrocarbylamino group, or trihydrocarbylsilyl group (all of which have up to 20 carbon atoms); 4) OBR<sup>A</sup><sub>2</sub>Or SO<sub>3</sub>R<sup>A</sup>(Here, R<sup>A</sup>Is an alkyl or aryl group, each of which has up to 12 carbon atoms); Substituents on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl groups are independently aliphatic groups, aromatic groups, cyclic groups, combinations of aliphatic and cyclic groups, Oxygen group, sulfur group, nitrogen group, phosphorus group, arsenic group, carbon group, silicon group, or boron group (all of which have 1 to 20 carbon atoms); halides; or hydrogen] Includes compounds with; b) At least one organoaluminum compound has the formula Al (X<sup>5</sup>)<sub>n</sub>(X<sup>6</sup>)<sub>3-n</sub>[In the formula, (X<sup>5</sup>) Is a hydrocarbyl containing 1 to 20 carbon atoms; (X)<sup>6</sup>) Are alkoxides or aryl oxides (all of which have 1 to 20 carbon atoms), halides, or hydrides; n is a number from 1 to 3 (including both ends)] Includes compounds with; c) At least one activator i) Solid oxides treated with electron-attracting anions, layered minerals, ion-exchangeable activators-carriers, or activators-carriers containing any combination thereof; ii) Organic aluminoxane compounds iii) Organoboron compounds or organoborate compounds; or iv) Any combination of them Is selected independently from.</p><p num="0009"> In one aspect of the invention:<sup>3</sup>) And (X<sup>4</sup>) Is a hydrocarbyl group with up to 20 carbon atoms, H, or BH<sub>4</sub>2) At least one activator comprises at least one organoaluminoxan compound; or 3) if both conditions 1 and 2 are present, at least one organoaluminum compound is optional. obtain. Thus, although not intended to be constrained by theory, metallocene-based compositions exhibit catalytic polymerization activity are usually 1) metallocene components; 2) components that give metallocene an activating ligand such as an alkyl or hydride ligand ( It will be appreciated by those skilled in the art that the metallocene compound does not yet contain such a ligand); and 3) contains a catalytic product of the activator component. In some cases, one component can function as both an activating ligand and an activating component-providing component, such as organic aluminoxane. In other cases, these two functions can be provided by two separate components, eg, organoaluminum compounds that can give metallocene an activating alkyl ligand and electron attraction that can give an activator function. It is a solid oxide treated with a sex anion. Moreover, in some cases, the metallocene compound can already contain an activating ligand, such as an alkyl ligand, and thus no component providing an activating ligand is required, but of any optional of the contact product. Can be an ingredient. Thus, by designating at least one organoaluminum compound as "optional" in the contact product, it is not necessary to impart catalytic activity to the composition containing the contact product, as will be appreciated by those skilled in the art. , It is intended to reflect that organoaluminum compounds can be optional.</p><p num="0010"> In another aspect of the invention, the invention provides a catalytic composition comprising at least one ansa-metallocene, at least one organoaluminum compound, and at least one activator-carrier contact product. Being done here a) At least one ansa-metallocene formula<chemistry num="1"><img id="000002" he="44" wi="56" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>[During the ceremony, M<sup>1</sup>Is zirconium or hafnium; X is independently F, Cl, Br, or I; E is C or Si; R<sup>1</sup>And R<sup>2</sup>Are independently alkyl or aryl groups (each of which has up to 10 carbon atoms) or hydrogen, where R<sup>1</sup>Or R<sup>2</sup>At least one of them is an aryl group; R<sup>3A</sup>And R<sup>3B</sup>Are independently hydrocarbyl or trihydrocarbylsilyl groups (both of which have up to 20 carbon atoms); or hydrogen; n is an integer from 0 to 10 (including both ends); R<sup>4A</sup>And R<sup>4B</sup>Is independently a hydrocarbyl group with up to 12 carbon atoms, or hydrogen] Includes compounds with; b) At least one organic aluminum compound is trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminumethoxydo, diisobutylaluminum hydride, Includes diethylaluminum chloride, or any combination thereof; c) At least one activator-carrier comprises a solid oxide treated with an electron-withdrawing anion, where. Solid oxides are silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or their mixture. Any combination; Electro-attracting anions include fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluorobolate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, Fluorotitanates, permanganates, substituted or unsubstituted alkane sulfonates, substituted or unsubstituted allene sulfonates, substituted or unsubstituted alkyl sulphates, or any combination thereof.</p><p num="0011"> In yet another embodiment, the invention provides a catalytic composition comprising 1) at least one ansa-metallocene; and 2) at least one catalytic product of an activator. a) At least one ansa-metallocene has the formula: (X<sup>1</sup>) (X<sup>2</sup>) (X<sup>3</sup>) (X<sup>4</sup>) M<sup>1</sup>[During the ceremony, M<sup>1</sup>Is titanium, zirconium, or hafnium; (X<sup>1</sup>) And (X<sup>2</sup>) Are independently substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl; (X<sup>1</sup>) And (X<sup>2</sup>The one substituent on) is given by the formula ER<sup>1</sup>R<sup>2</sup>In the formula, E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is (X).<sup>1</sup>) And (X<sup>2</sup>), And R<sup>1</sup>And R<sup>2</sup>Are independently alkyl or aryl groups (each of which has up to 12 carbon atoms) or hydrogen, where R<sup>1</sup>And R<sup>2</sup>At least one of them is an aryl group; (X<sup>1</sup>) Or (X<sup>2</sup>) At least one substituent is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms; (X<sup>3</sup>) And (X<sup>4</sup>) Are independently 1) F, Cl, Br, or I; a hydrocarbyl group having up to 20 carbon atoms, H, or BH.<sub>4</sub>3) Hydrocarbyl oxide group, hydrocarbylamino group, or trihydrocarbylsilyl group (all of which have up to 20 carbon atoms); 4) OBR<sup>A</sup><sub>2</sub>Or SO<sub>3</sub>R<sup>A</sup>(Here, R<sup>A</sup>Is an alkyl or aryl group, each of which has up to 12 carbon atoms; where (X)<sup>3</sup>) And (X<sup>4</sup>) Is a hydrocarbyl group with up to 20 carbon atoms, H, or BH<sub>4</sub>Is; Substituents on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl groups are independently aliphatic groups, aromatic groups, cyclic groups, combinations of aliphatic and cyclic groups, Oxygen group, sulfur group, nitrogen group, phosphorus group, arsenic group, carbon group, silicon group, or boron group (all of which have 1 to 20 carbon atoms); halide; or hydrogen] Includes compounds with; b) At least one activator i) Solid oxides treated with electron-attracting anions, layered minerals, ion-exchangeable activators-carriers, or activators-carriers containing any combination thereof; ii) Organic aluminoxane compounds; iii) Organoboron compounds or organoboron salt compounds; or iv) Any combination of them Is selected independently from.</p><p num="0012"> In yet another aspect of the invention, a catalytic composition comprising 1) at least one ansa-metallocene; and 2) at least one catalytic product of an activator is provided, wherein. a) At least one ansa-metallocene has the formula:<chemistry num="2"><img id="000003" he="47" wi="59" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>[During the ceremony, M<sup>1</sup>Is zirconium or hafnium; X is independent, H, BH<sub>4</sub>, Methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH<sub>2</sub>CMe<sub>2</sub>Ph; CH<sub>2</sub>SiMe<sub>2</sub>Ph; CH<sub>2</sub>CMe<sub>2</sub>CH<sub>2</sub>Ph; or CH<sub>2</sub>SiMe<sub>2</sub>CH<sub>2</sub>Ph; E is C or Si; R<sup>1</sup>And R<sup>2</sup>Are independently alkyl or aryl groups (each of which has up to 10 carbon atoms) or hydrogen, where R<sup>1</sup>Or R<sup>2</sup>At least one of them is an aryl group; R<sup>3A</sup>And R<sup>3B</sup>Are independently hydrocarbyl or trihydrocarbylsilyl groups (each of which has up to 20 carbon atoms) or hydrogen; n is an integer from 0 to 10 (including both ends); R<sup>4A</sup>And R<sup>4B</sup>Is independently a hydrocarbyl group with up to 12 carbon atoms, or hydrogen] Includes compounds with; b) At least one activator is an activator-carrier containing a solid oxide treated with an electron-attracting anion, where. Solid oxides are silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or their mixture. Any combination; Electro-attracting anions include fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluorobolate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, Fluorotitanates, permanganates, substituted or unsubstituted alkane sulfonates, substituted or unsubstituted allene sulfonates, substituted or unsubstituted alkyl sulphates, or any combination thereof.</p><p num="0013"> In a further aspect of the invention, the activator-carrier may comprise a solid oxide treated with an electron-attracting anion, where the solid oxide is silica, alumina, silica-alumina, aluminophosphate. , Aluminum phosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof. In this embodiment, the electron-attracting anion is fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluorobolate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate. , Fluorosilicates, fluorotitanates, permanganates, substituted or unsubstituted alcan sulfonates, substituted or unsubstituted alene sulfonates, substituted or unsubstituted alkyl sulphates, etc. (including any combination thereof). In addition, the activator-carrier may further comprise a metal or metal ion, such as zinc, nickel, vanadium, tungsten, molybdenum, silver, tin, or any combination thereof. In this embodiment, the electron-attracting anion is also fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirco. It can be nitrate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alcan sulfonate, substituted or unsubstituted allene sulfonate, substituted or unsubstituted alkyl sulphate, etc. (including any combination thereof).</p><p num="0014"> In yet another aspect of the invention, the activator-carrier can include layered minerals, ion exchange activation-carriers, and any combination thereof. In this embodiment, the activator-carrier is a clay mineral, columnar clay, exfoliated clay, exfoliated clay gelled into another oxide matrix, layered silicate mineral, non-layered silicate mineral, layered aluminosilicate mineral, non-layered aluminosilicate. It may include minerals, or any combination thereof.</p><p num="0015"> In another embodiment, the present invention is a method for producing a polymerization catalyst composition, wherein at least one ansa-metallocene compound; optionally at least one. Organoaluminium compounds; and methods comprising contacting at least one activator are further provided, wherein at least one ansa-metallocene, at least one organoaluminum compound, and at least one activity. The agents are as defined herein. In yet another embodiment, the invention provides a method of polymerizing an olefin, comprising contacting ethylene and an optional α-olefin comonomer with a catalytic composition under polymerization conditions to form a polymer or copolymer. Here; the catalytic composition is given as disclosed herein. In a further embodiment, the present invention comprises contacting ethylene and an optional α-olefin comonomer with a catalytic composition under polymerization conditions to form a polymer or copolymer, which is produced from the ethylene polymer and copolymer produced therein. Articles to be provided; where the catalytic composition is given as disclosed herein.</p><p num="0016"> In one embodiment of the invention, the activity of the catalytic composition of the invention is to pre-contact some of the polymerization reaction components to form a first mixture during the first period, followed by the mixture. It can be enhanced by contacting the remaining polymerization reaction components during the second period to form a second mixture. For example, the ansa-metallocene compound may be pre-contacted with some other polymerization reaction component, including, but not limited to, an α-olefin monomer and an organoaluminum co-catalyst for a period of time, after which the mixture may be limited. Although not, it is contacted with the remaining polymerization reaction components, including the solid oxide activator-carrier. The first mixture is usually referred to as the "pre-contact" mixture and contains the pre-contact component, and the second mixture is commonly referred to as the "post-contact" mixture and contains the post-contact component. For example, a mixture of at least one metallocene, at least one olefin monomer, and at least one organoaluminum cocatalyst compound before contacting this mixture with the activator-carrier is one of the "pre-contact" mixtures. It is a seed. Thus, the metallocene, monomer, organoaluminum cocatalyst, and acid activator-carrier mixtures formed by contacting the pre-contact mixture with the acid activator-carrier are referred to as "post-contact" mixtures. The term is used, if any, regardless of the type of reaction that occurs between the components of the mixture. For example, according to the present specification, pre-contact organoaluminum compounds, once mixed with metallocenes (s) or metallocenes (s), and olefin monomers, are clearly distinguishable organics used to prepare pre-contact mixtures. It is possible to have a chemical composition and structure different from those of an aluminum compound.</p><p num="0017"> The present invention also includes a method of producing a catalyst composition using at least one ansa-metallocene catalyst, optionally at least one organoaluminum compound, and at least one activator. In the methods of the invention, any selected catalyst component, such as a metallocene catalyst and an organoaluminum co-catalyst, is pre-contacted with an olefin, but not necessarily, a monomer to be polymerized or copolymerized, followed by this. The step of contacting the catalytic mixture with any remaining catalytic component, in this example a solid oxide activator-carrier, is included.</p><p num="0018"> In yet another embodiment, the invention further comprises a novel catalyst composition, a method of preparing the catalyst composition, and a method of polymerizing an olefin that may result in improved productivity. In one embodiment, these methods can be carried out without the need to use expensive organic aluminoxane co-catalysts such as methylaluminoxane (MAO) in large excess concentrations, or the catalyst composition is aluminoxane such as MAO. It can be substantially excluded. That is, the catalyst composition of the present invention can have polymerization activity in the substantially absence of aluminoxane. However, the present invention also provides a catalytic composition comprising ansa-metallocene compound and aluminoxane. Thus, in this embodiment, the catalyst composition does not need to include an acid activator-carrier containing a solid oxide in which the activator-carrier has been chemically treated, and the catalyst composition comprises an organoaluminum compound. I don't even need that.</p><p num="0019"> Furthermore, the present invention includes a method comprising contacting at least one monomer and a catalyst composition under polymerization conditions to form a polymer. Therefore, the present invention includes a method of polymerizing an olefin using a catalytic composition prepared as described herein.</p><p num="0020"> The present invention also includes novel polyolefins.</p><p num="0021"> The present invention also includes articles containing polymers produced using the catalyst compositions of the present invention.</p><p num="0022"> These and other features, embodiments, embodiments, and advantages of the present invention will become apparent after reviewing the following detailed description of the disclosed features.</p>
<figref num="1">It is a figure explaining the structure of the specific metallocene used in the Example of the invention.</figref><figref num="2">It is a figure explaining the structure of the specific metallocene used in the comparative example.</figref><figref num="3">Invention Examples 1 to 4 (R<sub>g</sub>Against M<sub>w</sub>It is a figure explaining the data obtained from the SEC-MALS analysis of the ethylene homopolymer produced in (Plot).</figref><figref num="4">Invention Examples 5 to 7 (R<sub>g</sub>Against M<sub>w</sub>It is a figure explaining the data obtained from the SEC-MALS analysis of the ethylene homopolymer produced in (Plot).</figref><figref num="5">Invention Examples 10 and 11 (R<sub>g</sub>Against M<sub>w</sub>It is a figure explaining the data obtained from the SEC-MALS analysis of the ethylene homopolymer produced in (Plot).</figref><figref num="6">For the polymers prepared according to Examples 1-11 of the invention, zero shear viscosity vs. molecular weight, in particular log (η).<sub>0</sub>) Vs log (M<sub>w</sub>) Is shown in the plot.</figref><figref num="7">For the polymers prepared by Comparative Examples 14-16, zero shear viscosity vs. molecular weight, especially log (η).<sub>0</sub>) Vs log (M<sub>w</sub>) Is shown in the plot.</figref><figref num="8">It is a figure which gives the comparison of the gel permeation chromatogram (GPC) about the ethylene homopolymer of Invention Examples 1 to 11 (E1 to E11) and Comparative Examples 14 to 16 (E14 to E16).</figref>
The present invention provides a novel catalyst composition, a method of preparing a catalyst composition, a method of using the catalyst composition to polymerize an olefin, an olefin polymer and articles made from it. In one embodiment, the invention presents at least one strongly crosslinked ansa-metallocene compound comprising an olefin-containing moiety pendant on a cyclopentadienyl-type ligand and at least one aryl group attached to a crosslinked atom of the crosslinked ligand. , And optionally, a catalytic composition comprising at least one organoaluminum compound. In another aspect, the invention includes a method of producing the catalytic composition disclosed herein, and in a further aspect, the invention uses the catalytic composition disclosed herein. Includes a method of polymerizing an olefin. As described above, the designation of at least one organoaluminum compound as an optional component in the contact product requires that the composition containing the contact product be catalyzed, as will be understood by those skilled in the art. If not, the organoaluminum compounds are intended to reflect that they can be optional. A detailed description of the components of the contact product is given below.
Catalyst composition and ingredients Metallocene compound In one embodiment, the invention comprises a robust containing an olefin-containing moiety attached to a cyclopentadienyl-type ligand and at least one aryl group attached to a crosslinked atom of the crosslinked ligand, as further disclosed herein. Provided is a catalytic composition comprising at least one ansa-metallocene compound crosslinked with, at least one activator, and optionally at least one organoaluminum compound.
As used herein, the term "crosslink or ansa-metallocene" refers to two ηs in the molecule.<sup>5</sup>-Simply refers to a metallocene compound to which a cycloalkazienyl ligand is attached by a crosslinked moiety. Useful ansa-metallocenes are usually "strongly cross-linked" with two ηs<sup>5</sup>-A cycloalkazienyl ligand is attached by a cross-linking group, where the η<sup>5</sup>-The shortest bond of the cross-linked moiety between cycloalkazienyl ligands is a single atom. Therefore, two η<sup>5</sup>-The cross-linking or chain length between the cycloalkazienyl ligands is one atom, but this cross-linking atom is substituted. Therefore, the metallocene of the present invention is a crosslinked screw (η).<sup>5</sup>-Cycloalkadienyl) type compound, where the η<sup>5</sup>-The cyclopentadienyl moiety includes a substituted cyclopentadienyl ligand, a substituted indenyl ligand, a substituted fluorenyl ligand, etc., where one substituent on these cyclopentadienyl ligands is , Expression ER<sup>1</sup>R<sup>2</sup>In the formula, E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is bound to both cyclopentadienyl-type ligands. In this embodiment, R<sup>1</sup>And R<sup>2</sup>Can be independently selected from alkyl or aryl groups (each of which has up to 12 carbon atoms), or hydrogen, where R<sup>1</sup>And R<sup>2</sup>At least one of them is an aryl group.
In this embodiment, a single substituent on the cyclopentadienyl ligand of metallocene has the formula> CR.<sup>1</sup>R<sup>2</sup>,> SiR<sup>1</sup>R<sup>2</sup>,> GeR<sup>1</sup>R<sup>2</sup>Or> SnR<sup>1</sup>R<sup>2</sup>Can be a cross-linking group with, where R<sup>1</sup>And R<sup>2</sup>Can be independently selected from alkyl or aryl groups (each of which has up to 12 carbon atoms), or hydrogen, where R<sup>1</sup>And R<sup>2</sup>At least one of them is an aryl group. Crosslink ER<sup>1</sup>R<sup>2</sup>Group examples, but not limited to> CPh<sub>2</sub>,> SiPh<sub>2</sub>,> GePh<sub>2</sub>,> SnPh<sub>2</sub>,> C (Trill)<sub>2</sub>,> Si (Trill)<sub>2</sub>,> Ge (Trill)<sub>2</sub>,> Sn (Trill)<sub>2</sub>,> CMePh,> SiMePh,> GeMePh,> SnMePh,> CEtPh,> CPrPh,> CBuPh,> CMe (Trill),> SiMe (Trill),> GeMe (Trill),> SnMe (Trill),> CHPh,> CH (trill) etc. are included.
Furthermore, η<sup>5</sup>-At least one substituent on at least a portion of the cycloalkazienyl ligand is a substituted or unsubstituted olefin-containing hydrocarbyl group having up to 12 carbon atoms, which is the position of the alkene functionality. Regardless of chemistry, it is referred to herein as an "alkenyl group". In this embodiment, the olefin-containing hydrocarbyl group is the η of the cross-linking ligand.<sup>5</sup>-It is bound to a part of a cycloalkazienyl type ligand, where the olefin bond is η.<sup>5</sup>-Distal from the cyclo-alkazienyl ligand and therefore can be described as a pendant alkenyl group. Thus, one substituent on the substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl of metallocene comprises an alkenyl group, in which case ansa-metallocene is one of the cyclopentadienyl-type ligands comprising an olefin moiety. It can be described as containing a hydrocarbyl chain attached to the moiety.
In another embodiment, at least one ansa-metallocene of the invention is expressed in the formula: (X<sup>1</sup>) (X<sup>2</sup>) (X<sup>3</sup>) (X<sup>4</sup>) M<sup>1</sup>[During the ceremony, M<sup>1</sup>Is titanium, zirconium, or hafnium; (X<sup>1</sup>) And (X<sup>2</sup>) Are independently substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl; (X<sup>1</sup>) And (X<sup>2</sup>The one substituent on) is given by the formula ER<sup>1</sup>R<sup>2</sup>In the formula, E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is (X).<sup>1</sup>) And (X<sup>2</sup>), And R<sup>1</sup>And R<sup>2</sup>Are independently alkyl or aryl groups (each of which has up to 12 carbon atoms) or hydrogen, where R<sup>1</sup>And R<sup>2</sup>At least one of them is an aryl group; (X<sup>1</sup>) Or (X<sup>2</sup>) At least one substituent is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms; (X<sup>3</sup>) And (X<sup>4</sup>) Are independently 1) F, Cl, Br, or I; 2) a hydrocarbyl group having up to 20 carbon atoms, H, or BH.<sub>4</sub>3) Hydrocarbyl oxide group, hydrocarbylamino group, or trihydrocarbylsilyl group (all of which have up to 20 carbon atoms); 4) OBR<sup>A</sup><sub>2</sub>Or SO<sub>3</sub>R<sup>A</sup>, Here, R<sup>A</sup>Is an alkyl or aryl group, each of which has up to 12 carbon atoms; Any additional substituent on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl group can be independently an aliphatic group, an aromatic group, a cyclic group, an aliphatic group and a cyclic group. Combination, oxygen group, sulfur group, nitrogen group, phosphorus group, arsenic group, carbon group, silicon group, or boron group (all of which have 1 to 20 carbon atoms); halides; or hydrogen. ] Includes compounds with.
