Polymerization process for producing polyolefin elastomer, cation-generating cocatalyst for activating a metallocene procatalyst, polyolefin elastomer possessing a unique combination of properties and products manufactured therefrom

Description: TECHNICAL FIELD [Detailed description of the invention]

Polymerization method for producing polyolefin elastomer, metallocene procatalyst Polyolefin co-catalyst for activation, polyolephy with unique properties Elastomers and products made from them Background of the invention 1. Field of invention The present invention is a polyolefin elastomer (eg ethylene, propylene, etc.) Other α-olefins and, in some cases, derived from diene) Regarding the liquid phase polymerization method for this purpose, it can be used in the polymerization method. Utilizing metallocene procatalyst With respect to the cation-forming co-catalyst for sexualization, the desired polymer obtained thereby. Amount (M_w), High Mooney Viscosity (ML at 125 ° C)₁₊₄), Low polydispersity index (polydispersity index) (M_w/ M_n), Low glass transition temperature Degree (T_g) And polyolefin elast with low hysteresis (tan δ) Regarding the mars, and the hoses, belts and molded articles made from them. Polymers containing eel rubber articles, one or more other hydrocarbon polymers A blend, and a lubricant in which the elastomer acts as a viscosity modifier. Regarding various products to be included. 2. Description of prior art The most common polyolefin elastomers produced today are ethylene and pro. Binary copolymer (EP) with pyrene and ethylene, propylene and diene It is a former copolymer (EPDM). Normal EP elastomers are organic peroxides It can be cured with a hardener, but with sulfur as a hardener It is necessary to introduce diene. EPDM elastomers are usually vanadium-organic Manufactured using an aluminum catalyst, a Ziegler-Natta catalyst. Like the relatively well-known EP and EPDM polymers, the cost of propylene Instead 1-butene, 1-pentene, 1-hexene, styrene and their combinations Also ternary and ternary copolymers containing other α-olefins such as conjugations Also known. EPDMs are a more common category, ethylene-α -Olefin-Diene is a representative of elastomers (EODEs). EOD Among the Es, EPDMs have good weather resistance, acid resistance and high temperature and low temperature characteristics. It became famous because of its many properties that are desirable for the application it requires. Attention of EPDM Applications should include hoses, gaskets, power transmission belts, conveyor belts, Bumpers, automobile extrusions and molded products, gap closure, polypropylene, poly Bren for plastics and rubbers such as styrene and butyl rubber Made of components, fabric coatings, viscosity modifiers for lubricants, tire sidewalls, etc. In goods and roofing and other membrane applications, soles, heels and many other rubber articles Their use is included. Other notable uses of EPDMs are their excellence Due to its dielectric properties, it is used for wire and cable insulation. It is desirable for EPDM to have a reasonably fast cure rate and a high cure state. For that purpose, the diene content must be relatively high, for example 3% or more. There is a need. Curing rate of EPDM elastomer and final properties of cured product Depends on the type of diene added. For example, a comparable diene weight% group 5-Etylidene-2-Norbornene (ENB) as a diene when compared in quasi EPDM produced using dicyclopentadiene when using a sulfur hardener Than EPDM containing ethylene (DCPD) or 1,4-hexadiene (HD) Will have a rapid curing rate. Regarding the properties of cured EPDM, hexadiene was used as the termonomer. EPDMs produced in the above are known to exhibit good heat resistance. Elastomer For most commercial uses, EPDM is at least about 300,000 Weight average molecular weight (M_w) Or at least about 20 when expressed in Mooney viscosity ML at 125 ° C₁₊₄Must have. In many applications The molecular weight distribution (MWD) of EPDMs is about 7 or less, preferably about 5 or less. Ratio of weight average molecular weight to child weight (M)_w/ M_n), That is, characterized by a polydispersity index It is even more desirable to be. Tensile strength, workability and tack-like properties of EPDM elastomers Quality may be related to the degree of its crystallinity. For most commercial uses Since the molecular weight