In another aspect of the invention, the olefin-containing hydrocarbyl group is the η of the cross-linking ligand.<sup>5</sup>-It is attached to a part of a cycloalkazienyl type ligand, that is, the alkenyl group can have up to about 20 carbon atoms. In another embodiment, the alkenyl group can have up to about 12 carbon atoms, up to about 8 carbon atoms, or up to about 6 carbon atoms. Examples of alkenyl groups include, but are not limited to, butenyl, pentenyl, hexenyl, heptenyl, or octenyl. In another embodiment, the alkenyl group is 3-butenyl or 4-pentenyl. Thus, in one embodiment, the pendant unsaturated group is about 3 to about 7 carbon atoms removed from the cyclopentadienyl ligand itself, and in another embodiment, the cyclopentadienyl ligand itself. Can contain carbon-carbon double bonds derived from 3 to about 4 carbon atoms removed from.
In yet another embodiment, the olefin-containing hydrocarbyl group, i.e. the alkenyl group, can be substituted or unsubstituted. For example, any substituent on the alkenyl group, if present, is an aliphatic group, an aromatic group, a cyclic group, a combination of an aliphatic group and a cyclic group, an oxygen group, a sulfur group, a nitrogen group, a phosphorus group. , Arethane groups, carbon groups, silicon groups, boron groups, or their substitution analogs (all of which have about 1 to about 20 carbon atoms); halides; or can be selected independently of hydrogen. Hydrogen is listed as a possible substituent on the alkenyl group in the context that hydrogen can add unsaturated moieties within the alkenyl group as long as the alkenyl group is not destroyed. Thus, hydrogen can be a substituent on any unsaturated moiety within an alkenyl group, unless hydrogen is added over the very olefin moiety required to be considered an alkenyl group. In addition, this description of other substituents on the atom of the alkenyl group may include analogs of these moieties of substituted, unsubstituted, branched, linear, or heteroatom-substituted.
Examples of olefin hydrocarbyl groups, especially alkenyl groups, which can be attached to at least some cyclopentadienyl type moieties are, but are not limited to, 3-butenyl (CH).<sub>2</sub>CH<sub>2</sub>CH = CH<sub>2</sub>), 4-Pentenyl (CH)<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH = CH<sub>2</sub>), 5-Hexenil (CH)<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH = CH<sub>2</sub>), 6-Heptenyl (CH)<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH = CH<sub>2</sub>), 7-Octenil (CH)<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH = CH<sub>2</sub>), 3-Methyl-3-butenyl [CH<sub>2</sub>CH<sub>2</sub>C (CH<sub>3</sub>) = CH<sub>2</sub>], 4-Methyl-3-pentenyl [CH<sub>2</sub>CH<sub>2</sub>CH = C (CH)<sub>3</sub>)<sub>2</sub>], 1,1-dimethyl-3-butenyl [C (CH)<sub>3</sub>)<sub>2</sub>CH<sub>2</sub>CH = CH<sub>2</sub>], 1,1-dimethyl-4-pentenyl [C (CH)<sub>3</sub>)<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH = CH<sub>2</sub>] Etc., or any replacement analogs thereof. In one embodiment, the unsaturated group attached to the cross-linking group is 3-butenyl (CH).<sub>2</sub>CH<sub>2</sub>CH = CH<sub>2</sub>), 4-Pentenyl (CH)<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH = CH<sub>2</sub>), Or their substitution analogs.
Equation ER as disclosed herein<sup>1</sup>R<sup>2</sup>In addition to containing a cross-linking group with, and at least one alkenyl group, the cyclopentadienyl ligand can also have other substituents. For example, these substituents are of ansa-metallocene (X).<sup>3</sup>) And (X<sup>4</sup>) Can be selected from the same chemical groups or moieties that can function as ligands. Therefore, any additional substituent on the cyclopentadienyl type ligand; and any substituent on the substituted alkenyl group; and (X).<sup>3</sup>) And (X<sup>4</sup>) Shall independently be an aliphatic group, an aromatic group, a cyclic group, a combination of an aliphatic group and a cyclic group, an oxygen group, a sulfur group, unless these groups terminate the activity of the catalytic composition. , Nitrogen group, phosphorus group, arsenic group, carbon group, silicon group, boron group, or their substitution analogs (all of which have about 1 to about 20 carbon atoms); halides; or hydrogen. be able to. In addition, this list includes substituents characterized beyond one of these categories, such as benzyl. The list also includes hydrogen, and thus is not limited to the concept of substituted indenyl and substituted fluorenyl, but partially saturated indenyl comprising tetrahydroindenyl, tetrahydrofluorenyl, and octahydrofluorenyl groups. And fluorenyl.
Examples of each of these substituents include, but are not limited to, the following groups: Unless otherwise stated, in each of the examples presented below, R is independently an aliphatic group; an aromatic group; a cyclic group; any combination thereof; any substituted derivative thereof (but not limited to them). Contains halide-, alkoxide-, or amide-substituted analogs or derivatives of; each of which has 1 to about 20 carbon atoms); or is selected from hydrogen. These groups also include any of their substitutions, branches, or linear analogs.
Examples of aliphatic groups include, but are not limited to, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an alkazienyl group, a cyclic group, etc. in each presence, and 1 in each presence. Includes all of their substituted, unsubstituted, branched, linear analogs or derivatives having about 20 carbon atoms from. Thus, aliphatic groups include, but are not limited to, hydrocarbyls such as paraffin and alkenyl. For example, the aliphatic groups used herein include methyl, ethyl, propyl, n-butyl, tert-butyl, sec-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, etc. Includes dodecyl, 2-ethylhexyl, pentenyl, butenyl and the like.
Examples of aromatic groups include, but are not limited to, phenyl, naphthyl, anthracenyl, etc. in their respective presences, including their substituted derivatives, each having 6 to about 25 carbons in each presence. Substituted derivatives of aromatic compounds include, but are not limited to, trills, xylyl, mesityl and the like, including any heteroatom substituted derivatives thereof.
Examples of cyclic groups include, but are not limited to, cycloparaffin, cycloolefin, cycloacetylene, arene (eg, phenyl, bicyclic group), etc. in each presence (about 3 to about 20 in each presence). Includes (including their substituted derivatives) having carbon atoms of. Therefore, heteroatom-substituted cyclic groups such as furanyl are included herein.
In each presence, the aliphatic and cyclic groups are groups that include an aliphatic moiety and a cyclic moiety, and examples thereof include, but are not limited to, groups such as-(CH).<sub>2</sub>)<sub>m</sub>C<sub>6</sub>H<sub>q</sub>R<sub>5-q</sub>[Where m is an integer from 1 to about 10 and q is an integer from 1 to 5 (including both ends)];-(CH<sub>2</sub>)<sub>m</sub>C<sub>6</sub>H<sub>q</sub>R<sub>11-q</sub>[Where m is an integer from 1 to about 10 and q is an integer from 1 to 11 (including both ends)]; or-(CH)<sub>2</sub>)<sub>m</sub>C<sub>5</sub>H<sub>q</sub>R<sub>9-q</sub>[Here, m is an integer from 1 to about 10, and q is an integer from 1 to 9 (including both ends)] is included. In each presence, as defined above, R is independently an aliphatic group; an aromatic group; a cyclic group; any combination of them; any of their substituted derivatives (but not limited to their halogens). Includes compound-, alkoxide-, or amide-substituted derivatives or analogs; each of which has 1 to about 20 carbon atoms); or is selected from hydrogen. In one embodiment, the aliphatic and cyclic groups are, but are not limited to, -CH.<sub>2</sub>C<sub>6</sub>H<sub>5</sub>;-CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>F; -CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>Cl; -CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>Br; -CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>I; -CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>OMe; -CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>OEt;-CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>NH<sub>2</sub>;-CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>NMe<sub>2</sub>;-CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>NEt<sub>2</sub>;-CH<sub>2</sub>CH<sub>2</sub>C<sub>6</sub>H<sub>5</sub>;-CH<sub>2</sub>CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>F; -CH<sub>2</sub>CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>Cl; -CH<sub>2</sub>CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>Br; -CH<sub>2</sub>CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>I; -CH<sub>2</sub>CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>OMe; -CH<sub>2</sub>CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>OEt;-CH<sub>2</sub>CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>NH<sub>2</sub>;-CH<sub>2</sub>CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>NMe<sub>2</sub>;-CH<sub>2</sub>CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>NEt<sub>2</sub>Includes any positional isomers thereof, and any substituted derivatives thereof.
Examples of halides, in their respective presence, include fluorides, chlorides, bromides, and iodides.
In each presence, the oxygen group is an oxygen-containing group, examples of which include, but are not limited to, an alkoxy group or an aryloxy group (-OR), etc. (including their substituted derivatives, where R is. Included (which is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl) having 1 to about 20 carbon atoms. Examples of alkoxy or aryloxy groups (-OR) include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy and the like.
In each presence, the sulfur group is a sulfur-containing group, examples of which are, but are not limited to, -SR, etc. (including their substituted derivatives, where R in each presence is from 1 to about. Includes alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl, which have 20 carbon atoms.
In each presence, the nitrogen group is a nitrogen-containing group, which is, but is not limited to, -NR.<sub>2</sub>Or pyridyl groups, etc. (including their substituted derivatives, where R in each presence is alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted, having 1 to about 20 carbon atoms. (Arylkill) is included.
In each presence, the phosphorus group is a phosphorus-containing group, including, but not limited to, -PR.<sub>2</sub>Etc. (including their substituted derivatives, where R in each presence is an alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having 1 to about 20 carbon atoms. ) Is included.
In each presence, the arsenic group is an arsenic-containing group, including, but not limited to, -AsR.<sub>2</sub>Etc. (including their substituted derivatives, where R in each presence is an alkyl, cycloalkyl, aryl, aralkyl, substituted alkyl, substituted aryl, or substituted aralkyl having 1 to about 20 carbon atoms. ) Is included.
In each presence, the carbon group is a carbon-containing group, including, but not limited to, an alkyl halide group containing a halide-substituted alkyl group having 1 to about 20 carbon atoms, 1 to about 20 carbon atoms. It includes an alkenyl group or an alkenyl halide group having an alkenyl halide, an aralkyl group having 1 to about 20 carbon atoms, an aralkyl halide group and the like (including derivatives thereof).
In each presence, the silicon group is a silicon-containing group, such as, but not limited to, an alkylsilyl group, an arylsilyl group, a silyl group such as an arylalkylsilyl group, a siloxy group, etc. Includes 1 to about 20 carbon atoms). For example, silicon groups include trimethylsilyl and phenyloctylsilyl groups.
In each presence, the boron group is a boron-containing group, which is, but is not limited to, -BR.<sub>2</sub>, -BX<sub>2</sub>, -BRX (where X is a monoanion group such as a halide, hydride, alkoxide, alkylthiolate, etc., and the R in each presence is alkyl, cyclo, which has 1 to about 20 carbon atoms. Alkoxides, aryls, alkoxides, substituted alkyls, substituted aryls, or substituted alkoxides) are included.
In another aspect of the invention, (X<sup>3</sup>) And (X<sup>4</sup>) Are independently an aliphatic group, a cyclic group, a combination of an aliphatic group and a cyclic group, an amide group, a phosphide group, an alkyl oxide group, an aryl oxide group, an alkane sulfonate, an allene sulfonate, or a trialkylsilyl group. , Or their substituted derivatives (all of which have about 1 to about 20 carbon atoms); or halides. In yet another embodiment, (X<sup>3</sup>) And (X<sup>4</sup>) Are independently 1) F, Cl, Br, or I; 2) a hydrocarbyl group with up to 20 carbon atoms, H, or BH.<sub>4</sub>3) Hydrocarbyl oxide group, hydrocarbylamino group, or trihydrocarbylsilyl group (all of which have up to 20 carbon atoms); 4) OBR<sup>A</sup><sub>2</sub>Or SO<sub>3</sub>R<sup>A</sup>(Here, R<sup>A</sup>Is an alkyl or aryl group, each of which has up to 12 carbon atoms). In yet another embodiment, (X<sup>3</sup>) And (X<sup>4</sup>) Are independently selected from hydrocarbyls having 1 to about 10 carbon atoms, or halides. In another aspect, (X<sup>3</sup>) And (X<sup>4</sup>) Are independently selected from fluoride, chloride, bromide, or iodide. In yet another embodiment, (X<sup>3</sup>) And (X<sup>4</sup>) Is chloride. In yet another embodiment, (X<sup>3</sup>) And (X<sup>4</sup>) Are independently hydrocarbyl groups with up to 20 carbon atoms, H, or BH.<sub>4</sub>Is.
In a further aspect of the invention, at least one ansa-metallocene of the invention is expressed in formula:<chemistry num="3"><img id="000004" he="44" wi="56" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>[During the ceremony, M<sup>1</sup>Is zirconium or hafnium; X is independently F, Cl, Br, or I; E is C or Si; R<sup>1</sup>And R<sup>2</sup>Are independently alkyl or aryl groups (each of which has up to 10 carbon atoms) or hydrogen, where R<sup>1</sup>Or R<sup>2</sup>At least one of them is an aryl group; R<sup>3A</sup>And R<sup>3B</sup>Are independently hydrocarbyl or trihydrocarbylsilyl groups (both of which have up to 20 carbon atoms) or hydrogen; n is an integer from 0 to 10 (including both ends); R<sup>4A</sup>And R<sup>4B</sup>Is independently a hydrocarbyl group with up to 12 carbon atoms, or hydrogen] It is provided to include a compound having.
In yet another embodiment, at least one ansa-metallocene of the invention is expressed in the formula:<chemistry num="4"><img id="000005" he="45" wi="57" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>[During the ceremony, M<sup>1</sup>Is zirconium or hafnium; X is F, Cl, Br, or I; E is C or Si; R<sup>1</sup>And R<sup>2</sup>Are independently alkyl or aryl groups (each of which has up to 10 carbon atoms) or hydrogen, where R<sup>1</sup>And R<sup>2</sup>At least one of them is an aryl group; R<sup>3A</sup>And R<sup>3B</sup>Are independently H, methyl, allyl, benzyl, butyl, pentyl, hexyl, or trimethylsilyl; n is an integer from 0 to 6 (including both ends); R<sup>4A</sup>And R<sup>4B</sup>Is independently a hydrocarbyl group with up to 6 carbon atoms, or hydrogen] Includes compounds with.
In yet another embodiment, at least one ansa-metallocene of the invention is expressed in the formula:<chemistry num="5"><img id="000006" he="44" wi="60" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>[During the ceremony, M<sup>1</sup>Is zirconium or hafnium; X is Cl, Br, or I; E is C or Si; R<sup>1</sup>And R<sup>2</sup>Are independently methyl or phenyl, where R<sup>1</sup>Or R<sup>2</sup>At least one of them is a phenyl group; R<sup>3A</sup>And R<sup>3B</sup>Is independently H or methyl; n is 1 or 2; R<sup>4A</sup>And R<sup>4B</sup>Is independently H or t-butyl] Includes compounds with.
In yet another embodiment, at least one ansa-metallocene of the invention is expressed in the formula:<chemistry num="6"><img id="000007" he="44" wi="59" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>[During the ceremony, M<sup>1</sup>Is zirconium or hafnium; X is independent, H, BH<sub>4</sub>, Methyl, phenyl, benzyl, neopentyl, trimethylsilylmethyl, CH<sub>2</sub>CMe<sub>2</sub>Ph; CH<sub>2</sub>SiMe<sub>2</sub>Ph; CH<sub>2</sub>CMe<sub>2</sub>CH<sub>2</sub>Ph; or CH<sub>2</sub>SiMe<sub>2</sub>CH<sub>2</sub>Ph; E is C or Si; R<sup>1</sup>And R<sup>2</sup>Are independently alkyl or aryl groups (each of which has up to 10 carbon atoms) or hydrogen, where R<sup>1</sup>Or R<sup>2</sup>At least one of them is an aryl group; R<sup>3A</sup>And R<sup>3B</sup>Are independently hydrocarbyl or trihydrocarbylsilyl groups (each of which has up to 20 carbon atoms) or hydrogen; n is an integer from 0 to 10 (including both ends); R<sup>4A</sup>And R<sup>4B</sup>Is independently a hydrocarbyl group with up to 12 carbon atoms, or hydrogen] Includes compounds with.
In a further embodiment, at least one ansa-metallocene of the invention is expressed in the formula:<chemistry num="7"><img id="000008" he="113" wi="155" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>Includes compounds having, or any combination thereof.
In yet another embodiment, at least one ansa-metallocene of the invention<chemistry num="8"><img id="000009" he="110" wi="150" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>Alternatively, it may include any combination thereof, or it may be selected from them and any combination thereof. In yet another aspect of the invention, the formula:<chemistry num="9"><img id="000010" he="40" wi="54" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, M<sup>2</sup>Is Zr or Hf) A metallocene compound having the above is provided.
Numerous methods have been reported for preparing metallocene compounds that can be used in the present invention. For example, U.S. Pat. Nos. 4939217, 5191132, 5210352, 5347026, 5399636, 5401817, 5420320, 5436305, 5451649, 5497781, 5489581, 5541272. No., No. 5554795, No. 5563284, No. 5565592, No. 5571880, No. 5594078, No. 5631203, No. 5631335, No. 5654454, No. 5668230, No. 5705578, No. 5705579, No. 6187880 and No. 6509427 describes such a method. Other methods for preparing metallocene compounds that can be used in the present invention have been reported in references such as: Koppl, A., Alt, HG, J. Mol. Catal A.2001, 165. , 23; Kajigaeshi, S., Kadowaki, T., Nishida, A., Fujisaki, S. The Chemical Society of japan, 1986, 59, 97; Alt, HG, Jung, M, Kehr, GJ Organomet.Chem.1998, 562, 153 ~ 181; Alt, HG, Jung, M., J.Organomet.Chem.1998,568, 87 ~ 112; Jung, M., Doctoral Dissertation, University of Bayreuth, Bayreuth, Germany, 1997; Piefer, B., Doctoral Dissertation, University of Bayreuth, Bayreuth, Germany, 1995; and Zenk, R., Doctoral Dissertation, University. of Bayreuth, Bayreuth, Germany, 1994. The following technical books also describe such methods: Wailes, PC, Coutts, RSP, Weigold, H, "Organometallic Chemistry of Titanium, Zirconium, and Hafnium. Titanium, Zironium, and Hafnium) , Academic, New York, 1974; Cardin, DJ, Lappert, MF, and Raston, CL, Chemistry of Organo-Zirconium and-Hafnium compounds , Halstead Press, New York, 1986.
Organoaluminium compound In one embodiment, the invention presents at least one strongly crosslinked ansa-metallocene compound containing an olefin-containing moiety attached to a cyclopentadienyl-type ligand and at least one aryl group attached to a crosslinked atom of the crosslinked ligand. , A catalyst composition comprising at least one solid oxide activator-carrier and optionally at least one organoaluminum compound. Thus, as disclosed herein, as will be appreciated by those skilled in the art, at least one organoaluminum of choice if it is not necessary to impart catalytic activity to the composition containing the contact product. The designation of the compound is intended to reflect that the organoaluminum compound can be optional.
The organoaluminum compounds that can be used in the present invention are not limited to the formula: Al (X<sup>5</sup>)<sub>n</sub>(X<sup>6</sup>)<sub>3-n</sub>[In the formula, (X<sup>5</sup>) Is a hydrocarbyl with 1 to about 20 carbon atoms; (X)<sup>6</sup>) Are alkoxides or aryl oxides (all of which have about 1 to about 20 carbon atoms), halides, or hydrides; n is a number from 1 to 3 (including both ends). Contains compounds that have. In one embodiment, (X<sup>5</sup>) Is an alkyl having 1 to about 10 carbon atoms. (X<sup>5</sup>Examples of the portion) include, but are not limited to, methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl and the like. In another aspect, (X<sup>5</sup>) Partial examples include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl, 1-hexyl, 2-hexyl, 3-hexyl, isohexyl, heptyl, octyl, etc. included. In another aspect, (X<sup>6</sup>) Can be independently selected from fluoride, chloride, bromide, methoxide, ethoxide, or hydride. In yet another embodiment, (X<sup>6</sup>) Can be chloride.
Equation Al (X<sup>5</sup>)<sub>n</sub>(X<sup>6</sup>)<sub>3-n</sub>In, n is a number from 1 to 3 (including both ends), and n is usually 3. The value of n is not limited to being an integer and therefore the formula includes sesquihalide compounds, other organoaluminum cluster compounds and the like.
In general, examples of organoaluminum compounds that can be used in the present invention include, but are not limited to, trialkylaluminum compounds, dialkylaluminum halide compounds, dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds, and combinations thereof. Examples of organic aluminum compounds useful in the present invention are, but are not limited to, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), trihexylaluminum. , Triisohexylaluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof. If no particular alkyl isomer is specified, the compound is intended to include all isomers that may arise from the particular designated alkyl group. Therefore, in another embodiment, examples of organic aluminum compounds that can be used in the present invention are, but are not limited to, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexyl. Includes aluminum, trioctylaluminum, diethylaluminum ethoxide, diisobutylaluminum hydride, diethylaluminum chloride, or any combination thereof.
In one embodiment, the present invention pre-contacts ansa-metallocene with at least one organoaluminum compound and an olefin monomer to form a pre-contact mixture, which is then combined with the solid oxide activator-. It comprises the step of contacting with a carrier to form an active catalyst. Usually, but not necessarily, when the catalytic composition is prepared in this way, one portion of the organoaluminum compound is added to the pre-contact mixture and another portion of the organoaluminum compound solid-oxidizes the pre-contact mixture. When contacted with a substance activator, it is added to the prepared post-contact mixture. However, all organoaluminum compounds can be used to prepare the catalyst in either the pre-contact or post-contact steps. Besides, all catalytic components can be contacted in a single step.
In addition, more than one organoaluminum compound can be used in either the pre-contact or post-contact steps, or in any procedure for contacting the catalytic components. When the organoaluminum compound is added in a multi-step process, the amount of the organoaluminum compound disclosed herein includes the organoaluminum compound used in both the pre-contact and post-contact mixture, and any addition to the polymerization reactor. Includes the total amount of additional organoaluminum compounds. Therefore, the total amount of organoaluminum compounds is disclosed regardless of whether a single organoaluminum compound is used or more than one organoaluminum compound is used. In another embodiment, conventional organoaluminum compounds used in the present invention include, but are not limited to, triethylaluminum (TEA), tri-n-butylaluminum, triisobutylaluminum, or any combination thereof.
Activator In one embodiment, the invention relates to at least one strongly crosslinked ansa-metallocene compound as disclosed herein; optionally at least one organoaluminum compound; and at least one activity. Includes catalytic compositions containing agents. In another embodiment, the at least one activator is an activator-carrier containing a solid oxide treated with an electron-attracting anion; a layered mineral; an ion-exchangeable activator-carrier; an organic aluminoxane compound. It can be an organoboron compound; an organic borate compound; or any combination of any of these activators, each of which is provided herein.
Chemically treated solid oxide activator-carrier In one embodiment, the invention includes a catalytic composition comprising an acidic activator-carrier, which can include chemically treated solid oxides and is typically used in combination with organoaluminum compounds. In another embodiment, the activator-carrier comprises at least one solid oxide treated with at least one electron-attracting anion; where the solid oxide is silica, alumina, silica. -Alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, etc., or any mixture or combination thereof. Can; where the electron-attracting anions are fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluoroborate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirco. It can be a nitrate, a fluorosilicate, a fluorotitanate, a permanganate, a substituted or unsubstituted alcan sulfonate, a substituted or unsubstituted allene sulfonate, a substituted or unsubstituted alkyl sulphate, or any combination thereof.
Activator-Carriers include at least one solid oxide compound and at least one contact product of an electron-attracting anion source. In one embodiment, the solid oxide compound comprises an inorganic oxide. The solid oxide can optionally be calcinated and then contacted with an electron-attracting anion source. The contact product can also be burned either during or after the solid oxide compound is in contact with the electron-attracting anion source. In this embodiment, the solid oxide compound can be calcinated or non-calcinated. In another embodiment, the activator-carrier may comprise a contact product of at least one calcined solid oxide compound with at least one electron attracting anion source.
The activator-carrier exhibits enhanced activity compared to the corresponding untreated solid oxide compound. Activator-The carrier also functions as a catalytic activator compared to the corresponding untreated solid oxide. Although not intended to be constrained by theory, activator-carriers function by further ionizing, polarifying, and weakening the bond by weakening the metal-ligand bond between the anionic ligand and the metal in the metallocene (collectively). It is believed that it can function as a solid oxide supporting compound (referred to as the "activation" function). Thus, the activator-carrier, when in contact with the activator-carrier, ionizes metallocene, removes the anionic ligand to form an ion pair, weakens the metal-ligand bond in metallocene, simply becomes an anionic ligand. The activator-carrier is believed to exhibit an "activating" function, regardless of whether it is coordinated or any other mechanism by which ionization, polarization, or binding weakening may occur. In preparing the metallocene-based catalytic compositions of the present invention, if the metallocene compound does not yet contain such a ligand, the activator-carrier usually comprises the metallocene with an activating ligand such as an alkyl or hydride ligand. Used with the giving component, including, but not limited to, at least one organoaluminum compound.
In yet another embodiment, the activator-carrier of the invention is a solid inorganic oxide material that is chemically treated with an electron-attracting component and optionally at least one other metal ion. , Mixed oxide substances, or combinations of inorganic oxide substances. Thus, solid oxides of the invention include oxide substances such as alumina, "mixed oxide" compounds such as silica-alumina or silica-zirconia or silica-titania, and combinations and mixtures thereof. Mixed metal oxide compounds such as silica-alumina, which have more than one metal combined with oxygen to form a solid oxide compound, can be made by co-gelling, impregnation or chemical precipitation and Included by the invention.
In yet another aspect of the invention, the activator-carrier further comprises a metal or metal ion, such as zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or any combination thereof. Including. Examples of activator-carriers further comprising a metal or metal ion are, but are not limited to, zinc-impregnated alumina chloride, zinc-impregnated alumina fluoride, zinc-impregnated silica chloride-alumina, zinc-impregnated silica-alumina fluoride. , Zinc-impregnated sulfated alumina, or any combination thereof.
In another embodiment, the activator-carrier of the invention comprises a solid oxide with a relatively high porosity that behaves like a Lewis acid or Bronsted acid. Solid oxides are chemically treated with an electron-attracting component, usually an electron-attracting anion, to form an activator-carrier. Although not intended to be constrained by the following description, treatment of an inorganic oxide with an electron-attracting component appears to increase or increase the acidity of the oxide. Therefore, activator-carriers typically exhibit Lewis or Bronsted acidity greater than Lewis or Bronsted acidity of untreated solid oxides. One way to quantify the acidity of chemically treated and untreated solid oxide materials is by comparing the polymerization activity of the treated and untreated oxides under an acidic catalytic reaction.
In one embodiment, the chemically treated solid oxides are oxygen and groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or It contains at least one element selected from 15 or a solid inorganic oxide containing at least one element selected from oxygen and lanthanide or actinide elements. (See: Hawley's Condensed Chemical Dictionary, 11th Edition, John Wiley & Sons, 1995; Cotton, FA, Wilkinson, G., Murillo, CA, and Bochmann, M, Advanced Inorganic Chemistry, 6th Edition, Wiley-Interscience , 1999). Usually, the inorganic oxides are oxygen and Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti. , V, W, P, Y, Zn or Zr contains at least one element selected from.
Suitable examples of solid oxide substances or compounds that can be used in the chemically treated solid oxides of the present invention are, but are not limited to, Al.<sub>2</sub>O<sub>3</sub>, B<sub>2</sub>O<sub>3</sub>, BeO, Bi<sub>2</sub>O<sub>3</sub>, CdO, Co<sub>3</sub>O<sub>4</sub>, Cr<sub>2</sub>O<sub>3</sub>, CuO, Fe<sub>2</sub>O<sub>3</sub>, Ga<sub>2</sub>O<sub>3</sub>, La<sub>2</sub>O<sub>3</sub>, Mn<sub>2</sub>O<sub>3</sub>, MoO<sub>3</sub>, NiO, P<sub>2</sub>O<sub>5</sub>, Sb<sub>2</sub>O<sub>5</sub>, SiO<sub>2</sub>, SnO<sub>2</sub>, SrO, ThO<sub>2</sub>, TiO<sub>2</sub>, V<sub>2</sub>O<sub>5</sub>, WO<sub>3</sub>, Y<sub>2</sub>O<sub>3</sub>, ZnO, ZrO<sub>2</sub>Etc. (including their mixed oxides) and combinations thereof. Examples of mixed oxides that can be used in the activator-carrier of the present invention are, but are not limited to, Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Includes any combination of mixed oxides such as Ni, P, Sb, Si, Sn, Sr, Th, Ti, V, W, Y, Zn, Zr and the like. Examples of mixed oxides that can be used in the activator-carriers of the present invention are also not limited to, but are not limited to, silica-alumina, silica-titania, silica-zirconia, zeolite, many clay minerals, columnar clays, alumina-titania. , Alumina-zirconia, aluminophosphate, etc. are included.
In a further aspect of the invention, the solid oxide is chemically treated by contact with at least one electron-attracting component, usually an electron-attracting anion source. Further, the solid oxide material is optionally chemically treated with at least one other metal ion which can be the same as or different from any metal element constituting the solid oxide material, and then It is calcined to form metal-containing or metal-impregnated chemically treated solid oxides. Alternatively, the solid oxide material and the electron-attracting anion source are simultaneously contacted and calcinated. Gelation, co-gelling, to another compound of one compound, but not limited to the method by which the oxide is contacted with an electron-attracting component, usually a salt or acid of an electron-attracting anion. Impregnation etc. are included. Usually, following any contact method, the contact mixture of oxide compounds, electron-attracting anions, and optionally metal ions is calcinated.
The electron-attracting component used to treat the oxide can be any component that increases the acidity of the solid oxide Lewis or Bronsted after treatment. In one embodiment, the electron-attracting component is usually an electron-attracting anion derived from another compound, such as a salt, acid, or volatile organic compound, which can act as a source or precursor of the anion. Examples of electron-attracting anions include, but are not limited to, fluorides, chlorides, bromides, iodides, phosphates, trifurates, bisulfates, sulfates, fluorobolates, fluorosulfates, trifluoroacetates, phosphates, fluorophosphates, Fluorozirconate, fluorosilicate, fluorotitanate, permanganate, substituted or unsubstituted alkanesulfonate, substituted or unsubstituted allene sulfonate, substituted or unsubstituted alkylsulfate, etc. (including any mixture and combination thereof). Is included. In addition, other ionic or non-ionic compounds that serve as sources for these electron-attracting anions can also be used in the present invention. In one embodiment, the chemically treated solid oxide comprises a sulfated solid oxide, and in the other embodiment, the chemically treated oxide comprises a sulfated alumina.
The terms "alkane sulfonate and alkyl sulphate" have their respective general formulas [R.<sup>B</sup>SO<sub>2</sub>O]<sup>-</sup>And [(R<sup>B</sup>O) SO<sub>2</sub>O]<sup>-</sup>(Here, R<sup>B</sup>Is F, Cl, Br, I, OH, OMe, OEt, OCF<sub>3</sub>, Ph, xsilyl, mesityl, or an anion having a linear or branched alkyl group with up to 20 carbon atoms, optionally substituted with at least one group independently selected from OPh). .. Therefore, alkane sulfonates and alkyl sulphates can be said to be either substituted or unsubstituted. In one embodiment, the alkyl group of alkylsulfonate or alkylsulfate can have up to 12 carbon atoms. In another embodiment, the alkyl group of an alkylsulfonate or alkylsulfate can have up to 8 carbon atoms or up to 6 carbon atoms. In yet another embodiment, examples of alkane sulfonates are, but are not limited to, methane sulphonates, ethane sulphonates, 1-propane sulphonates, 2-propane sulphonates, 3-methylbutane sulphonates, trifluoromethane sulphonates, trichloromethane sulphonates, chloromethanes. Sulfonates, 1-hydroxyethanesulfonates, 2-hydroxy-2-propanesulfonates, 1-methoxy-2-propanesulfonates and the like are included. In yet another embodiment, examples of alkyl sulphates are, but are not limited to, methyl sulphate, ethyl sulphate, 1-propyl sulphate, 2-propyl sulphate, 3-methylbutyl sulphate, trifluoromethane sulphate. , Trichloromethylsulfate, chloromethylsulfate, 1-hydroxyethylsulfate, 2-hydroxy-2-propylsulfate, 1-methoxy-2-propylsulfate and the like.
The term "arene sulfonate" is the general formula [Ar<sup>A</sup>SO<sub>2</sub>O]<sup>-</sup>[Here, Ar<sup>A</sup>Is an aryl group with up to 14 carbon atoms, which are F, Cl, Br, I, Me, Et, Pr, Bu, OH, OMe, OEt, OPr, OBu, OCF.<sub>3</sub>, Ph, OPh, or R<sup>C</sup>(Here, R<sup>C</sup>Is an anion optionally substituted with at least one group independently selected from (which is a linear or branched alkyl group having up to 20 carbon atoms). Therefore, the arene sulfonate can be referred to as a substituted or unsubstituted arene sulfonate. Aryl group Ar<sup>A</sup>Is an alkyl side chain R containing a long alkyl side chain<sup>C</sup>The term "arene sulfonate" is intended to include the surfactant, as it can be substituted with. In one embodiment, the aryl group of arene sulfonate can have up to 10 carbon atoms. In another embodiment, the aryl group of arene sulfonate can have 6 carbon atoms. In yet another embodiment, examples of arene sulfonates include, but are not limited to, benzenesulfonate, naphthalenesulfonate, p-toluenesulfonate, m-toluenesulfonate, 3,5-xylenesulfonate, trifluoromethoxybenzenesulfonate, trichloromethoxybenzene. Includes sulfonate, trifluoromethylbenzene sulfonate, trichloromethylbenzene sulfonate, fluorobenzene sulfonate, chlorobenzene sulfonate, 1-hydroxyethanebenzene sulfonate, 3-fluoro-4-methoxybenzene sulfonate and the like.
If the electron-attracting component contains a salt of an electron-attracting anion, the counterion or cation of the salt is any cation that allows the salt to be converted back to the acid or decomposed back during firing. Can be. Factors that determine the suitability of a particular salt to act as a source for an electron-attracting anion are, but are not limited to, the solubility of the salt in the desired solvent, the lack of reverse reactivity of the cation, the said. Includes ion pairing effects between cations and anions, hygroscopic properties imparted to the salt by the cations, and the thermal stability of the anions. Examples of suitable cations in salts of electron-attracting anions include, but are not limited to, ammonium, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H.<sup>+</sup>, [H (OEt)<sub>2</sub>)<sub>2</sub>]<sup>+</sup>Etc. are included.
In addition, a combination of one or more different electron-attracting anions in varying rates can be used to adjust the particular acidity of the activator-carrier to the desired level. The combination of electron-attracting components can be contacted simultaneously with or separately from the oxide material and can be in any order that imparts the acidity of the desired activator-carrier. For example, one aspect of the invention is the use of two or more electron-attracting anion source compounds in two or more separate contact steps. Therefore, an example of how an activator-carrier is prepared is as follows. The selected solid oxide compound, or combination of oxide compounds, is contacted with the first electron-attracting anion source compound to form a first mixture, which is then baked. The calcined first mixture is then contacted with a second electron-attracting anion source compound to form a second mixture, which is then calcined to treat the solid oxide. Form a compound. In such a method, the first and second electron-attracting anion source compounds are usually different compounds, but can also be the same compound.
In one embodiment of the invention, the solid oxide activator-carrier is 1) A step of contacting a solid oxide compound with at least one electron-attracting anion source compound to form a first mixture; and 2) Step of calcining the first mixture to form a solid oxide activator-carrier Manufactured by methods including.
In another aspect of the invention, the solid oxide activator-carrier is 1) A step of contacting at least one solid oxide compound with a first electron-attracting anion source compound to form a first mixture; and 2) The step of calcinating the first mixture to produce the first calcinated mixture; 3) The step of contacting the calcined first mixture with the second electron-attracting anion source compound to form the second mixture; and 4) Step of calcining the second mixture to form a solid oxide activator-carrier Manufactured by methods including. Therefore, the solid oxide activator-carrier may simply be referred to as the treated solid oxide compound.
Another aspect of the present invention is to produce or form a solid oxide activator-carrier by contacting at least one solid oxide with at least one electron-attracting anion source compound. Here, at least one solid oxide compound is calcinated before, during, or after contact with an electron-attracting anion source, where aluminoxane and organic borate are substantially absent. ..
In one embodiment of the invention, the solid oxide can be continuously calcined as soon as it is treated and dried. The smoldering of the treated solid oxide is generally carried out in an ambient or inert atmosphere, usually a dry ambient atmosphere, at a temperature of about 200 ° C to about 900 ° C for about 1 minute to about 100 hours. In another embodiment, calcination is carried out at a temperature of about 300 ° C to about 800 ° C, and in another embodiment, calcination is carried out at a temperature of about 400 ° C to about 700 ° C. In yet another embodiment, the calcination is carried out for about 1 hour to about 50 hours, and in another embodiment the calcination is carried out for about 3 hours to about 20 hours. In yet another embodiment, the calcination can be carried out at a temperature of about 350 ° C to about 550 ° C for about 1 hour to about 10 hours.
In addition, any suitable surrounding type can be used during calcination. Generally, calcination is carried out in an oxidizing atmosphere, for example in air. Alternatively, an inert atmosphere, such as nitrogen or argon, or a reducing atmosphere, such as hydrogen or carbon monoxide, can be used.
In another aspect of the invention, the solid oxide component used to prepare the chemically treated solid oxide has a pore volume greater than about 0.1 cc / g. In another embodiment, the solid oxide component has a pore volume greater than about 0.5 cc / g, and in yet another embodiment, greater than about 1.0 cc / g. In yet another embodiment, the solid oxide component is from about 100 to about 1000 m.<sup>2</sup>It has a surface area of / g. In another embodiment, the solid oxide component is from about 200 to about 800 m.<sup>2</sup>It has a surface area of / g and in yet another embodiment about 250 to about 600 m<sup>2</sup>/ g.
The solid oxide material can be treated with a source of halogen or sulfate ions, or a combination of anions, and can optionally be treated with at least one metal ion, then calcinated into a particulate solid. The activator-carrier can be provided in the form of. In one embodiment, the solid oxide material is a source of sulfate called a sulfate agent, a source of chloride ions called a chloride agent, a source of fluoride ions called a fluoride agent, or them. And bake to give a solid oxide compound activator. In another embodiment, useful acid activator-carriers include, but are not limited to, alumina bromide; alumina chloride; alumina fluoride; alumina sulfate; silica bromide-alumina; silica chloride-alumina; silica fluoride. -Alumina; Sulfated Silica-Alumina; Bromide Silica-Zirconia; Silica Chloride-Zirconia; Silica Fluoride-Zirconia; Sulfated Silica-Zirconia; Zinc Chloride-Alumina; (Sometimes treated with fluoride, chloride, or sulfate); Alumina oxide, or other aluminate (sometimes treated with sulfate, fluoride, or chloride); or any of them Combinations are included. In addition, any activator-carrier can optionally be treated with at least one other metal ion (usually derived from a metal salt or compound), where the metal ion constitutes a solid oxide material. It can be the same as or different from any metal.
In one embodiment of the invention, the treated oxide activator-carrier comprises a fluoride solid oxide in the form of a particulate solid, thus the source of fluoride ions is a treatment with a fluoride agent. Is added to the oxide. In yet another embodiment, the oxide slurry is formed in a suitable solvent such as alcohol or water, including, but not limited to, 1 to 3 carbon alcohols due to their volatility and low surface tension. By doing so, fluoride ions can be added to the oxide. Examples of fluoride agents that can be used in the present invention are, but are not limited to, hydrofluoric acid (HF) and ammonium fluoride (NH).<sub>4</sub>F), ammonium fluoride (NH)<sub>4</sub>HF<sub>2</sub>), Ammonium tetrafluoroborate (NH<sub>4</sub>BF<sub>4</sub>), Ammonium silicate (hexafluorosilicate) ((NH<sub>4</sub>)<sub>2</sub>SiF<sub>6</sub>), Ammonium hexafluorophosphate (NH<sub>4</sub>PF<sub>6</sub>), Fluoroboric acid (HBF)<sub>4</sub>), Ammonium hexafluorotitanate (NH<sub>4</sub>)<sub>2</sub>TiF<sub>6</sub>, Ammonium hexafluorozirconate (NH)<sub>4</sub>)<sub>2</sub>ZrF<sub>6</sub>, Their analogs, and combinations thereof. For example, ammonium fluoride NH<sub>4</sub>HF<sub>2</sub>Can be used as a fluorinating agent because of its use cases and ease of use.
In another aspect of the invention, the solid oxide can be treated with a fluorinated agent during the calcination step. Any fluorophore that allows complete contact with the solid oxide during the calcination process can be used. For example, in addition to those fluorinated agents described above, volatile organic fluorinated agents can be used. Examples of volatile organic fluorides useful in this aspect of the invention include, but are not limited to, Freon, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, and combinations thereof. Gaseous hydrogen fluoride or fluorine itself can be used with solid oxides, which are fluorinated during calcination. One convenient way to bring the solid oxide into contact with the fluorinating agent is to volatilize the fluorinating agent in the air stream used to fluidize the solid oxide during calcination.
Similarly, in another aspect of the invention, the chemically treated solid oxide comprises a chloride solid oxide in the form of a granular solid, thus the source of chloride ions is a chloride agent. Is added to the oxide by the treatment of. Chloride ions can be added to the oxide by forming a slurry of the oxide in a suitable solvent. In another aspect of the invention, the solid oxide can be treated with a chlorinating agent during the calcination step. Any chloride agent that acts as a source of chloride and is capable of complete contact with the oxide during the calcination process can be used. For example, volatile organochlorides can be used. Examples of volatile organochlorides useful in this aspect of the invention include, but are not limited to, certain Freon, perchlorobenzene, chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, or any combination thereof. included. Gaseous hydrogen chloride or chlorine itself can be used with solid oxides during calcination. One convenient way to bring the oxide into contact with the chloride is to volatilize the chloride in the air stream used to fluidize the solid oxide during calcination.
Activator-If the carrier contains a chemically treated solid oxide containing a solid oxide treated with an electron-attracting anion, the electron-attracting anion is typically about 1% by weight of the solid oxide. It can be added to the solid oxide in an amount exceeding. In another embodiment, the electron-attracting anion is greater than about 2% by weight of the solid oxide, more than about 3% by weight of the solid oxide, more than about 5% by weight of the solid oxide, or the solid oxide. It can be added to the solid oxide in an amount exceeding about 7% by weight of.
In one embodiment, the amount of electron-attracting ions, such as fluoride or chloride ions, present prior to calcining the solid oxide is generally from about 2% to about 50% by weight, where. The weight percent is based on the weight of the solid oxide before calcination, for example silica-alumina. In another embodiment, the amount of electron-attracting ions, such as fluoride or chloride ions, present prior to calcining the solid oxide is from about 3 to about 25% by weight, and in another embodiment. , About 4 to about 20% by weight. When a halide ion is used as the electron-attracting anion, it is used in an amount sufficient to precipitate after calcination, in an amount of about 0.1% by weight to about 50% by weight of the weight of the solid oxide. In another embodiment, the halide is in an amount sufficient to precipitate after scouring, from about 0.5% to about 40% by weight of the halide ion, or from about 1% to about 1% by weight, based on the weight of the solid oxide. Used in an amount of 30% by weight halide ion. When fluoride or chloride ions are added during calcination, for example CCl<sub>4</sub>When calcinated in the presence of calcination, the fluoride or chloride ions in the solid oxide before calcination are usually at zero level or only trace levels. Immediately after being impregnated with the halide, the halogenated oxide is dried by any method known in the art, including but not limited to evaporation after suction filtration, vacuum drying, spray drying, etc. However, the calcination process can be started immediately without drying the impregnated solid oxide.
The silica-alumina used to prepare the treated silica-alumina can have a pore volume of greater than about 0.5 cc / g. In one embodiment, the pore volume can exceed about 0.8 cc / g, and in the other embodiment, the pore volume can exceed about 1.0 cc / g. Furthermore, silica-alumina is about 100m<sup>2</sup>Can have a surface area greater than / g. In one embodiment, the surface area is about 250 m<sup>2</sup>Exceeding / g, in another embodiment, the surface area is about 350 m<sup>2</sup>Can exceed / g. In general, the silica-alumina of the present invention has an alumina content of about 5 to about 95%. In one embodiment, the alumina content of silica-alumina can be from about 5 to about 50%, and in another embodiment, the alumina content of silica-alumina can be from about 8% to about 30% by weight. Can be alumina.
Sulfated solid oxides contain sulfates and solid oxide components (eg, alumina or silica-alumina) in the form of particulate solids. In some cases, the sulfated oxide is further treated with metal ions so that the calcined sulfated oxide contains a metal. In one embodiment, the sulfated solid oxide comprises sulfate and alumina. In one embodiment of the invention, the sulfated alumina is such that the alumina is on a sulfate source, including, but not limited to, sulfate or sulfate, such as ammonium sulfate, zinc sulfate, aluminum sulfate, nickel sulfate or copper sulfate. Formed by the method being processed. In one embodiment, the method can be carried out by forming a slurry of alumina in a suitable solvent such as alcohol or water, to which the desired concentration of sulfated agent has been added. Suitable organic solvents include, but are not limited to, 1 to 3 carbon alcohols due to their volatility and low surface tension.
In this embodiment, the amount of sulfate ions present before calcination is generally from about 1% to about 50%, from about 2% to about 30%, or from about 5% to about 25%. Here, the weight percent is based on the weight of the solid oxide before calcination. Immediately upon impregnation with sulfate, the sulfated oxide is dried by any method known in the art, including but not limited to suction filtration followed by evaporation, vacuum drying, spray drying, and the like. However, it is also possible to start the calcination process immediately.
In addition to being treated with electron-attracting components such as halide or sulfate ions, the solid inorganic oxides of the invention can optionally be treated with a metal source containing a metal salt or metal-containing compound. .. In one embodiment of the invention, these compounds can be added or impregnated into a solid oxide in solution form and then converted to a supported metal after calcination. Thus, solid inorganic oxides can further include metals selected from zinc, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum, or combinations thereof. For example, it can be used to impregnate solid oxides with zinc because it provides good catalytic activity and low cost. The solid oxide can be treated with a metal salt or metal-containing compound before, after, or at the same time as treating the solid oxide with an electron-attracting anion.
Further, any method of impregnating the solid oxide material with a metal can be used. Methods of contacting the oxide with a metal source, usually a salt or a metal-containing compound, include, but are not limited to, gelation, co-gelling, impregnation of one compound into another, and the like. Following any contact method, a contact mixture of oxide compounds, electron-attracting anions, and metal ions is usually calcined. Alternatively, the solid oxide material, the electron-attracting anion source, and the metal salt or metal-containing compound are brought into contact with each other and calcinated at the same time.
In another embodiment, the ansa-metallocene compound can be contacted with an olefin monomer and organoaluminum cocatalyst during the first period, after which the mixture can be contacted with an acid activator-carrier. As soon as a pre-contact mixture of metallocenes, monomers, and components that give the metallocene an activating ligand (including, but not limited to, organoaluminum cocatalysts) is contacted with the acid activator-carrier The composition further comprising is referred to as a "post-contact" mixture. The post-contact mixture can be left in place for further contact in the second period, after which it is filled into the reactor where the polymerization treatment is carried out.
Various methods for preparing solid oxide activator-carriers that can be used in the present invention have been reported. For example, U.S. Pat. Nos. 6107230, 6165929, 6294494, 6300271, 6316553, 6355594, 6376415, 6391816, 6395666, 6524987, and 6548441 Such methods are described, each of which is incorporated herein by reference in its entirety.
Ion-exchangeable activators-carriers and layered mineral activators-carriers In one embodiment of the invention, the activator-carrier used to prepare the catalytic composition of the invention can include, but is not limited to, an ion-exchangeable activator-carrier. Includes silicate and aluminosilicate compounds or minerals having either a layered or non-layered structure, as well as any combination thereof. In another aspect of the invention, an ion exchange layered aluminosilicate such as columnar clay can be used as the activator-carrier. If the acid activator-carrier comprises an ion-exchangeable activator-carrier, it can optionally be treated with at least one electron-attracting anion, such as those disclosed herein. Normally, ion exchange activator-carriers are not treated with electron-attracting anions.
In one embodiment, the activator-carriers of the invention may comprise clay minerals with interchangeable cations and expandable layers. Typical clay mineral activators-carriers include, but are not limited to, ion-exchange layered aluminosilicates such as columnar clays. Although the term "carrier" is used, it does not mean that it is interpreted as an inert component of the catalytic composition, but rather should be considered as the active portion of the catalytic composition, for the reason ansa-metallocene and metallocene. Because of its close association with components that provide activable ligands, such as organoaluminum. Although not intended to be constrained by theory, the ion-exchangeable activator-carrier is an insoluble reactant that reacts with ansa-metallocene and organoaluminum components to form the catalytic composition used to make the polymer. Is thought to function as.
In one embodiment, the clay materials of the present invention include materials that are in their natural state or have been treated with various ions by wetting, ion exchange, or columnarization. Generally, the clay material activator-carrier of the present invention comprises a clay ion-exchanged with a large cation containing a polynuclear highly charged metal complex cation. However, the clay material activator-carriers of the invention are also, but not limited to, Al (III), Fe (II), Fe with ligands such as halides, acetates, sulfates, nitrates, or nitrites. Includes ion-exchanged clay with simple salts, including salts (III) and Zn (II).
In one embodiment, the clay activator-carrier of the present invention comprises a columnar clay. The term "columnar clay" is used to refer to large, typically multi-nucleated, highly charged metal complex cations and ion-exchanged clay materials. Examples of such ions include, but are not limited to, charges such as 7+, various polyoxometallates, and kegin ions which can have other large ions. Thus, the term "columnarization" refers to a simple exchange reaction in which the ion-exchangeable cations of a clay material are replaced by large, highly charged ions, such as kegin ions. These polymeric cations are then immobilized within the layers of the clay and, when calcined, are converted to metal oxide "pillars", effectively supporting the clay layer as a column-like structure. Therefore, as soon as the clay is dried and calcinated to form a supporting "columnar" between the clay layers, the expanded lattice structure is maintained and the porosity is increased. The resulting pores can vary in shape and size depending on the columnarized material and the parent clay material used. Examples of columnarized and columnarized clays are TJPinnavaia, Science. 220 (4595), 365-371 (1983); JMThomas, Intercalation Chemistry, (S. Whittington and A. Jacobson), Chapter 3, pp. 55-99, Academic Press, Inc. (1972); US Pat. No. 4,45910 No., U.S. Pat. No. 5,376,611; and U.S. Pat. No. 4060480, each of which is incorporated herein in its entirety.
The columnarization process uses clay minerals with exchangeable cations and expandable layers. Any columnar clay that can enhance the polymerization of olefins in the catalyst composition of the present invention can be used. Therefore, suitable clay minerals for columnarization are not limited to allophans; smectite, both dioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof, such as montmorillonite (bentonite), nontronite, Hectrite or Laponite; Halloysite; Vermiculite; Mica; Fluoromica; Chlorite; Mixed Layer Clay; Fibrous Clay (including but not limited to Sepiolite, Attapurgateite, and Parigolskite); Serpentine Clay; Illite; Laponite; Saponite; or Any combination thereof is included. Note that in one embodiment, the columnar clay activator-carrier comprises bentonite or montmorillonite, the major component of bentonite being montmorillonite.
Columnar clay can be pretreated in the present invention. For example, in one embodiment, columnar bentonite is pretreated by drying in an inert atmosphere, usually under dry nitrogen, at about 300 ° C. for about 3 hours before adding to the polymerization reactor. This example of pretreatment is not limiting, because such preheating steps include many other temperature and time (combination of temperature and time steps, all of which are the present invention. Because it can be done by).
Ion-exchangeable activators such as columnar clays used to prepare the catalyst compositions of the present invention-carriers are, but are not limited to, other inorganic carrier materials including zeolites, inorganic oxides, phosphorylated inorganic oxides and the like. Can be combined with. In one embodiment, typical carrier materials that can be used in this context include, but are not limited to, silica, silica-alumina, alumina, titania, zirconia, magnesia, boria, alumina fluoride, silylated alumina, tria, aluminolin. Includes acid salts, aluminum phosphate, zinc aluminate, silica phosphate, alumina phosphate, silica-titania, co-precipitated silica / titania, fluorinated / silylated alumina, and any combination or mixture thereof.
The amount of ansa-metallocene compound associated with the ion-exchangeable activator-carrier used to prepare the catalytic composition of the present invention is usually relative to the weight of the activator-elemental component (final metallocene-clay). About 0.1% to about 15% by weight of ansa-metallocene complex (without reference to the mixture). It has also been found that from about 1% to about 10% by weight ansa-metallocene is sufficiently useful to provide a catalyst that acts with the desired activity.
The mixture of ansa-metallocene and clay activator-carrier can be contacted and mixed for any length of time to allow complete contact between ansa-metallocene and activator-carrier. Sufficient deposition of the metallocene component on the clay can be achieved without heating the mixture of clay and metallocene complex. For example, ansa-metallocene compounds and clay materials are simply mixed from about room temperature to about 200 ° F to achieve deposition of ansa-metallocene on clay activator-carriers. In another embodiment, the ansa-metallocene compound and the clay material are mixed at about 100 ° F to about 180 ° F to achieve deposition of ansa-metallocene on the clay activator-carrier.
In another embodiment, the invention includes a catalytic composition comprising an acid activator-carrier that may include layered minerals. The term "layered mineral" refers to clay minerals, columnar clays, ion exchange clays, exfoliated clays, exfoliated clays gelled into another oxide matrix, layered minerals mixed with or diluted with other substances, etc. Or used herein to describe substances such as any combination thereof. Acid activators-If the carrier contains layered minerals, it can optionally be treated with at least one electron-attracting anion, such as those disclosed herein, but layered minerals are usually electron-optimized. Not treated with attracting anions. For example, at least one clay mineral can be used as an activator-carrier.
Clay minerals generally include a large group of fine crystalline, sheet-like layered minerals naturally found in fine-grained deposits, sedimentary rocks, etc., which are hydrous silicates and aluminosilicates with a sheet-like structure and extremely high surface area. Consists of a class of silicate minerals. The term is also used to describe hydrous mabnesium silicates that have a phyllosilicate structure. Examples of clay minerals that can be used in the present invention are, but are not limited to, allophan; smectite, both dioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof, such as montmorillonite (bentonite), nontronite, hectorite. Light or laponite; halloysite; vermiculite; mica; fluoromica; chlorite; mixed layer clay; fibrous clay (including, but not limited to, sepiolite, attapurgate, and parigolskite); sirpentine clay; illite; laponite; saponite; or them. Includes any combination of. Many common clay minerals belong to the group of clay kaolinite, montmorillonite, or illite. As disclosed herein, columnar clay can also be used as the activator-carrier of the present invention. Columnar clays typically contain sepiolite and parigolite as well as smectites and other phyrosilicate clay minerals, which ion exchange with large, typically polynuclear, highly charged metal complex cations. Has been done.
In one embodiment of the invention, when layered minerals are used as activator-carriers or metallocene activators, the layered minerals are usually calcinated prior to their use as activators. Normal baking temperatures can range from about 100 ° C to about 700 ° C, from about 150 ° C to about 500 ° C, or from about 200 ° C to about 400 ° C.
Non-limiting examples of catalyst compositions Examples of the catalyst composition of the present invention include, but are not limited to,: In one embodiment or non-limiting example, the catalytic composition may comprise at least one ansa-metallocene, at least one organoaluminum compound, and at least one activator-carrier, or catalytic composition. Objects can include those contact products, where: a) At least one ansa-metallocene formula<chemistry num="10"><img id="000011" he="44" wi="57" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>[During the ceremony, M<sup>1</sup>Is zirconium or hafnium; X is independently F, Cl, Br, or I; E is C or Si; R<sup>1</sup>And R<sup>2</sup>Are independently alkyl or aryl groups (each of which has up to 10 carbon atoms), or hydrogen, where R<sup>1</sup>Or R<sup>2</sup>At least one of them is an aryl group; R<sup>3A</sup>And R<sup>3B</sup>Are independently hydrocarbyl or trihydrocarbylsilyl groups (both of which have up to 20 carbon atoms); or hydrogen; n is an integer from 0 to 10; R<sup>4A</sup>And R<sup>4B</sup>Is independently a hydrocarbyl group with up to 12 carbon atoms, or hydrogen] Includes compounds with; b) At least one organic aluminum compound is trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, diethylaluminumethoxydo, diisobutylaluminum hydride, Includes diethylaluminum chloride, or any combination thereof; c) At least one activator-carrier comprises a solid oxide treated with an electron-attracting anion, where. Solid oxides are silica, alumina, silica-alumina, aluminophosphate, aluminum phosphate, zinc aluminate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or their mixture. Any combination; Electro-attracting anions include fluoride, chloride, bromide, iodide, phosphate, triflate, bisulfate, sulfate, fluorobolate, fluorosulfate, trifluoroacetate, phosphate, fluorophosphate, fluorozirconate, fluorosilicate, Fluorotitanates, permanganates, substituted or unsubstituted alkane sulfonates, substituted or unsubstituted allene sulfonates, substituted or unsubstituted alkyl sulphates, or any combination thereof.
In this embodiment, at least one ansa-metallocene is also expressed in the formula:<chemistry num="11"><img id="000012" he="45" wi="57" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>[During the ceremony, M<sup>1</sup>Is zirconium or hafnium; X is F, Cl, Br, or I; E is C or Si; R<sup>1</sup>And R<sup>2</sup>Are independently alkyl or aryl groups (each of which has up to 10 carbon atoms) or hydrogen, where R<sup>1</sup>Or R<sup>2</sup>At least one of them is an aryl group; R<sup>3A</sup>And R<sup>3B</sup>Are independently H, methyl, allyl, benzyl, butyl, pentyl, hexyl, or trimethylsilyl; n is an integer from 1 to 6 (including both ends); R<sup>4A</sup>And R<sup>4B</sup>Is independently a hydrocarbyl group with up to 6 carbon atoms, or hydrogen] Can include or be selected from the compounds having.
In this embodiment, at least one ansa-metallocene is also expressed in the formula:<chemistry num="12"><img id="000013" he="45" wi="59" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>[During the ceremony, M<sup>1</sup>Is zirconium or hafnium; X is Cl, Br, or I; E is C or Si; R<sup>1</sup>And R<sup>2</sup>Are independently methyl or phenyl, where R<sup>1</sup>Or R<sup>2</sup>At least one of them is a phenyl group; R<sup>3A</sup>And R<sup>3B</sup>Is independently H or methyl; n is 1 or 2; R<sup>4A</sup>And R<sup>4B</sup>Is independently H or t-butyl] Can include or be selected from the compounds having.
Also in this embodiment, at least one ansa-metallocene is also<chemistry num="13"><img id="000014" he="114" wi="140" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>Or any combination thereof may be included, or may be selected from the compound or any combination thereof.
In another embodiment or non-limiting example, the catalyst composition may comprise at least one ansa-metallocene, at least one organoaluminum compound, and at least one activator-carrier or catalyst. The compositions may include their contact products, where a) At least one ansa-metallocene<chemistry num="14"><img id="000015" he="112" wi="141" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>Or any combination thereof, including b) At least one organoaluminum compound comprises triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof. c) At least one activator-carrier comprises a sulfated solid oxide.
In yet another embodiment or non-limiting example, the catalyst composition may comprise at least one ansa-metallocene, at least one organoaluminum compound, and at least one activator-carrier. Catalytic compositions can include their contact products, where a) At least one ansa-metallocene<chemistry num="15"><img id="000016" he="76" wi="141" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>Or any combination thereof, including b) At least one organoaluminum compound includes triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, or any combination thereof; c) At least one activator-carrier comprises sulfated alumina.
In yet another embodiment or non-limiting example, the catalyst composition comprises at least one precontact ansa-metallocene, at least one precontact organoaluminum compound, at least one precontact olefin, and at least one precontact olefin. Post-contact activators-carriers can be included, or catalytic compositions can include their contact products, where ansa-metallocenes, organoaluminum compounds, olefins, and activators-carriers are present. As disclosed in the specification.
In a further aspect of the invention, at least one strongly crosslinked containing a pendant olefin-containing moiety attached to at least a portion of the cyclopentadienyl type ligand and one or two aryl groups attached to the crosslinked atom of the crosslinked ligand. The species ansa-metallocene, and at least one reaction capable of functioning to convert the metallocene into an active catalyst different from the solid oxide activator-carrier and organoaluminum compound combinations disclosed herein. Catalytic compositions comprising contact products of agents are provided. Thus, in one embodiment, it can usually involve converting the metallocene compound to its cation form, either before, after, or between, after activation of the metallocene, to a cation capable of initiating olefin polymerization. By donating a hydrocarbyl ligand to metallocene, an active catalytic composition can be formed. At least one reactant capable of converting a metallocene into an active catalyst usually activates such as alkyl if the metallocene compound does not yet contain a ligand and an activator component as provided herein. Includes components that donate possible ligands to metallocenes. In some cases, both functions can be achieved with one component, eg, organic aluminoxane. In other cases, these two functions are two different components, such as an organoaluminum compound capable of providing an activable alkyl ligand to metallocene, and another component capable of providing the activator function. Can be given by.
In one embodiment, for example, the activator and alkylating agent for the ansa-metallocene compound can be at least one organic aluminoxane, such as methylaluminoxane or isobutylaluminoxane. In another embodiment, for example, the activator is tris (pentafluoro) commonly used in combination with an alkylating agent such as an acid organic boron Lewis acid compound capable of removing anionic ligands from metallocenes, such as organoaluminum compounds. It can be phenyl) boron or triphenylcarbenium tetrakis (pentafluorophenyl) borate. In yet another embodiment, the strongly crosslinked ansa-metallocene compounds of dialkylation as disclosed herein are Bronsted acidic borate activators such as tri (n-butyl) ammonium tetrakis (p-). It can react with trill) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate to remove one alkyl ligand to form an alkylated metallocene cation. In yet another embodiment, the reaction with a borate activator of Lewis acid, such as triphenylcarbenium tetalakis (pentafluorophenyl) borate, removes one alkyl ligand to form an alkylated metallocene cation. Provided are ansa-metallocene compounds that are strongly crosslinked with dialkylation. Thus, although not intended to be constrained by theory, the active catalyst is believed to contain alkylated metallocene cations and any number of reaction steps can be used to produce such catalysts.
In a further aspect of the invention, at least one strongly crosslinked ansa containing at least one hydrocarbyl ligand capable of initiating olefin polymerization without the need for organoaluminum compounds to form contact products. -Catalyst compositions comprising metallocenes and at least one solid oxide activator-carrier contact products are provided. In this embodiment, the ansa-metallocene compound initiates pendant olefin-containing moiety attached to at least a portion of the cyclopentadienyl ligand, one or two aryl groups attached to the crosslinked atom of the crosslinked ligand, and olefin polymerization. Contains at least one possible hydrocarbyl ligand. Organoaluminium compounds will not be required to alkylate this type of "pre-alkylated" ansa-metallocene, as it already contains a hydrocarbyl ligand capable of initiating olefin polymerization.
Organic aluminoxane activator In one embodiment, the invention presents a catalytic composition comprising at least one ansa-metallocene; optionally at least one organoaluminum compound; and at least one activator, or a catalytic product thereof. A catalyst composition comprising the above is provided, wherein the activator is: i) Solid oxides treated with electron-attracting anions, layered minerals, ion-exchangeable activators-carriers, or activators-carriers containing any combination thereof; ii) At least one organic aluminoxane compound; iii) At least one organoboron compound or organoborate compound; or iv) Any combination of them Can be selected independently of.
In another embodiment, in the present invention, at least one ansa-metallocene; at least one organoaluminum compound; at least one activator-carrier containing a solid oxide treated with an electron-attracting anion; And optionally, a catalytic composition comprising a catalytic product of an aluminoxane cocatalyst is provided. In yet another embodiment, the present invention provides a catalytic composition comprising ansa-metallocene compound containing a pendant unsaturated moiety, an aluminoxane cocatalyst, an optional activator-carrier, and an optional organoaluminum compound. To. However, in one embodiment, the catalyst composition of the present invention is substantially free of aluminoxane, and in another embodiment, the catalyst composition of the present invention has polymerization activity in the substantially absence of aluminoxane. ..
In another aspect, the present invention provides a catalytic composition comprising at least one ansa-metallocene compound and aluminoxane. In this embodiment, the catalyst composition does not need to contain an acidic activator-carrier containing a chemically treated solid oxide, nor does the catalyst composition need to contain an organoaluminum compound. .. Thus, any ansa-metallocene compound disclosed herein is with any aluminoxane (poly (hydrocarbyl alumina oxide)) disclosed herein, or any combination of aluminoxane disclosed herein. In combination, the catalyst composition of the present invention can be formed. In addition, any ansa-metallocene compounds disclosed herein are any aluminoxane or combination of aluminoxanes and, in some cases, activators-carriers; in some cases layered minerals; in some cases ion exchangeable activators. -Carriers; optionally at least one organoboron compound; and optionally at least one organoborate compound can be combined to form the catalytic compositions of the invention.
Alminoxane is also referred to as poly (hydrocarbyl aluminum oxide) or organic aluminoxane. Other catalytic components are usually contacted with aluminoxane in a saturated hydrocarbon compound solvent, but any solvent that is substantially inert to the reactants, intermediates, and products of the activation step can be used. The catalyst composition formed by this method can be recovered by methods known to those skilled in the art, including but not limited to filtration, or the catalyst composition is introduced into the polymerization reactor without isolation. be able to.
In one embodiment, the aluminoxane compound of the present invention is an oligomeric aluminum compound, wherein the aluminoxane compound may comprise a linear structure, a cyclic or cage structure, or usually a mixture of the three. formula:<chemistry num="16"><img id="000017" he="22" wi="33" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>Cyclic aluminoxane compounds having (where R is a linear or branched alkyl having 1 to 10 carbon atoms and n is an integer of 3 to about 10) are included by the present invention. .. Shown here (AlRO)<sub>n</sub>The moiety also constitutes a repeating unit in linear aluminoxane. Therefore, the formula:<chemistry num="17"><img id="000018" he="26" wi="43" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>Linear aluminoxans having (where R is a linear or branched alkyl having 1 to 10 carbon atoms and n is an integer from 1 to about 50) are also included in the invention.
In addition, aluminoxane has the formula R<sup>t</sup><sub>5m + α</sub>R<sup>b b</sup><sub>m-α</sub>Al<sub>4m</sub>O<sub>3m</sub>Can also have a cage structure, where m is 3 or 4 and α = n<sub>Al (3)</sub>-n<sub>O (2)</sub>+ n<sub>O (4)</sub>Is; here, n<sub>Al (3)</sub>Is the number of tri-coordinated aluminum atoms, n<sub>O (2)</sub>Is the number of dicoordinated oxygen atoms, n<sub>O (4)</sub>Is the number of 4-coordinated oxygen atoms, R<sup>t</sup>Represents a terminal alkyl group, R<sup>b b</sup>Represents a crosslinked alkyl group; where R is a linear or branched alkyl having 1 to 10 carbon atoms.
Therefore, aluminoxane is (R-Al-O).<sub>n</sub>, R (R-Al-O)<sub>n</sub>AlR<sub>2</sub>, Etc., where the R group is usually a linear or branched C.<sub>1</sub>~ C<sub>6</sub>Alkyl, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl, where n is usually an integer from 1 to about 50. In one embodiment, the aluminoxane compounds of the present invention are not limited to, but are not limited to, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, Includes isobutylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, or a combination thereof.
Methylaluminoxane (MAO), ethylaluminoxane, or isobutylaluminoxane are the usual optional cocatalysts used in the catalyst compositions of the present invention, while organic aluminoxans with different types of R groups are included by the present invention. .. These aluminoxans are prepared from trimethylaluminum, triethylaluminum, or triisobutylaluminum, respectively, and are sometimes referred to as poly (methylaluminum oxide), poly (ethylaluminum oxide), and poly (isobutylaluminum oxide), respectively. For example, the use of aluminoxane in combination with trialkylaluminum is also within the scope of the invention, as disclosed in US Pat. No. 4794096, which is incorporated herein by reference in its entirety.
In the present invention, the formula of aluminoxane (R-Al-O)<sub>n</sub>And R (R-Al-O)<sub>n</sub>AlR<sub>2</sub>Many values of n in are intended, where n is usually at least about 3. However, depending on how the organic aluminoxane is prepared, stored, and used, the value of n can vary within a single sample of aluminoxane, and such combinations of organic aluminoxane are the methods and compositions of the present invention. Included in things.
In preparing the catalytic compositions of the present invention comprising an optional aluminoxane, the molar ratio of metallocene to aluminum in the aluminoxane is typically from about 1:10 to about 100,000: 1. In another embodiment, the molar ratio of metallocene in the aluminum to composition in aluminoxane is typically from about 5: 1 to about 15,000: 1. The amount of optional aluminoxane added to the polymerization region ranges from about 0.01 mg / L to about 1000 mg / L, about 0.1 mg / L to about 100 mg / L, or about 1 mg / L to about 50 mg / L. The amount.
Organic aluminoxane can be prepared by various procedures well known in the art. Examples of organic aluminoxane preparations are disclosed in US Pat. Nos. 3242099 and 4808651, each of which is incorporated herein by reference in its entirety. An example of how alminoxane can be prepared is as follows. Water dissolved in an inert organic solvent is AlR<sub>3</sub>The desired organic aluminoxane compound can be formed by reacting with an aluminum alkyl compound such as. Although not intended to be constrained by this description, this synthetic method is both linear and cyclic (R-Al-O).<sub>n</sub>It is believed that mixtures of alminoxane species can be provided, both of which are included by the present invention. Alternatively, organic aluminoxane can be used in AlR in an inert organic solvent.<sub>3</sub>It can be prepared by reacting an aluminum alkyl compound such as hydrated with a hydrated salt such as hydrated copper sulfate.
Activators of Organoboron and Organoboron Salts As provided herein, in one embodiment, the invention comprises a catalytic composition comprising at least one ansa-metallocene; optionally at least one organoaluminum compound; and at least one activator. A catalyst composition comprising a product or a contact product thereof is provided. The activator is at least one activator-carrier as provided herein; at least one organic aluminoxane compound; at least one organoboron or organic borate compound; or any of them. It can be selected independently of the combination. Thus, in one embodiment of the invention, the at least one activator can be selected from at least one organoboron compound, at least one organoborate compound, or a combination thereof.
In a further embodiment, in the present invention, at least one ansa-metallocene; at least one organoaluminum compound; at least one activator-carrier containing a solid oxide treated with an electron-attracting anion; and. Optionally, a catalytic composition comprising a catalytic contact product of an organoboron or an organoborate cocatalyst is provided. In another embodiment, in the present invention, at least one ansa-metallocene compound containing a pendant unsaturated moiety; a cocatalyst of organoborate or organoborate; an organoaluminum compound; and optionally an activator-carrier. A catalyst composition comprising a contact product is provided. In this embodiment, the catalyst composition does not need to contain an activator-carrier. Any ansa-metallocene compound disclosed herein includes an activable ligand such as an alkyl or hydride ligand if it does not yet contain a ligand such as an organoaluminum compound to form a catalytic composition. Combined with any combination of organic boron or organic borate cocatalysts disclosed herein, or any combination of organic boron or organic borate cocatalysts disclosed herein, with the components given to the metallocene. be able to. In addition, any ansa-metallocene compound disclosed herein is a cocatalyst of any organoboron or organic borate to form the catalytic compositions of the invention; organoaluminum compounds; optionally at least. It can be combined with one type of aluminoxane; and optionally an activator-carrier. However, in one embodiment, the catalyst composition of the present invention is substantially free of compounds of organoboron or organic borate, and in another embodiment, the catalyst composition of the present invention is organoboron or organic. It has polymerization activity in the substantially absence of the borate compound.
In one embodiment, as provided herein, the term "organoboron" compound can be used to refer to a neutral boron compound, a borate, or a combination thereof. For example, the organoboron compound of the present invention can include a fluoroorganoboron compound, a fluoroorganoborate compound, or a combination thereof. Any fluoro-organoboron or fluoro-organoborate compound known in the art can be used. The term "fluoroorganoboron compound" is of type BY<sub>3</sub>It has its usual meaning to refer to a neutral compound. The term "fluoroorganic borate compound" is also of type [cation]<sup>+</sup>[BY<sub>4</sub>]<sup>-</sup>(Here, Y represents a fluorinated organic group) has its usual meaning to refer to a monoanion salt of a fluoroorganoboron compound. For convenience, the compounds of fluoroorganoboron and fluoroorganoborate are usually referred to collectively by organoboron compounds or, depending on the content, by either name.
Examples of fluoroorganic borate compounds that can be used as cocatalysts in the present invention are, but are not limited to, fluorinated aryl borates such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium. Nium tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl ) borate, N, N-dimethylanilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, triphenylcarbenium tetrakis [3,5 -Bis (trifluoromethyl) phenyl] borate and the like (including mixtures thereof) are included. Examples of fluoroorganoboron compounds that can be used as cocatalysts herein include, but are not limited to, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, etc. (they). Includes a mixture of).
Although not intended to be bound by the following theories, these examples of fluoroorganoborate and fluoroorganoboron compounds, as well as related compounds, are with organometallic compounds, as disclosed in US Pat. No. 6,599,93. When combined, they are thought to form "weakly coordinated" anions.
In general, any amount of organoboron compound can be used in the present invention. In one embodiment, the molar ratio of organoboron compound to metallocene compound in the composition is from about 0.1: 1 to about 10: 1. Generally, the amount of fluoroorganoboron or fluoroorganoborate compounds used as co-catalysts for metallocenes ranges from about 0.5 mol to about 10 mol of boron compounds per mole of metallocene compound. In one embodiment, the amount of fluoroorganoboron or fluoroorganoborate compound used as a cocatalyst for metallocene ranges from about 0.8 mol to about 5 mol of boron compound per mole of metallocene compound.
Optional Ionizable Ionic Compound Cocatalyst In one embodiment, the invention comprises 1) an olefin-containing moiety attached to a cyclopentadienyl-type ligand and at least one aryl group attached to a crosslinked atom of a crosslinked ligand, as disclosed herein. Containing at least one strongly crosslinked ansa-metallocene compound; 2) optionally at least one organoaluminum compound; and 3) a catalytic composition comprising at least one activator, or a catalytic product thereof. A catalyst composition is provided. In another aspect, the invention provides a catalytic composition as disclosed herein, which comprises, in addition to these other components, an optionally optional ionizable ionic compound co-catalyst. However, in one embodiment, the catalytic composition of the present invention is substantially free of an ionic ionic compound, and in another embodiment, the catalytic composition of the present invention is substantially free of an ionicizable ionic compound. Has polymerization activity in the absence. In yet another embodiment, the invention presents at least one ansa-metallocene compound as disclosed herein, at least one ionizable ionic compound cocatalyst, and optionally at least one activation. A catalyst composition comprising an agent-carrier and optionally at least one organoaluminum compound is provided. Examples of ionizable ionic compounds are disclosed in US Pat. Nos. 5576259 and 5807938.
Ionicizable ionic compounds are ionic compounds that can function to enhance the activity of the catalytic composition. Without being bound by theory, it is believed that ionizable ionic compounds can react with metallocene compounds to convert metallocenes to cationic metallocene compounds. Again, not intended to be constrained by theory, ionizable ionic compounds are anionic ligands, perhaps (X).<sup>3</sup>) Or (X<sup>4</sup>) Etc. non-η<sup>5</sup>-By withdrawing the alkadienyl ligand completely or partially from the metallocene, it is believed that it can function as an ionizable compound. But in a way to form an ion pair that ionizes metallocene (X)<sup>3</sup>) Or (X<sup>4</sup>) Metals in metallocenes that remove ligands-(X)<sup>3</sup>) Or metal-(X<sup>4</sup>) Weakens the bond, (X<sup>3</sup>) Or (X<sup>4</sup>) Is simply coordinated to the ligand of), or the ionizable ionic compound is an activator, regardless of any other mechanism by which activity may occur. Moreover, the ionizable ionic compound does not need to activate only metallocenes. The activation function of the ionizable ionic compound is apparently enhanced as a whole as compared with the catalyst composition containing the catalyst composition containing no ionizable ionic compound.
Includes 3-hexafluoroisopropanolato) aluminate, or silver tetrakis (perfluoro-t-butoxy) aluminate, or any combination thereof. However, those ionizable ionic compounds are exemplary, and the ionizable ionic compounds are not limited to them in the present invention.
Olefin monomer In one embodiment of the invention, unsaturated reactants useful in polymerization methods using the catalytic compositions and methods of the invention have from about 2 to about 30 carbon atoms per molecule and at least 1 Includes olefin compounds with two olefin double bonds. The present invention includes homopolymerization methods using a single olefin such as ethylene or propylene, and copolymerization reactions using at least one different olefin compound. In one embodiment of the ethylene copolymerization reaction, the ethylene copolymer comprises a large amount of ethylene (> 50 mol percent) and a small amount of comonomer (<50 mol percent), but this is not a requirement. Comonomers that can be copolymerized with ethylene must have 3 to about 20 carbon atoms in their molecular chains.
Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched, substituted, unsubstituted, functionalized, and non-functionalized olefins can be used in the present invention. For example, conventional unsaturated compounds that can be polymerized with the catalysts of the invention are, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-. Penten, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, Includes 4 normal octenes, 4 normal nonenes, 5 normal decenes, and any mixture of 2 or more of them. Cyclic and bicyclic olefins, including, but not limited to, cyclopentene, cyclohexene, norbornene, norbornadiene, etc., can also be polymerized as described above.
In one embodiment, the monomeric ethylene can be copolymerized with the comonomer if a copolymer is desired. In another embodiment, examples of comonomer are, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-. Penten, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 4 normal octenes, 4 species Normal nonen or 5 kinds of normal decene are included. In another embodiment, the comonomer can be 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or styrene.
In one embodiment, the amount of comonomer introduced into the reactor region to produce the copolymer is generally from about 0.001 to about 99 weight percent comonomer relative to the total weight of the monomer and comonomer. In one embodiment, the amount of comonomer introduced into the reactor region to produce the copolymer is from about 0.01 to about 50% by weight of comonomer relative to the total weight of the monomer and comonomer. In another embodiment, the amount of comonomer introduced into the reactor region is from about 0.01 to about 10 weight percent of comonomer relative to the total weight of the monomer and comonomer, and in yet another embodiment from about 0.1. It is about 5 weight percent. Alternatively, in the copolymers produced, sufficient amounts can be used to give the above concentrations by weight.
Although not intended to be constrained by theory, it is conceivable that steric hindrance may interfere with and / or slow down the polymerization process when branched, substituted, or functionalized olefins are used as reactants. Be done. Thus, some olefin branching and / or cyclic moieties removed from the carbon-carbon double bond react so that similar olefin substituents located closer by the carbon-carbon double bond may have interfered. Would not be expected to prevent. In one embodiment, the at least one reactant for the catalytic composition of the invention is ethylene, thus the polymerization may be homopolymerized or different acyclic, cyclic, terminal, internal, linear. , Branched, substituted, or unsubstituted olefin. In addition, the catalytic composition of the present invention can be used for the polymerization of diolefin compounds containing, but not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.
Preparation of catalyst composition In one embodiment, the invention presents the catalytic composition and at least one strongly crosslinked ansa-metallocene compound, at least one activator, and optionally at least one activator, as disclosed herein. Includes methods involving contacting one organoaluminum compound. The methods disclosed herein include any series of contact steps that allow each given component to be contacted, and any sequence of contacting the component or mixture of components. Although not intended to be limited, examples of contact steps are typically exemplified herein with treated solid oxide activator-carriers and organoaluminum co-catalysts. These exemplary steps may include any number of pre-contact and post-contact steps and may further include the use of olefin monomers as the contact component in any of these steps. Examples of preparation methods for preparing the catalyst composition of the present invention follow below.
In one embodiment of the invention, ansa-metallocene is pre-contacted with an olefin monomer (not necessarily polymerizing the olefin monomer) and an organoaluminum co-catalyst during the first period, after which the pre-contact mixture is solidified. Oxide activator-can be contacted with a carrier. For example, the first period for contact between ansa-metallocene, olefin monomer, and organoaluminum cocatalyst, i.e. pre-contact time, can typically range from about 1 minute to about 24 hours, about 0.1. Approximately 1 hour is typical. Pre-contact times of about 10 to about 30 minutes are also typical.
As soon as the pre-contact mixture of ansa-metallocene, olefin monomer, and organoaluminum cocatalyst is contacted with the solid oxide activator, this composition (including the solid oxide activator further) is combined with the post-contact mixture. Is called. Generally, the post-contact mixture can be left in contact during a second period, i.e. the post-contact time, after which the polymerization step is initiated. In one embodiment, the post-contact time between the solid oxide activator-carrier and the pre-contact mixture typically ranges from about 1 minute to about 24 hours, typically about 0.1 to about 1 hour. Post-contact times of about 10 to about 30 minutes are also typical.
In another embodiment of the invention, various catalytic components (eg, ansa-metallocene, activator-carrier, organoaluminum cocatalyst, and optionally unsaturated hydrocarbons) are polymerized simultaneously while the polymerization reaction is in progress. Can be contacted in the reactor. Alternatively, two or more of any of these catalytic components can be "pre-contacted" in a vessel or tube, after which they enter the reaction region. This pre-contact step can be a continuous step in which the pre-contact product is continuously fed to the reactor, or a batch of pre-contact products can be added to produce the catalyst composition, stepwise or It can be a batch process. This pre-contact step can be carried out for a period of time ranging from a few seconds to a few days, or even longer. In this embodiment, the continuous pre-contact step can typically last from about 1 second to about 1 hour. Also in this embodiment, the continuous pre-contact step can typically last from about 10 seconds to about 45 seconds, or from about 1 minute to about 30 minutes.
Alternatively, the pre-contact method can be carried out in a multi-step process in which a large number of mixtures, each containing a different set of catalytic components, are prepared, rather than a single step. For example, at least two catalytic components may be contacted to form a first mixture, and then the first mixture may be contacted with at least one other catalytic component to form a second mixture, and so on. ..
The multi-stage pre-contact step can be performed in a single container or in multiple containers. Further, the multi-stage pre-contact step can be performed in series (continuous), parallel, or a combination thereof. For example, the first mixture of two catalytic components is formed in the first container, and the second mixture containing one additional catalytic component in addition to the first mixture is the first container or the first mixture. It can be formed in a second container usually located downstream of one container.
In another embodiment, one or more catalyst components can be split and used in different precontact treatments. For example, some catalyst components are fed into a first pre-contact vessel for pre-contact with at least one other catalyst component, while the remainder of the same catalyst component is at least one other catalyst. It can be fed into a second pre-contact vessel for pre-contact with the ingredients, or can be fed directly into the reactor, or a combination thereof. Pre-contact can be performed in any suitable device, such as a tank, a stirring mixing tank, various static mixing devices, tubes, flasks, containers of any type, or any combination thereof.
In one embodiment, for example, the catalytic compositions of the invention contact 1-hexene, triisobutylaluminum or tri-n-butylaluminum, and ansa-metallocene for at least about 30 minutes, after which the pre-contact mixture is sulfated. Alumina activator-Prepared by contacting the carrier for at least about 10 minutes to 1 hour to form an active catalyst.
The pre-contact step usually increases the productivity of the polymer as compared to the same catalytic composition prepared without this pre-contact step. The enhanced active catalyst composition of the present invention can be used for homopolymerization of α-olefin monomers such as ethylene or copolymerization of α-olefins and comonomer. However, neither the pre-contact step nor the post-contact step is necessary for the present invention.
The post-contact mixture is an adsorption of the pre-contact mixture and the solid oxide activator-carrier so that some components of the pre-contact mixture are immobilized, absorbed or precipitated on the solid oxide activator-carrier. , Impregnation, or can be heated at a temperature and duration sufficient to allow interaction. For example, the post-contact mixture can be heated from about 0 ° F to about 150 ° F. If the mixture is to be heated, temperatures typically from about 40 ° F to about 95 ° F.
In one embodiment, the molar ratio of ansa-metallocene compound to organoaluminum compound can be from about 1: 1 to about 1: 10,000. In another embodiment, the molar ratio of ansa-metallocene compound to organoaluminum compound can be from about 1: 1 to about 1: 1,000, and in another embodiment from about 1: 1 to about 1: 100. possible. These molar ratios represent the ratio of the total amount of organoaluminum compounds in which both the ansa-metallocene compound to pre-contact mixture and the post-contact mixture are combined.
When using the pre-contact step, the molar ratio of olefin monomer to ansa-metallocene compound in the pre-contact mixture can generally be from about 1:10 to about 100,000: 1 or from about 10: 1 to about 1,000: 1.
In another aspect of the invention, the weight ratio of solid oxide activator to organoaluminum compound can range from about 1: 5 to about 1,000: 1. In another embodiment, the weight ratio of solid oxide activator to organoaluminum compound can be from about 1: 3 to about 100: 1, and in yet another embodiment, from about 1: 1 to about 50. Can be 1.
In a further aspect of the invention, the weight ratio of ansa-metallocene to solid oxide activator-carrier can be from about 1: 1 to about 1: 1,000,000. Yet another aspect of the invention is the weight ratio of ansa-metallocene to solid oxide activator-carrier, which can be from about 1:10 to about 1: 100,000, and in another aspect, about 1:20. Can be about 1: 1000.
One aspect of the invention is that no aluminoxane is required to form the catalytic compositions disclosed herein, which is a feature that allows for lower polymer production costs. Therefore, in one embodiment, in the present invention, AlR in the absence of aluminoxane.<sub>3</sub>-Type organoaluminum compounds and activators-carriers can be used. Although not intended to be constrained by theory, it is believed that organoaluminum compounds may not activate metallocene catalysts in the same way as organoaluminoxans.
In addition, expensive borate compounds or MgCl for forming the catalytic compositions of the present invention.<sub>2</sub>Does not require, but aluminoxane, borate compounds, MgCl<sub>2</sub>, Or any combination thereof can optionally be used in the catalytic compositions of the present invention. Further, in one embodiment, cocatalysts such as aluminoxane, organoboron compounds, ionizable ionic compounds, or any combination thereof, together with ansa-metallocene in the presence or absence of an activator carrier. It can be used as a co-catalyst of. In addition, cocatalysts such as aluminoxane, organoboron compounds, ionizable ionic compounds, or any combination thereof, are ansa in the presence or absence of organoaluminum compounds, as specified herein. -Can be used with metallocene. Therefore, at least one ligand on the metallocene is a hydrocarbyl group, H, or BH.<sub>4</sub>If at least one activator comprises an organoaluminoxane compound; or if both of these conditions are present, then at least one organoaluminum compound is optional. However, the catalyst compositions of the present invention are active in the substantially absence of cocatalysts such as aluminoxane, organoboron compounds, ionizable ionic compounds, or any combination thereof.
Therefore, in one embodiment, the present invention is a method of producing a catalyst composition. At least one ansa-metallocene, at least one olefin, and at least one organoaluminum compound are contacted during the first period to at least one pre-contact ansa-metallocene, at least one pre-contact organic. The step of forming a pre-contact mixture containing an aluminum compound and at least one pre-contact olefin, and The pre-contact mixture is contacted with at least one activator-carrier and optionally an additional organoaluminum compound during the second period to contact at least one post-contact ansa-metallocene, at least one post-metallocene. The step of forming a retrocontact mixture containing a catalytic organoaluminum compound, at least one retrocontact olefin, and at least one retrocontact activator-carrier. Methods are provided, including. In one embodiment, at least one ansa-metallocene has the formula: (X<sup>1</sup>) (X<sup>2</sup>) (X<sup>3</sup>) (X<sup>4</sup>) M<sup>1</sup>[During the ceremony, M<sup>1</sup>Is titanium, zirconium, or hafnium; (X<sup>1</sup>) And (X<sup>2</sup>) Are independently substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl; (X<sup>1</sup>) And (X<sup>2</sup>The one substituent on) is given by the formula ER<sup>1</sup>R<sup>2</sup>Where E is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and E is (X).<sup>1</sup>) And (X<sup>2</sup>), And R<sup>1</sup>And R<sup>2</sup>Are independently alkyl or aryl groups (each of which has up to 12 carbon atoms), or hydrogen, where R<sup>1</sup>And R<sup>2</sup>At least one of them is an aryl group; (X<sup>1</sup>) Or (X<sup>2</sup>) At least one substituent is a substituted or unsubstituted alkenyl group having up to 12 carbon atoms; (X<sup>3</sup>) And (X<sup>4</sup>) Are independently 1) F, Cl, Br, or I; 2) a hydrocarbyl group with up to 20 carbon atoms, H, or BH.<sub>4</sub>3) Hydrocarbyl oxide group, hydrocarbylamino group, or trihydrocarbylsilyl group (all of which have up to 20 carbon atoms); 4) OBR<sup>A</sup><sub>2</sub>Or SO<sub>3</sub>R<sup>A</sup>(Here, R<sup>A</sup>Is an alkyl or aryl group, each of which has up to 12 carbon atoms). Any additional substituents on the substituted cyclopentadienyl, substituted indenyl, substituted fluorenyl, or substituted alkenyl groups can be independently of aliphatic, aromatic, cyclic, aliphatic and cyclic groups. Combination, oxygen group, sulfur group, nitrogen group, phosphorus group, arsenic group, carbon group, silicon group, or boron group (all of which have 1 to 20 carbon atoms); halide; or hydrogen] Can include compounds having.
In one embodiment, the catalytic activity of the catalysts of the present invention typically comprises approximately 100 grams of polyethylene (abbreviated as gP / (gCTSO · hr)) per gram of chemically treated solid oxide per hour. Exceeds or is equal to it. In another embodiment, the catalyst of the invention can be characterized by an activity greater than or equal to about 250 gP / (gCTSO · hr) and in another embodiment about 500 gP / (gCTSO · hr). Can be characterized by activity greater than or equal to. In yet another embodiment, the catalyst of the present invention can be characterized by an activity of greater than or equal to about 1000 gP / (gCTSO · hr) and in another embodiment about 2000 gP / (gCTSO · hr). ) Can be characterized by activity greater than or equal to. In one embodiment, this activity is usually measured under slurry polymerization conditions with isobutane as a diluent at a polymerization temperature of about 90 ° C and an ethylene pressure of about 550 psig. In another embodiment, this activity is measured under slurry polymerization conditions using isobutane as a diluent at a polymerization temperature of about 80 ° C to about 105 ° C and an ethylene pressure of about 450 psig to about 550 psig. It is desirable that the reactor shows virtually no signs of any wall scale, coating or other form of deposit after making these measurements.
Usefulness of catalyst composition in polymerization method The catalysts of the present invention are intended for any olefin polymerization method known in the art that uses various types of polymerization reactors. As used herein, a "polymerization reactor" includes any polymerization reactor capable of polymerizing an olefin monomer to produce a homopolymer or copolymer. Such homopolymers and copolymers are referred to as resins or polymers. Various types of reactors include what can be referred to as batch, slurry, gas phase, solution, high pressure, tubular or autoclave reactors. Gas phase reactors may include fluidized bed reactors or stepwise horizontal reactors. The slurry reactor may include vertical or horizontal loops. High pressure reactors may include autoclaves or tubular reactors. Reactor types can include batch or continuous methods. In the continuous method, intermittent or continuous product discharge may be used. The method may also include partial or complete direct recycling of unreacted monomers, unreacted comonomer, and / or diluent.
The polymerization reactor system of the present invention may include one type of reactor in one system, or a plurality of reactors of the same or different types. For the production of polymers in multiple reactors, at least two separate polymerization reactors interconnected by a switching device that allows the polymer obtained from the first polymerization reactor to be transferred to the second reactor. Includes several steps in. The desired polymerization conditions in one reactor may differ from the operating conditions of the other reactors. In addition, polymerization in multiple reactors may include the manual transfer of polymer from one reactor to the next for continuous polymerization. Multiple reactor systems, but not limited to, multiple loop reactors, multiple gas phase reactors, loop and gas phase reactor combinations, multiple high pressure reactors, or high pressure reactor and loop and / or Any combination may be included, including a combination with a gas reactor. Multiple reactors may be operated continuously or in parallel.
According to one aspect of the invention, the polymerization reactor system may include at least one loop slurry reactor. Such reactors are known in the art and may include vertical or horizontal loops. Monomers, diluents, catalysts and, optionally, any comonomer are continuously fed to the loop reactor where polymerization takes place. In general, the continuous method can include the continuous introduction of monomers, catalysts, and diluents into a polymerization reactor, and the continuous removal of suspensions containing polymer particles and diluents from this reactor. The reactor effluent can be flushed to remove the solid polymer from the liquid containing diluents, monomers and / or comonomer. Various techniques may be used for this separation process, including, but not limited to, flushing, which may include any combination of heat addition and depressurization; separation by cyclone action in either a cyclone or water cyclone; or separation by centrifugation. it can.
Typical slurry polymerization methods (also known as granular morphological methods) well known in the art are, for example, US Pat. Nos. 3248179, 4501885, 5565175, 5575979, 6239235, 6262191. Disclosed in No. and No. 6833415, each of which is incorporated herein by reference in its entirety.
Suitable diluents used in slurry polymerization are well known in the art and include, but are not limited to, monomers being polymerized and hydrocarbons that are liquid under reaction conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some loop polymerization reactions can be carried out under bulk conditions without the use of diluents. One example is the polymerization of propylene monomers as disclosed in US Pat. No. 5,455,314, which is incorporated herein by reference in its entirety.
According to yet another aspect of the invention, the polymerization reactor may include at least one gas phase reactor. Such systems are known in the art and may use a continuous recirculation flow containing one or more monomers that are continuously circulated through a fluidized bed in the presence of a catalyst under polymerization conditions. .. The recirculated flow can be recovered from the fluidized bed and recirculated back to the reactor. At the same time, the polymer product is recovered from the reactor and new or unused monomers can be added to replace the polymerized monomers. A method for multi-stage vapor phase polymerization of an olefin in which the catalyst-containing polymer formed in the first polymerization region is supplied to the second polymerization region while the olefin is polymerized in the gas phases of at least two independent vapor phase polymerization regions. Such a vapor phase reactor may include. One type of gas reactor is disclosed in US Pat. Nos. 5352749, 4588790, and 5436304, each of which is incorporated herein by reference in its entirety.
According to yet another aspect of the invention, the high pressure polymerization reactor may include a tubular reactor or an autoclave reactor, both of which are known in the art. Tubular reactors may have several regions to which unused monomers, initiators, or catalysts are added. The monomer can be incorporated into the inert air stream and introduced in one region of the reactor. Initiators, catalysts, and / or catalytic components can be mixed into the air stream and introduced in another region of the reactor. The airflow can be mixed for polymerization. Heat and pressure may be used appropriately to obtain optimum polymerization reaction conditions.
According to yet another aspect of the invention, the polymerization reactor may include a solution polymerization reactor in which the monomer is brought into contact with the catalyst composition by suitable stirring or other means. Carriers containing an inert organic diluent or excess monomer may be used. If desired, the monomer may be contacted with the catalytic reaction product in the gas phase in the presence or absence of a liquid substance. The polymerization region is maintained at a temperature and pressure that results in the formation of a solution of the polymer in the reaction medium. Stirring may be used to obtain better temperature control over the polymerization region and to maintain a uniform polymerization mixture. Appropriate means are used to dissipate the exothermic reaction of the polymerization. These reactors are known in the art.
A polymerization reactor suitable for the present invention may further comprise any combination of at least one feedstock supply system, at least one feedstock for the catalyst or catalyst component, and / or at least one polymer recovery system. Reactor systems suitable for the present invention include systems for feedstock purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractional distillation, recirculation, storage, shipping, laboratory analysis, and process control. Further may be included.
Conditions controlled to provide polymerization efficiency and resin properties include temperature, pressure and concentrations of various reactants. The polymerization temperature can affect the catalyst productivity, the molecular weight and molecular weight distribution of the polymer. A suitable polymerization temperature can be any temperature below the depolymerization temperature according to the Gipps free energy equation. Usually this includes, for example, from about 60 ° C to about 280 ° C, and from about 70 ° C to about 110 ° C, depending on the type of polymerization reactor.
Suitable pressures also vary depending on the reactor and the type of polymerization. The pressure for liquid phase polymerization in the loop reactor is typically less than 1000 psig. The pressure for vapor phase polymerization is typically about 200-500 psig. High-pressure polymerization of tubular or autoclave reactors is typically performed at about 20,000 to 75,000 psig. The polymerization reactor can also be operated in the supercritical range, which is generally performed at higher temperatures and pressures. Operation above the critical point (supercritical phase) of the pressure / temperature diagram can provide advantages.
The concentrations of various reactants can be controlled to produce resins with specific physical and mechanical properties. The proposed end-use product formed by the resin and the method of forming the product determine the desired resin properties. Mechanical properties include tensile, bending, impact, creep, stress relaxation and hardness testing. Physical properties include measurements of density, molecular weight, molecular weight distribution, melting point, glass transition point, crystal melting temperature, stereoregularity, crack growth, long chain branching and rheology.
Concentrations of monomers, comonomer, hydrogen, cocatalysts, denaturants, and electron donors are important in producing these resin properties. Comonomers are used to control product density. Hydrogen is used to control the molecular weight of the product. Cocatalysts can be used for alkylating, scavenging toxins, and controlling molecular weight. Denaturants can be used to control product properties and electron donors affect stereoregularity. In addition, the concentration of poison should be minimized as it affects the reaction and product properties.
Polymers or resins can be formed into a variety of articles including, but not limited to, bottles, drums, toys, household containers, kitchen utensils, film products, fuel tanks, pipes, geomembranes, and liners. Various methods can be used to form these articles, including, but not limited to, blow molding, extrusion molding, rotary molding, thermoforming, cast molding and the like. After polymerization, additives and denaturants can be added due to the desired properties of the final product in order to give a better treatment during production. Additives include surface modifiers such as slip agents, anti-adhesives, adhesives; antioxidants such as primary and secondary antioxidants; pigments; treatment aids such as wax / oil and fluoroelastomers; There are special additives such as flame retardants, antioxidants, scavengers, absorbents, odor enhancers, decomposing agents and the like.
Ethylene polymer prepared by the present invention In one embodiment, the ethylene polymer produced using the catalytic composition of the invention typically uses a strongly crosslinked ansa-metallocene compound that does not have an olefin-containing moiety bound to a cyclopentadienyl-type ligand. If the metallocene of comparison also contains at least one aryl group attached to the cross-linked atom of the cross-linking ligand, it is also characterized by lower levels of long-chain branching (LCB) that are usually observed. In a further embodiment, the ethylene polymer produced using the catalytic compositions of the present invention typically comprises a strongly crosslinked ansa-metallocene compound that does not have at least one aryl group attached to the crosslinked atom of the crosslinked ligand. When used, it is also characterized by higher molecular weights that are usually observed, even when the comparative metallocene contains an olefin-containing moiety bound to a cyclopentadienyl-type ligand. 3 to 8 illustrate various aspects of the olefin homopolymers produced by the present invention.
Size Exclusion Chromatography (SEC) and Polygonal Light Scattering (MALS) combination detection was used to detect and characterize polymer branches. Turn (R<sub>g</sub>Molecular size vs. M of the ethylene homopolymers produced in Examples 1-7 and 10-11, as illustrated in FIGS. 3-5, which are diagrams obtained from the SEC-MALS analysis plotting the radii of).<sub>w</sub>One measurement of shows one aspect of the usefulness of the invention in reducing LCB. Turn (R) from a known linear control (in this case, HiD9640)<sub>g</sub>) Radius deviation indicates branching. Therefore, according to the data of FIGS. 3 to 5, the polymer prepared by using the catalyst composition according to the present invention is R.<sub>g</sub>Against M<sub>w</sub>It is shown in the plot of that at the high molecular weight end, there is only a very slight deviation from the linear standard (HiD9640).
6 and 7 show the log (η) of the polymer prepared according to Examples 1 to 11 of the invention and Comparative Examples 14 to 16.<sub>0</sub>) Vs log (M<sub>w</sub>) Is illustrated, and how to clarify the decrease in LCB level is illustrated (see: Table 1). Linear polyethylene polymers have their zero shear viscosity η<sub>0</sub>According to the exponential law relationship between and their weight average molecular weight Mw, it is found to have an index very close to 3.4. This relationship is η<sub>0</sub>Logarithm of M<sub>W</sub>When plotted against the logarithm of, it is indicated by a straight line with a slope of 3.4. It is generally accepted that the deviation of this linear polymer from the line is due to the presence of long chain branching (LCB). Janzen and Colby wrote log (η) about a given frequency of LCB.<sub>0</sub>) Vs log (M<sub>w</sub>) Is presented as a function of predicting the expected deviation from the linear plot as a function of the weight average molecular weight of the polymer. See also: [Diagnosing long-chain branching in polyethylenes, J.Mol.Struct.485-486, 569-584 (1999)], which is hereby by reference in its entirety. Incorporated in.
Therefore, FIGS. 6 and 7 show η for the polymers prepared according to the present invention.<sub>0</sub>Logarithm vs. M<sub>w</sub>Plot the logarithm of and the weight average molecular weight of zero shear melt viscosity (M)<sub>w</sub>) Dependence is illustrated, and these polymers deviate very slightly from the well-known 3.4 exponential law "Arnett line" (J. Phys. Chem. 1980) used as an indicator of linear polymers. To prove. Consistent with this measurement, both SEC-MALS and rheological data show that the metallocenes of the invention produce very low LCB in ethylene polymerization, as illustrated in FIG. 6 for Examples 1-11. In contrast, the polymers made by Comparative Examples 14-16 have a much lower M than the polymers prepared by Examples 1-11 of the present invention.<sub>w</sub>Had. Typically, these polymers also had the same or slightly higher levels of LCB, as illustrated in FIG.
FIG. 8 shows a comparison of gel permeation chromatography (GPC) experiments on the polymers produced according to Examples 1-11 and 14-16 of the present invention. These GPC results (Table 1 and FIG. 8) show that polyethylene (PE) produced according to the present invention generally has a high molecular weight. The polymers made by Comparative Examples 14-16 were characterized by low levels of LCB (Fig. 8), but these comparative polymers had a relatively low M compared to the polymers prepared according to the present invention.<sub>w</sub>Had. Comparative Examples 12 and 13 also demonstrate that the catalyst prepared with the comparative metallocene C-1 showed poor activity (Table 1). In addition, during the process of preparing GPC and SEC-MALS samples of these materials, significant amounts of insoluble polymers (about 50% by weight) were observed in the polymeric samples prepared by Comparative Examples 12 and 13. .. Therefore, using the polymeric samples prepared according to Comparative Examples 12 and 13, 25 mg to 28 mg of polymer was mixed in 25 mL of 1,2,4-trichlorobenzene and the mixture was maintained at 150 ° C. Stirred for 5 hours. Visual inspection of the sample vial containing the sample prepared as described revealed that a precipitate had formed on the sides of the sample vial. This observation shows that the polymers prepared according to Examples 12 and 13 using metallocene C-1 were non-linear polymers. No insoluble polymer was observed in the polymers prepared by any of the other examples.
Definition In order to define the terms used herein more clearly, the following definitions are provided. To the extent that any definition or use specified by any document incorporated herein by reference conflicts with the definition or use specified herein, the definition or use specified herein governs. To do.
The term "polymer" is used herein to mean a homopolymer containing ethylene and / or a copolymer of ethylene with another olefinic comonomer. "Polymer" is also used herein to mean homopolymers and copolymers of any other polymerizable monomer disclosed herein.
The term "cocatalyst" generally refers to an organoaluminum compound that may constitute one component of a catalyst composition, but is not limited to, as disclosed herein, an aluminoxane, an organoboron compound, an organoborate. It is also used herein to refer to a compound or an optional component of a catalytic composition comprising an ionizable ionic compound. In one embodiment, the cocatalyst is of formula Al (X).<sup>5</sup>)<sub>n</sub>(X<sup>6</sup>)<sub>3-n</sub>Can be an organoaluminum compound in the formula, (X<sup>5</sup>) Is a hydrocarbyl with 1 to about 20 carbon atoms; (X)<sup>6</sup>) Are alkoxides or aryl oxides (all of which have about 1 to about 20 carbon atoms), halides, or hydrides; n is a number from 1 to 3 (including both ends). The term "cocatalyst" can be used regardless of the actual function of the compound or any chemical mechanism by which the compound acts.
The term "pre-contact" mixture is referred to as "post-contact" of the catalytic components to be contacted in the second period, i.e. contact in the first period before the first mixture used to form the second mixture. As used herein to represent a first mixture of catalytic components to cause. Usually, the pre-contact mixture represents a mixture of metallocene, olefin monomer, and organoaluminum compound prior to contact with the acid activator-carrier and optionally the organoaluminum compound. Thus, "pre-contact" refers to the components that are in contact with each other but before being contacted in the second, post-contact mixture. Therefore, in the present invention, it is possible to distinguish between the ingredients used to prepare the pre-contact mixture and the ingredients after the mixture has been prepared. For example, according to this expression, once contacted with metallocene and olefin monomers, the pre-contact organoaluminum compound is at least one chemical compound, formulation that differs from the separate organoaluminum compounds used to prepare the pre-contact mixture. , Or it is possible that they have reacted to form a structure. In this case, the pre-contact organoaluminum compound or component is represented as comprising the organoaluminum compound used to prepare the pre-contact mixture.
Similarly, the term "post-contact" mixture is used herein to represent a second mixture of catalytic components that are contacted in the second period, one component of which is contacted in the first period. It is the "pre-contact" or first mixture of catalyst components. Usually, the term "post-contact" mixture is a mixture of metallocenes, olefin monomers, organoaluminum compounds, and acid activators-carriers (some pre-contact compounds of these components are added to form a post-contact mixture). As used herein to represent (formed in contact with any additional component to be made). Generally, an additional component added to make up the post-contact mixture is a solid oxide activator, which is optionally used to prepare the pre-contact mixture, as described herein. It may contain the same or different organoaluminum compounds as the organoaluminum compounds. Therefore, in the present invention, it is possible to distinguish between the components used to prepare the post-contact mixture and the components after the mixture has been prepared.
The term "strongly crosslinked ansa-metallocene" refers to the two ηs in the molecule.<sup>5</sup>-A cycloalkazienyl ligand is attached at the cross-linking moiety, where the two ηs<sup>5</sup>-Represents a metallocene compound in which the shortest bond between cycloalkazienyl ligands contains one atom. Therefore, the cross-linking or chain length between the two cyclopentadienyl ligands is a single atom, but this cross-linking atom is substituted. Therefore, the metallocene of the present invention is a crosslinked screw (η).<sup>5</sup>-Cycloalkadienyl) type compound, where η<sup>5</sup>-Cyclo alkazienyl moieties include cyclopentadienyl ligands, indenyl ligands, fluorenyl ligands and the like (including their substitution analogs and partially saturated analogs). Possible substituents on these ligands include hydrogen, and thus the expression "their substituted derivatives" in the present invention refers to partially saturated ligands such as tetrahydroindenyl, tetrahydrofluorenyl, octahydro. Includes fluorenyl, partially saturated indenyl, partially saturated fluorenyl, substituted partially saturated indenyl, substituted partially saturated fluorenyl and the like. In some contexts, metallocenes are simply referred to as "catalysts", much as the term "cocatalyst" is used herein to refer to organoaluminum compounds.
The terms "catalyst composition", "catalyst mixture", etc. are used to prepare the actual product of the reaction of the components of the mixture, the nature of the active catalyst moiety, or the aluminum cocatalyst, ansa-metallocene, precontact mixture. It does not depend on the dynamics of the solid oxide activator after mixing any olefin monomer or these components. Therefore, the terms "catalyst composition", "catalyst mixture" and the like include both heterogeneous compositions and homogeneous compositions.
The term "hydrocarbyl" includes, but is not limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkazienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, etc., and all of them substituted, unsubstituted, branched. Used to identify hydrocarbon radicals, including linear, heteroatom-substituted derivatives. Unless otherwise stated, the hydrocarbyl groups of the present invention typically contain up to about 20 carbon atoms. In one embodiment, the hydrocarbyl group can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.
The term "hydrocarbyl oxide" group is used generically to collectively refer to both alkoxide and aryl oxide groups. Unless otherwise stated, the hydrocarbyl oxide groups of the present invention typically contain up to about 20 carbon atoms. In one embodiment, the hydrocarbyl oxide group can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.
The term "hydrocarbylamino" group refers to alkylamino (NHR), arylamino (NHAr), dialkylamino (NR).<sub>2</sub>), And diarylamino (NAr)<sub>2</sub>) Is used generically to collectively refer to the groups. Unless otherwise stated, the hydrocarbylamino group of the present invention typically contains up to about 20 carbon atoms. In one embodiment, the hydrocarbylamino group can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.
The term "alkenyl" is used broadly to identify a hydrocarbyl group containing an alkene moiety that includes all steric chemical isomers, regardless of the particular position chemistry of the alkene moiety. So, for example, the term "alkenyl" can be any CH = CH, regardless of the position of the substitution that occurs within the alkyl group.<sub>2</sub>-Substituted alkyl group or CH = CMe<sub>2</sub>-Intended to contain substituted alkyl groups. Terms such as "olefin-containing hydrocarbyl group" or "olefin-containing pendant group" are commonly used synonymously with alkenyl groups, and these terms depend on the specific position of the C = C double bond within the group. Show again that you do not intend to be restrained. Unless otherwise stated, the alkenyl groups of the present invention typically contain up to about 20 carbon atoms. In one embodiment, the alkenyl group can have up to 12 carbon atoms, up to 8 carbon atoms, or up to 6 carbon atoms.
The terms "solid oxide activator-carrier", "acid activator-carrier", "activator-carrier", "treated solid oxide", "treated solid oxide compound", etc. To exhibit the behavior of Lewis acid or Bronsted acid, a treated solid inorganic oxide with a relatively high porosity, treated with an electron-attracting component, which is usually an anion, and calcinated. As used herein. The electron-attracting component is usually an electron-attracting anion source compound. Thus, the treated solid oxide compound comprises a calcined contact product of at least one solid oxide compound and at least one electron-attracting anion source compound. Usually, the activator-carrier or "treated solid oxide compound" comprises at least one ionizable acidic solid oxide compound. The term "carrier" or "activator-carrier" is not used to mean that these components are inactive and this component should be construed as the inactive component of the catalytic composition. is not it.
As used herein, the term "activator" refers to 1) metallocene components; and 2) metallocenes that can be activated, such as alkyl or hydride ligands, if the metallocene compound does not yet contain a ligand or the like. Generally, a substance capable of converting a contact product of a component to be given to a catalyst capable of polymerizing an olefin. The term refers to activators ionizing metallocenes, drawing out anionic ligands to form ion pairs, weakening metal-ligand bonds in metallocenes, simply coordinating to anionic ligands, or any other mechanism. Regardless, it is used. As disclosed herein, contact products are i) activators-carriers, layered minerals, ion-exchangeable activators-carriers, or theirs, containing solid oxides treated with electron-withdrawing anions. Any combination of; ii) organic aluminoxane compounds; iii) organoboron compounds or organoborate compounds; or iv) include at least one activator that can be independently selected from any combination of their components.
The term "clay" is a clay mineral that can be used as an activator-carrier in the catalytic compositions described herein, pretreated by either exchanging cations, columnarizing or simply moistening. Alternatively, it is used herein to refer to a component of a catalytic composition that is a substantial part of a mixture of clay minerals. The transition metal compound and the organometallic cocatalyst react with the clay activator-carrier to form an active catalyst. Although not intended to be constrained by the following description, the clay components of the catalyst compositions of the present invention are not only as cocatalysts from the perspective of being in close physicochemical contact with the transition metal compounds, but also the transition metal compounds. Activator for-Perhaps functions as a carrier.
As used herein, the collective term "clay minerals" is used herein to describe a broad group of microcrystalline sheet-like clay minerals naturally found in microsediments, sedimentary rocks, etc. .. Clay minerals are a class of hydrous silicates and hydrous aluminosilicate minerals with a sheet-like structure and a very high surface area. The term is also used to describe hydrous magnesium silicate with a phyllosilicate structure. Many common clay minerals belong to the kaolinite group, montmorillonite group, or illite group clay. Therefore, the term "clay mineral" is not used herein to refer to fine soil consisting of mineral particles that are not necessarily clay minerals and have dimensions less than about 0.002 mm.
The term "columnar clay" usually includes large, typically polynuclear, highly charged metal complex cations ion-exchanged smectites as well as other phyllosilicate clay minerals in addition to sepiolite and parigolite. It is used herein to refer to the components of the catalyst composition. Examples of such ions include, but are not limited to, kegin ions that can have a charge such as 7+, various polyoxometallates, and other large ions. Thus, the term "columnarization" refers to a simple exchange reaction in which the exchangeable cations of clay minerals are replaced by large, highly charged ions, such as kegin ions. These polymeric cations are then immobilized within the intermediate layer of clay and, when calcined, are converted into metal oxide "columnars" that effectively support the clay layer as a strut-like structure. Examples of columnar clays and columnar clays are TJPinnavaia, Science 220 (4595), 365 ~ 371 (1983); JMThomas, Intercalation Chemistry, (S. Whittington ans). A. Jacobson ed.) Ch.3, pp.55-99, Academic Press, Inc., (1972); U.S. Pat. Nos. 4425910; 5376611; and 4060480, each of which is in its entirety. Is incorporated herein by.
Any method, device, and material similar to or equivalent to that described herein can be used in the practice or testing of the present invention, while typical methods, devices, and materials are described herein. Will be done.
All publications and patents described herein are hereby referenced for purposes of describing and disclosing, for example, the structures and methodologies described in the publications that may be used in connection with the inventions described herein. Incorporated into the specification. Publications considered above and throughout the text are provided solely for their disclosure prior to the filing date of this application. It is not herein to be construed as an admission that the inventors are not entitled to precede such disclosure by conventional inventions.
For any particular compound disclosed herein, any general structure presented may be any conformational isomer, positional isomer, stereoisomer, etc. that may result from a particular set of substituents, etc. Also includes. The general structure also includes, depending on the content, all enantiomers, diastereomers, other optical isomers, whether in enantiomer or racemic forms, as well as mixtures of stereoisomers.
The present invention is further illustrated by the following examples, which should never be construed as imposing a limitation on its scope. On the other hand, for various other aspects, embodiments, modifications, and equivalents thereof that may be suggested to those skilled in the art without departing from the spirit of the invention or the appended claims after reading the description herein. It should be clearly understood that there may be means.
In the following examples, unless otherwise stated, the synthesis and preparation described herein was carried out under an inert atmosphere such as nitrogen and / or argon. Solvents were purchased from commercial sources and usually dried on activated alumina prior to use. Unless otherwise stated, reactants were obtained from commercial sources.
General test procedures, characterization, and synthetic procedures are provided herein. Synthetic methods for preparing metallocenes, treated solid oxides, and other reactants of the invention are also provided herein.
General test procedure Melt index (MI, g / 10 min) was measured at 190 ° C. with 2,160 gram weight according to ASTM D1238 condition F.
High load melt index (HLMI, g / 10 min) was measured at 190 ° C. using 21,600 grams of weight according to ASTM D1238 Condition E.
Polymer densities were measured in grams (g / cc) per cubic centimeter of compression molded samples cooled at about 15 ° C. per hour and adjusted at room temperature for about 40 hours according to ASTM D1505 and ASTM D1928, Procedure C.
Molecular weight and molecular weight distribution at 145 ° C using a PL-GPC220 (Polymer Labs, UK) equipped with a differential index detector and three 7.5 mm x 300 mm, 20 μm Mixed A-LS columns (Polymer Labs). Obtained by operating. The flow velocity of the mobile phase of 1,2,4-trichlorobenzene (TCB) containing 0.5 g / L of 2,6-di-t-butyl-4-methylphenol (BHT) was set to 1 mL / min and the molecular weight was set to 1 mL / min. Depending on, the concentration of the polymer solution was generally kept in the range of 1.0-1.5 mg / mL. Sample preparation was performed at 150 ° C. for 4 hours with occasional gentle agitation, after which the solution was transferred to a sample vial for injection. Solvents with the same composition as the mobile phase were used in solution preparation to minimize unbalanced solvent peaks. The molecular weight and molecular weight distribution were estimated using the Chevron Phillips Chemical Company's wide-area linear polyethylene, Marlex BHB5003, as a broad standard using the integral test method. Broad standard integral tables were predetermined in separate experiments with SEC-MALS.
Melt viscosity measurement to determine shear viscosity properties Small strain oscillator shear measurements were performed with an ARES vibration rheometer (TA Instrument, formerly Rheometrics Inc.) using parallel plate geometry. Data were typically obtained over an angular frequency range of 0.03 to 100 rad / sec at a temperature of 190 ° C.
The fluffy sample was stabilized with 0.1% by weight BHT dispersed in acetone and then vacuum dried prior to molding. The sample was compression molded at 184 ° C for a total of 3 minutes. The sample was melted at a relatively low pressure for 1 minute and then subjected to a high molding pressure for an additional 2 minutes. The molded sample was then quenched at cold (room temperature) pressure. A disk with dimensions of 2 mm x 25.4 mm was punched out of the molded slab for rheological characterization.
The rheometer laboratory was covered with nitrogen to minimize polymer degradation. The rheometer was preheated to the starting temperature of the test. The sample was placed and after thermal equilibrium in the oven, the test pieces were squeezed between the plates to a thickness of 1.6 mm to remove excess.
Strain was generally maintained at a single value over frequency sweep, but relatively large strain values were used to maintain measurable torque for low viscosity samples. For high viscosity samples, relatively small strain values were used to avoid overloading the torque transducer and keep the sample within the linear viscoelastic limits. If necessary, the device automatically reduces distortion at high frequencies to protect the torque transducer from overloading.
Viscosity data for modified Carreau-Yasuda models [R. Byron Bird, Robert C. Armstrong, and Ole Hassager, Dynamics of Polymer Liquids, Volume 1, Fluid Mechanics, (John Wiley & Sons, New York, 1987), p171-172], which is incorporated herein by reference to obtain estimates of zero shear viscosity, viscosity relaxation time, and width parameters, as shown below.
| η<sup>*</sup>| = η<sub>0</sub>/ [1+ (ωτ)<sub>η</sub>)<sup>a</sup>]<sup>((1-n) / a)</sup>(In the formula, | η<sup>*</sup>| = Magnitude of complex viscosity (Pa · sec) ω = angular frequency (rad / sec) η<sub>0</sub>= Zero shear viscosity (Pa · sec) τ<sub>η</sub>= Viscosity relaxation time (seconds) a = width parameter n = exponential law parameter, fixed at 0.1818)
Absolute molecular weight measured by light scattering Molecular weight data were measured using SEC-MALS, which combines size exclusion chromatography (SEC) and polygonal light scattering (MALS) detection. DAWN EOS 18-Santa Barbara, CA through a thermally controlled thermal transfer line at the same temperature as the SEC column and its differential refractometer (DRI) detector (145 ° C). ) Was combined with the PL-210 SEC system (Polymer Labs, UK) or the Waters 150CV Plus system (Mitford, MA). Mobile phase [1,2,4-trichlorobenzene (TCB)] with three 7.5 mm x 300 mm, 20 μm Mixed A-LS columns (Polymer) at a flow rate setting of 0.7 mL / min. Eluted through Labs). Depending on the sample, a polyethylene (PE) solution at a concentration of about 1.2 mg / mL was prepared at 150 ° C. for 4 hours and then transferred to a SEC infusion vial in a carousel heated to 145 ° C. For higher molecular weight polymers, longer heating times were needed to obtain a true homogeneous solution. In addition to obtaining concentration chromatograms, 17 light scattering chromatograms at different angles were also obtained for each injection using Wyatt's Astra® software. For each chromatographic intercept, both the absolute molecular weight (M) and the root mean square (RMS) radius [also known as the radius of the swirl (Rg)] were obtained from the intercept and slope of the device plot, respectively. The method of this process is detailed in Wyatt, PJ, Anal.Chim.Acta, 272, 1 (1993), which is incorporated herein by reference in its entirety. The control of the linear PE used was a linear high density broad molecular weight distribution (MWD) polyethylene sample (Chevron Phillips Chemical Co.). This weight average molecular weight (M<sub>w</sub>), Molar mass distribution (M<sub>n</sub>), Z-Average molecular weight (M)<sub>z</sub>) And molecular weight distribution (M<sub>w</sub>/ M<sub>n</sub>) Is calculated from these data and presented in various tables.
The amount of LCB in the ethylene polymer was determined using the Zimm-Stockmayer method. SEC-MALS is M and R<sub>g</sub>Is measured simultaneously on each section of the chromatogram, so Equation 1:<maths num="1"><img id="000019" he="23" wi="105" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></maths>(In the formula, the subscripts br and lin represent branched and linear polymers, respectively). Mean square (R) of branched molecules with the same M, as shown in<sub>g</sub>) Mean square of paired molecules (R)<sub>g</sub>) Branch index g as a function of M by determining<sub>M</sub>Could be determined directly on each section.
Given g<sub>M</sub>And the average weight of LCB per molecule (B)<sub>3w</sub>), Equation 2:<maths num="2"><img id="000020" he="20" wi="119" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></maths>As shown in, it was calculated using the Zimm-Stockmayer equation, where the branch was presumed to be trifunctional or Y-shaped. Then the LCB frequency (LCB) of the i-th intercept, which is the number of LCBs per 1000C.<sub>Mi</sub>), Equation 3: LCB<sub>Mi</sub>= 1000 * 14 * B<sub>3w</sub>/ M<sub>i</sub>Where M<sub>i</sub>Is the MW of the i-th intercept) Was calculated directly using. Therefore, an LCB distribution (LCBD) that intersected the molecular weight distribution (MWD) was established for the complete polymer.
The specific surface area (surface area) and specific pore volume (pore volume) were determined using the Quantachrome Autosorb-6 Nitrogen Pore Size Distribution Instrument. This device was obtained from Quantachrome Corporation, Syosset, NY.
Silica Fluoride-Alumina Activator-Preparation of Carrier The silica-alumina used to prepare the silica-alumina acid activator-carrier in this example typically contains 13% alumina, with a pore volume of about 1.2 cc / g and about 400 m.<sup>2</sup>It was Davison silica-alumina obtained from WRGrace as grade MS13-110 with a surface area of / g. This material was fluorinated by impregnating with a solution containing ammonium difluoride in a sufficient amount equal to 10% by weight of silica-alumina to the initial dampness. The impregnated material was then dried in a vacuum oven at 100 ° C. for 8 hours. The silica-alumina sample thus fluorinated was then calcined as follows. Approximately 10 grams of alumina was placed in a 1.75 inch crystal tube with a sintered crystal disk at the bottom. While supporting this silica-alumina on the disc, dry air was blown through the disc at a linear rate of 1.6 to 1.8 standard cubic feet per hour. An electric furnace around the quartz tube was used to raise the tube temperature to a final temperature of about 500 ° C at a rate of about 400 ° C per hour. At this temperature, silica-alumina was suspended in dry air for about 3 hours. The silica-alumina was then recovered, stored under dry nitrogen and used without exposure to the atmosphere.
Sulfated Alumina Activator-Preparation of Carrier Alumina sulfate was formed by a method of chemically treating alumina with, but not limited to, sulfuric acid, ammonium sulfate, or a sulfate or hydrogen sulfate usually selected from ammonium hydrogen sulfate. An example is as follows.
Approximately 15-20% (NH) of commercially available alumina sold as WRGrace Alumina A<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>Or H<sub>2</sub>SO<sub>4</sub>It was sulfated by impregnating it with an aqueous solution containing. The sulfated alumina was calcined in air at 550 ° C (inclination rate of 240 ° C / hour) and held at this temperature for 3 hours. The alumina was then recovered, stored under dry nitrogen and used without exposure to the atmosphere.
Metallocene preparation Unless otherwise stated, the reactants were obtained from the Aldrich Chemical Company and used as accepted. 2,7-Di-tert-butylfluorene was purchased from Degussa. The Grignard reagent CpMgCl (1M in THF) was purchased from the Boulder Scientific Company. Hafnium chloride (IV) was purchased from Strem. Solvent THF was distilled from potassium and anhydrous diethyl ether, methylene chloride, pentane, and toluene were purchased from Fisher Scientific Company and stored on activated alumina. All solvents were degassed and stored under nitrogen. The reaction product,<sup>1</sup>1 H NMR spectroscopy (300MHz, CDCl<sub>3</sub>, CHCl<sub>3</sub>(Based on either the peak of residual protons at 7.24 ppm of TMS or 0 ppm of TMS) or<sup>13</sup>C NMR (75MHz, DCCl<sub>3</sub>, CDCl at 77.00ppm<sub>3</sub>Analyzed by (based on the central line of).
The following fulvenes (F-1 to F-5) were prepared as disclosed herein and used to prepare the ligands L-1 to L-5 given herein.
<chemistry num="18"><img id="000021" he="95" wi="115" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
The following ligands L-1 to L-5 were prepared as disclosed herein.
<chemistry num="19"><img id="000022" he="69" wi="116" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
Synthesis of 2- (pent-4-enyl) -6,6-diphenylpentafulvene (F-1) To 5-bromo-1-pentene (95 wt% 100 g, 0.637 mol) was added cyclopentadienyl magnesium chloride (700 mL, 0.7 mol, 1 M solution in THF) at 0 ° C. for 1 hour. After stirring at 0 ° C. for an additional 30 minutes, the mixture was warmed to room temperature. After stirring overnight, the reaction was quenched with a mixture of ice and water. The mixture was extracted with pentane. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was removed at room temperature under vacuum to obtain a yellowish brown liquid (98 g, crude pent-4-enylcyclopentadiene). To crude pent-4-enylcyclopentadiene (89 g) dissolved in THF (500 mL) was added n-BuLi (10 M 60 mL in hexanes, 0.6 mol) at -78 ° C. The mixture was warmed to room temperature and stirred overnight. This anionic solution was added to benzophenone (110 g, 0.604 mol) dissolved in THF (500 mL) at 0 ° C. for 25 minutes. The mixture was warmed to room temperature and stirred overnight. The reaction was quenched with a mixture of ice and 10% aqueous HCl. The mixture was extracted with pentane. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was removed under vacuum at 40 ° C. to give a dark red viscous oil. The oil was dissolved in heptane and filtered through silica gel. 5-10% CH of silica gel in heptane<sub>2</sub>Cl<sub>2</sub>The product was recovered by washing with. The solvent was removed to give the desired product (145 g, 84% yield based on 5-bromo-1-pentene) as a dark red viscous oil.<chemistry num="20"><img id="000023" he="49" wi="151" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
Synthesis of 1- (3- (pent-4-enyl) cyclopentadienyl) -1- (2,7-di-tert-butylfluorenyl) -1,1-diphenylmethane (L-1) Et<sub>2</sub>To 2,7-di-tert-butylfluorene (125.1 g, 0.45 mol) dissolved in O (700 mL), n-BuLi (10 M 47 mL in hexane, 0.47 mol) was added at 0 ° C. The mixture was warmed to room temperature and stirred overnight. This anion solution, Et<sub>2</sub>It was added to 2- (pent-4-enyl) -6,6-diphenylpentafluven (F-1) (145 g, 0.487 mol) dissolved in O (300 mL) at -78 ° C for 10 minutes. The mixture was warmed to room temperature and stirred overnight. The reaction was quenched with a mixture of ice and 10% aqueous HCl. Et the mixture<sub>2</sub>Extracted with O. The organic phase was washed with water and dried over anhydrous sodium sulfate. The solvent was removed under vacuum to give a light brown solid. The solid was washed with heptane and dried under vacuum. A mixture of isomers (191.7 g, 74% yield) for the desired product was obtained as a white solid.
Synthesis of 2- (Gnat-3-enyl) -6,6-diphenylpentafulvene (F-2) To 4-bromo-1-butene (97 wt% 100 g, 0.719 mol) was added cyclopentadienyl magnesium chloride (800 mL, 0.8 mol, 1 M solution in THF) at 0 ° C. for 50 minutes. After stirring at 0 ° C. for an additional 15 minutes, the mixture was warmed to room temperature. After stirring overnight, the reaction was quenched with a mixture of ice and water. The mixture was extracted with pentane. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was removed under vacuum at room temperature to give a brown liquid (94.2 g, crude but-3-enylcyclopentadiene). To crude buto-3-enylcyclopentadiene (94.2 g) dissolved in THF (500 mL) was added n-BuLi (10 M 70 mL in hexanes, 0.7 mol) at -78 ° C. The mixture was warmed to room temperature and stirred overnight. This anionic solution was added to benzophenone (133.8 g, 0.735 mol) dissolved in THF (400 mL) at 0 ° C. for 35 minutes. The mixture was warmed to room temperature and stirred overnight. The reaction was quenched with a mixture of ice and 10% aqueous HCl. The mixture was extracted with pentane. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was removed under vacuum at 40 ° C. to give a dark red viscous oil. The oil was dissolved in pentane and filtered through silica gel. Product, 5-10% CH in heptane<sub>2</sub>Cl<sub>2</sub>The silica gel was washed and recovered. The solvent was removed to give the desired product (152 g, 74.4% yield relative to 4-bromo-1-butene) as a dark red viscous oil.<chemistry num="21"><img id="000024" he="46" wi="150" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
Synthesis of 1- (3- (Gnat-3-enyl) cyclopentadienyl) -1- (2,7-di-tert-butylfluorenyl) -1,1-diphenylmethane (L-2) Et<sub>2</sub>To 2,7-di-tert-butylfluorene (91.7 g, 0.33 mol) dissolved in O (500 mL) was added n-BuLi (10 M 35 mL in hexanes, 0.35 mol) at 0 ° C. The mixture was warmed to room temperature and stirred overnight. This anion solution, Et<sub>2</sub>It was added to 2- (but-3-enyl) -6,6-diphenylpentafluven (Compound F-2) (104 g, 0.366 mol) dissolved in O (200 mL) at 0 ° C. for 35 minutes. After stirring at 0 ° C. for an additional 30 minutes, the mixture was warmed to room temperature and stirred overnight. The reaction was quenched with a mixture of ice and 10% aqueous HCl. CH the mixture<sub>2</sub>Cl<sub>2</sub>Extracted with. The organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was removed under vacuum to give a light brown solid. The solid was washed with peptane and dried under vacuum. A mixture of isomers (142 g, 76.5% yield) for the desired product was obtained as a white solid.
Synthesis of 2- (1,1-dimethylpent-4-enyl) -6,6-diphenylpentafulvene (F-3) 6-butenyl-6-methylpentafluben (17.8 g, 122 mmol) in dry THF (50 mL) while cooling with dry ice (KJ Stone and A solution of methyllithium (1.6M 75 mL in ether, 120 mmol) was added to a solution of RDLittle, J.Org.Chem., 1984, 49 (11), prepared by the method 1849-1853). The yellow solution was gradually added to a solution of benzophenone (21.87 g, 120 mmol) in THF (50 mL) while stirring for 20 hours, warming to room temperature and then cooling in ice. A red color was formed immediately, and analysis of the aliquots after 4 hours showed that the reaction was almost complete. After an additional hour, the mixture was cooled with the addition of a solution of water (200 mL) and concentrated hydrochloric acid (20 mL). Following the addition of pentane (150 mL), the organic layer was washed with water and dried over sodium sulphate. The solvent was removed under vacuum and the red liquid was cooled to -15 ° C overnight. The red crystalline product was washed with cold methanol and dried under vacuum to give a red solid (32.8 g, 84% yield).<chemistry num="22"><img id="000025" he="45" wi="150" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
Of 1- (3-1,1-dimethylpent-4-enyl) cyclopentadienyl) -1- (2,7-di-tert-butylfluorenyl) -1,1-diphenylmethane (L-3) Synthetic Et<sub>2</sub>A solution of 2,7-di-tert-butylfluorene (27.8 g, 100 mmol) in O (200 mL) was cooled with dry ice and n-BuLi (1.6 M 68 mL in hexane, 0109 mmol) was added dropwise. The slurry was warmed to room temperature and stirred for 24 hours. This dark solution is cooled in dry ice and then Et.<sub>2</sub>A solution of 2- (1,1-dimethylpent-4-enyl) -6,6-diphenylpentafluvene (Compound F-3) (32.8 g, 54.3 mmol) in O (100 mL) was added rapidly. The mixture was warmed to room temperature and stirred for 20 hours. After cooling in ice, a solution of water (200 mL) and concentrated hydrochloric acid (20 mL) was added. Following the addition of pentane (100 mL), the organic layer was separated and washed with water. After drying over sodium sulfate and filtering, the solvent was removed under vacuum to give a glassy solid. The solid was heated with methanol (100 mL) and the hot methanol solution was discarded. This process was repeated 4 times. The solid was then dissolved in hot pentane and then removed under vacuum with heating. The solid was ground, dried under vacuum and then heated with ethanol (70 mL). After cooling, the solid was filtered and dried. A mixture of isomers (18.1 g, 30% yield) for the desired product was obtained as a white solid.
Synthesis of 6,6-diphenylpentafulvene (F-4) Benzophenone (63.8 g, 350 mmol) was dissolved in anhydrous 1,2-dimethoxyethane (DME) (150 mL) under nitrogen. In a 1 liter flask, powdered potassium hydroxide (30 g, 535 mmol) was slurried in DME (200 mL). The slurry was cooled in an ice bath and freshly crushed cyclopentadiene (35 mL, 430 mmol) was added. After 30 minutes, a solution of benzophenone was added over 15 minutes. The flask was stirred in the refrigerator for 90 hours, then 3M HCl (450 mL) was added while cooling in ice. The mixture was diluted with pentane (500 mL) and separated. The organic layer was washed with water (2 x 200 mL) and dried over sodium sulfate. The solution was filtered and led to drying under vacuum. The solid was dissolved in boiling pentane (600 mL) and then concentrated to 400 mL. Cooling to -15 ° C for 40 hours gave a red solid (69.5 g, 86.3% yield).<chemistry num="23"><img id="000026" he="32" wi="152" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
Synthesis of 1-cyclopentadienyl-1- (2,7-di-tert-butylfluorenyl) -1,1-diphenylmethane (L-4) Add n-BuLi (2.5M 43.0 mL in hexanes, 107.5 mmol) to a solution of 2,7-di-tert-butylfluorene (29.8 g, 107 mmol) in dry THF (100 mL) cooled with dry ice. It was. The bath was removed and the dark solution was stirred for 2 hours. The solution was then added dropwise to a solution of 6,6-diphenylpentafluven (Compound F-4) (26.0 g, 113 mmol) in THF (100 mL) while cooling in ice. The reaction mixture was stirred at room temperature for 86 hours and then cooled in ice. 1 M HCl solution (100 mL) was added. The mixture was diluted with chloroform (100 mL) and separated. The chloroform layer was washed with water (3 x 100 mL) and dried over sodium sulfate. The solution was filtered and evaporated to a light orange solid. The solid was dissolved in boiling chloroform (150 mL) and methanol (150 mL) was added slowly. After cooling to -15 ° C for 2 days, the solid was filtered off, pulverized and dried under vacuum. A mixture of isomers (25.4 g, 46.7% yield) for the desired product was obtained as an off-white solid.
Synthesis of 5- (3-pent-4-enyl) cyclopentadienyl-5- (2,7-di-tert-butylfluorenyl) nonane (L-5) In a flask, cool to -78 ° C under nitrogen, 2,7-di-tert-butylfluorene (10 g, 36 mmol), Et.<sub>2</sub>O (150 mL) was added and n-BuLi (10 M 4.3 mL in hexane, 43 mmol) was added via syringe with stirring. The reaction mixture was warmed to room temperature, stirred overnight, cooled to -78 ° C and 2- (pent-4-enyl) -6,6-dibutylpentafulvene (Compound F-5) (13 g, 50 mmol). ) (Prepared by the method of KJ Stone and RD Little, J.Org.Chem., 1984, 49 (11), 1849-1853) was added rapidly. The reaction mixture was warmed to room temperature and stirred overnight. Saturate reaction NH<sub>4</sub>Quenched with Cl solution. Et organic layer<sub>2</sub>Extract with O, wash with water, anhydrous Na<sub>2</sub>SO<sub>4</sub>Dried on. The solvent was removed under vacuum to give a yellow oil. The oil was eluted with heptane through a silica-gel column to give a mixture of isomers (12.8 g, 66% yield) as the oil for the desired product.
Diphenylmethidene {η<sup>5</sup>-[3- (Pent-4-enyl) cyclopentadiene-1-ylidene]} [η<sup>5</sup>-(2,7-di-tert-butylfluorene-9-iriden)] Synthesis of hafnium dichloride (I-1) Et<sub>2</sub>1- (3- (pent-4-enyl) cyclopentadienyl) -1- (2,7-di-tert-butylfluorenyl) -1,1-diphenylmethane (compound) dissolved in O (400 mL) To L-1) (45.3 g, 78.6 mmol), n-BuLi (2.5 M 68.5 mL in hexanes, 171.3 mmol) was slowly added at 0 ° C. The mixture is warmed to room temperature, stirred overnight, then through a cannula with pentane (450 mL) and Et.<sub>2</sub>HfCl suspended in a mixture with O (30 mL)<sub>4</sub>It was added to (26.8 g, 83.6 mmol) at 0 ° C. for 30 minutes. The mixture was warmed to room temperature and stirred for 2 days. The slurry was concentrated and centrifuged. The liquid was decanted and removed. The remaining solid was washed twice with pentane (100 mL), then extracted with methylene chloride and centrifuged. The solution was led to drying under vacuum to give a yellow solid (46.4 g, 71.7%).<chemistry num="24"><img id="000027" he="68" wi="152" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
Diphenylmethidene {η<sup>5</sup>-[3- (Gnat-3-enyl) cyclopentadiene-1-ylidene]} [η<sup>5</sup>-(2,7-di-tert-butylfluorene-9-iriden)] Hafnium dichloride (I-2) Et<sub>2</sub>1- (3- (Buto-3-enyl) cyclopentadienyl) -1- (2,7-di-tert-butylfluorenyl) -1,1-diphenylmethane (compound) dissolved in O (30 mL) To L-2) (3.2 g, 5.7 mmol), n-BuLi (2.5 M 5.2 mL in hexanes, 13 mmol) was slowly added at 0 ° C. The mixture is warmed to room temperature, stirred overnight, then through a cannula with pentane (30 mL) and Et.<sub>2</sub>HfCl suspended in a mixture with O (5 mL)<sub>4</sub>It was added to (2.1 g, 6.5 mmol) at 0 ° C. for 10 minutes. The mixture was warmed to room temperature and stirred for 2 days. The slurry was concentrated and centrifuged. The liquid was decanted and removed. The remaining solid was washed twice with pentane (80 mL), then extracted with methylene chloride and centrifuged. The solution was allowed to dry under vacuum to give a yellow solid (3.1 g, 67.4% yield).<chemistry num="25"><img id="000028" he="74" wi="152" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
Diphenylmethidene {η<sup>5</sup>-[3- (Gnat-3-enyl) cyclopentadiene-1-ylidene]} [η<sup>5</sup>-(2,7-di-tert-butylfluorene-9-iriden)] Synthesis of zirconium dichloride (I-3) Et<sub>2</sub>1- (3- (Buto-3-enyl) cyclopentadienyl) -1- (2,7-di-tert-butylfluorenyl) -1,1-diphenylmethane suspended in O (400 mL) To (Compound L-2) (40.5 g, 72.1 mmol), n-BuLi (10 M 15.2 mL in hexanes, 152 mmol) was slowly added at 0 ° C. The mixture is warmed to room temperature, stirred overnight, then through a cannula with pentane (400 mL) and Et.<sub>2</sub>ZrCl suspended in a mixture with O (30 mL)<sub>4</sub>It was added to (18.5 g, 79.4 mmol) at 0 ° C. for 15 minutes. The mixture was warmed to room temperature, stirred for 1 day and evaporated to dryness. The residue was stirred in pentane (300 mL) and centrifuged. The supernatant was discarded. The remaining solid was washed twice with pentane (100 mL), then extracted with methylene chloride and centrifuged. The solution was allowed to dry under vacuum to give a red solid (38.1 g, 73.3% yield).<chemistry num="26"><img id="000029" he="65" wi="152" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
Diphenylmethidene {η<sup>5</sup>-[3- (Pent-4-enyl) cyclopentadiene-1-ylidene]} [η<sup>5</sup>-(2,7-di-tert-butylfluorene-9-iriden)] Synthesis of zirconium dichloride (I-4) Et<sub>2</sub>1- (3- (pent-4-enyl) cyclopentadienyl) -1- (2,7-di-tert-butylfluorenyl) -1,1-diphenylmethane dissolved in O (300 mL) To compound L-1) (34.7 g, 60.2 mmol), n-BuLi (2.5 M 52 mL in hexanes, 130 mmol) was slowly added at 0 ° C. The mixture is warmed to room temperature, stirred overnight, then through a cannula with pentane (250 mL) and Et.<sub>2</sub>ZrCl suspended in a mixture with O (20 mL)<sub>4</sub>It was added to (14.7 g, 63.1 mmol) at 0 ° C. for 30 minutes. The mixture was warmed to room temperature, stirred for 1 day and evaporated to dryness. The residue was stirred in pentane (200 mL) and centrifuged. The supernatant was discarded. The remaining solid was washed twice with pentane (50 mL), then extracted with methylene chloride and centrifuged. The solution was led to drying under vacuum to give a red solid (33.5 g, 75.6%).<chemistry num="27"><img id="000030" he="71" wi="150" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
Diphenylmethidene {η<sup>5</sup>-[3- (1,1-dimethylpent-4-enyl) cyclopentadiene-1-ylidene]} [η<sup>5</sup>-(2,7-di-tert-butylfluorene-9-iriden)] Synthesis of zirconium dichloride (I-5) Et<sub>2</sub>1- (3- (1,1-dimethylpent-4-enyl) cyclopentadienyl) -1- (2,7-di-tert-butylfluorenyl) -1,1-diphenylmethane in O (50 mL) (Compound L-3) (10.8 g, 17.9 mmol) was cooled in dry ice and n-BuLi (1.6 M 22.2 mL in hexane, 35.5 mmol) was added dropwise. After 1 hour, the bath was removed and the mixture was stirred at room temperature for 48 hours. ZrCl suspended in pentane (50 mL) while cooling the mixture in ice<sub>4</sub>Added to (4.37 g, 18.8 mmol). The slurry was stirred at room temperature for 65 hours. The slurry was concentrated to viscosity and pentane (70 mL) was added. The slurry was stirred overnight and the liquid was removed by dencating. The solid was washed twice with pentane, then extracted with methylene chloride and centrifuged. The solution was allowed to dry under vacuum to give a red solid (11.65 g, 85.2% yield).<chemistry num="28"><img id="000031" he="71" wi="151" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
Diphenylmethidene [η]<sup>5</sup>-(Cyclopentadiene-1-iriden)] [η<sup>5</sup>-(2,7-di-tert-butylfluorene-9-iriden)] Synthesis of zirconium dichloride (C-1) Dry Et. 1-Cyclopentadienyl-1- (2,7-di-tert-butylfluorenyl) -1,1-diphenylmethane (Compound L-4) (15.26 g, 30.0 mmol) under nitrogen.<sub>2</sub>Suspended in O (250 mL). While cooling in dry ice, n-BuLi (2.5M 24.0 mL in hexane, 60 mmol) was added dropwise. The bath was then removed and the mixture was stirred for 24 hours. This solution was gradually added to zirconium tetrachloride (7.38 g, 31.7 mmol) suspended in pentane (50 mL) and cooled in ice. The orange slurry was stirred for 90 hours and warmed to room temperature. The resulting slurry was centrifuged and the solid was mixed with dry methylene chloride (120 mL). The mixture was centrifuged, the solution was removed and led to drying under vacuum. The desired product (9.63 g, 48% yield) was obtained as an orange solid.<chemistry num="29"><img id="000032" he="46" wi="150" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
Dibutylmethidene {η<sup>5</sup>-[3- (Pent-4-enyl) cyclopentadiene-1-ylidene]} [η<sup>5</sup>-(2,7-di-tert-butylfluorene-9-iriden)] Synthesis of zirconium dichloride (C-2) In a flask, 5- (3- (pent-4-enyl) cyclopentadienyl) -5- (2,7-di-tert-butylfluorenyl) nonane (Compound L-5) (12.8 g, 23.8 mmol) ), Et<sub>2</sub>O (200 mL), a stir bar was added, and n-BuLi (10 M 5.3 mL in hexane, 53 mmol) was slowly added and cooled to -78 ° C. The mixture is warmed to room temperature, stirred overnight and then stirred in a pentane at 0 ° C via a cannula ZrCl.<sub>4</sub>Added to (5.5 g, 23.6 mmol). The mixture was warmed to room temperature, stirred for 7 days and evaporated to dryness. The residue was extracted with pentane, filtered and the filtrate was discarded. CH the remaining solid<sub>2</sub>Cl<sub>2</sub>The mixture was extracted with, filtered, and the filtrate was evaporated to dryness to give a red solid (7.8 g, 47% yield).<chemistry num="30"><img id="000033" he="67" wi="151" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
Dibutylmethidene {η<sup>5</sup>-[3- (Pent-4-enyl) cyclopentadiene-1-ylidene]} [η<sup>5</sup>-(2,7-di-tert-butylfluorene-9-iriden)] Synthesis of hafnium dichloride (C-3) Et<sub>2</sub>5- (3- (Pent-4-enyl) cyclopentadienyl) -5- (2,7-di-tert-butylfluorenyl) nonane dissolved in O (150 ml) (Compound L-5) To (14.6 g, 272.2 mmol), n-BuLi (2.5 M 26 mL in hexane, 65 mmol) was slowly added at 0 ° C. The mixture is warmed to room temperature, stirred overnight, then through a cannula with pentane (150 mL) and Et.<sub>2</sub>HfCl suspended in a mixture with O (20 mL)<sub>4</sub>It was added to (9.2 g, 28.7 mmol) at -78 ° C for 15 minutes. The mixture was warmed to room temperature, stirred for 2 days and evaporated to dryness. The residue was stirred in pentane (150 mL) and centrifuged. The supernatant was discarded. The remaining solid was extracted with methylene chloride and centrifuged. The solution was led to drying under vacuum to give a yellow solid (6.6 g, 31% yield).<chemistry num="31"><img id="000034" he="66" wi="151" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
(Examples 1 to 16) Metallocene, activator-carrier, and catalytic experiments with varying conditions Examples 1-16 in Table 1 show ethylene polymerization experiments performed in a 1 gallon (3.785 liter) stainless steel autoclave reactor at various temperatures using 2 liters of isobutane diluent and aluminum alkyl cocatalyst and scavenger. Shown. No hydrogen or comonomer was added. A metallocene solution (2 mg / mL) was usually prepared by dissolving 30 mg of metallocene in 15 mL of toluene. A typical polymerization procedure is as follows. The aluminum alkyl compound, the treated solid oxide, and the metallocene solution were usually added in this order through the filling port while releasing the isobutane vapor. The filling port was closed and 2 liters of isobutane was added. The contents of the reactor were stirred and heated to the desired experimental temperature (Table 1). Ethylene was supplied as needed to maintain a particular pressure for a particular length of the polymerization experiment. The reactor was maintained at the desired experimental temperature throughout the experiment by an automatic heating and cooling system.
After the allocated polymerization time, the ethylene flow was stopped and the reactor was slowly depressurized and opened to recover the granular polymer. In all cases, the reactor showed no wall scales, coatings or other forms of deposits and was clean. The polymer was then removed and weighed (Table 1).
<tables num="1"><img id="000035" he="191" wi="158" file="JP5774085B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>
51 sheets
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Every citation, both waysCites: the store holds 5 of 6
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| Helmut G. Alt, Michael Jung,Journal of Organometalic Chemistry,1998年,第229頁~第253頁 | Non-patent | – |
| Helmut G. Alt, Michael Jung, Gerald Kehr,Journal of Organometalic Chemistry,1998年,第153頁~第181頁 | Non-patent | – |
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Numbers
- Publication
- 5774085
- Publication, DOCDB
- 5774085
- Publication, EPODOC
- JP5774085B
- Application
- 264314
- Application, DOCDB
- 2013264314
- Application, EPODOC
- JP20130264314
Titles2
- Japanese
- 低レベルの長鎖分岐を有するポリマーを製造するための重合触媒
- English
- Polymerization catalysts for producing polymers with low levels of long chain branching
Classification
- CPC, 9
- C08F10/00
- C08F4/659
- C08F4/65916
- C08F4/65912
- C08F110/02
- Y10S526/943
- C08F2410/07
- C08F4/65
- C07F15/00
- IPC, 2
- C07C13 567
- C07F17 00