of the elastomer is higher than that of the plastic, the crystallinity is high. If it is too high, it can be difficult to process EPDM at normal temperatures. Good physics, especially in applications such as hoses, tubing, wires and cables Although the properties are desirable, if the crystallinity becomes too high, the hardness and rigidity of EPDM will increase. Higher and less surface viscosity (tack), "plastic" rather than "rubber" There is a risk of bringing about a surface. In general, ethylene, propylene and α-olefins with higher carbon atoms alone Commercially useful plastics, which are polymers and copolymers, are commercially useful. Molecules as high as elastomers of ethylene-α-olefins such as EPDM You don't have to have a quantity. Speaking of catalysts used for each, elastomer -Range M_wWhen a copolymer is produced with the composition of_wGives a highly plastic copolymer The catalyst is not suitable for use as an elastomer, M_wProduces a low polymer There are times. Similarly, unwanted MWD changes occur or composition distribution changes. There is a risk of That is, the performance of the catalyst for the production of plastics is It is not an indicator of catalyst performance for the production of elastomers. Traditionally high molecular weight EPDM elastomers in most current EPDM production The catalysts used in the production of V are combined with organoaluminum compounds. Cl₄, VOCl₃, VO (Ac)₃Or VO (OR)₃(In the formula, R is an alkyl group Is a soluble vanadium catalyst. Activity of such vanadium catalyst The property is relatively low, for example, producing 5 to 20 kg of polymer per 1 g of vanadium. To. In the current commercial grade of EPDM, the crystallinity is the ethylene content of the polymer. It depends on both the quantity and the catalytic system used for its production. Given With respect to the polymer composition, the catalyst system is capable of crystallizing with ethylene present for a long time. Control the part of the chillene unit. Polymerization in any given catalyst and reactor arrangement The body has a high ethylene content but has a long ethylene chain and is more crystalline. In current EPDM production based on vanadium catalysts, the product E PDM polymer is completely amorphous with an ethylene content of less than about 55% by weight (non-crystalline) Is. Conversely, at an ethylene content of about 55% by weight or higher, EPDM crystallizes significantly. Will have a degree. The degree of crystallinity is higher than the diene content of EPDM. Sensitive to the percentage of In order to make the catalytic system useful for the commercial production of EPDM elastics, Crystallization of the polymer of commercially available general purpose EPDM It is desirable to make it roughly comparable to the crystallinity. Metallocene catalysts typically address steric lesions It consists only of transition metal atoms sandwiched between ring structures to form. For metallocene catalyst The resulting plastics have high impact strength and toughness, and have good melting properties. , The transparency of the film tends to be improved. In practice, metallocene catalysts are present in traditional catalysts in polymer production. The extent to which it can replace the effect depends on the cost and efficiency of the system. Meta Rosen catalysts are considerably more expensive than traditional Ziegler-Natta catalysts, but The Tarosen system is highly productive. Ziegler-Natta catalyst metallocene touch Increased media productivity is tens to hundreds of times higher than the resulting polymer per pound of catalyst. In some cases. Recent polyethylene, polypropylene and chain low density polyethylene (LLDP) Alkenes for the production of copolymers of ethylene and α-olefins such as E) Since the introduction of the sun (aluminoxane) activated metallocene catalyst, these touches Considerable efforts have been made to apply the medium to the production of EPDM elastomers. Ta. For such applications, the catalyst is M_wAllows good control over a wide range of Reasonable polymerization time while enabling and producing a relatively narrow molecular weight distribution (MWD) After that, a high yield of EPDM is produced, and a diene monomer is appropriately added to the monomer. It is desirable to give an underground distribution. J.Poly.Sc., Vol.23, p2151 by Kaminsky et al. ~ 2164 (1985), metallocene-methylaluminoxane (MAO) tactile The medium weight is low molecular weight, i.e. not greater than about 150,000 M_wEPDM elast It is described to be used to produce mer. Long for such catalysts It requires a long reaction time and low yield, so it is practical for commercial EPDM production. Not the target. Similarly, Japanese Patent 62-121771 has a high ethylene content. Produces ethylene-1-butene-diene elastomer in low yield, with metallocene A catalyzed polymerization method is described. Use metallocene catalysts activated by aluminoxane such as MAO Other polymerization methods for producing EPDMs, characterized in that, are described, for example, in the United States. Xu No. 4,871,705, No. 5,001,205, No. 5,229,47 No. 8 and No. 5,442,020, EP347,129 and WO95 / It is described in No. 16716. Metallocene, as discussed in more detail below Catalysts have been widely commercialized for the production of high molecular weight elastomers Not active at least in part to acceptable levels of metallocene Because it is necessary to use a very large amount of aluminoxane co-catalyst to make it. To. EPA593,083 is a crosslinked metallocene catalyst (1):<img file="JP2000507635A_D0001.tif" /> Diphenylmethylene (cyclopentadienyl) (Fluolenil) Zirconium dichloride A gas phase polymerization method for producing EPDM using is described. However, vapor phase polymerization is for this type of producer of EPDM elastomers. Many that need to be overcome before the law is generally accepted in the industry It is easy to suffer from technical difficulties (some of these are clogged reactors). Metallocene for both EPA612,769 and EP653,445 Catalyst (1) chain low (molecular weight) propylene-diene elastomer (LLPDE) Although it is described that it is used in a solution polymerization method for the production of Molecular weight elastomers are the object of the present invention. U.S. Pat. No. 5,401,817 states a crosslinked metallocene catalyst (2):<img file="JP2000507635A_D0002.tif" /> Diphenylsilyl (cyclopentadienyl) (Fluolenil) Zirconium dichloride The polymerization method using is described. However, this patent does not mention the manufacture of elastomers. J. Chem. Soc. Dalton Trans., P by Green et al. Cross-linked metallocene catalysts in 657-665 (1994) (3):<img file="JP2000507635A_D0003.tif" /> Diphenylmethylene (cyclopentadienyl) (Indenyl) Zirconium dichloride The polymerization of propylene and styrene using is described. However, this publication mentions the production of elastomers. Not. Angew, Chem, Int. Ed. Engl. By Kaminsky et al. , 34 p2273-2275 (1995) with ethylene and bulky (bulky) ) Cross-linked metallocene catalyst for copolymerization with cycloalkenes (4):<img file="JP2000507635A_D0004.tif" /> Diphenylsilyl (cyclopentadienyl) (Indenyl) Zirconium dichloride Is listed with MAO. The other aspect of the invention is that all cross-linked metallocene catalysts are ultra-high molecular weight elastomers. The point is that we have discovered that we do not provide it. That is, for example, cyclopentane Only in the nature of the cross-linking group that binds the two ligands derived from tadienyl Cross-linked metallocene catalysts different from talocene (1)-(4):<img file="JP2000507635A_D0005.tif" /> Dimethylmethylene (cyclopentadienyl) (Fluolenil) Zirconium dichloride To give a low molecular weight (&lt;50,000) ethylene-propylene copolymer I understood. In contrast to this result and as found in the present invention Activated metallocene catalyst (1) is high molecular weight (&gt; 300,000) elast Give Mar. A rack with a bis (indenyl) structure and a bis (fluorenyl) structure, respectively. Bridge metallocene catalysts (6) and (7) have high molecular weight amorphous ethylene-propire Copolymers can be provided:<img file="JP2000507635A_D0006.tif" /> Racemic-dimethylsilyl bis (2-methylindenyl) Zirconium dichloride<img file="JP2000507635A_D0007.tif" /> Ethylene-crosslinked bis (fluorenyl) zirconium dichloride Metallocenes (6) and (7) are used in the production of homopolymers, U.S. Pat. No. 5,1 No. 45,819 (Indenil) and No. 5,436,305 (Fluolenil) )It is described in. Manufactures EPDM-type elastomers for both patents There is no mention of using the disclosed metallocenes to do so. As mentioned earlier, for the widespread commercial commercialization of metallocene catalysts. One of the obstacles to this is the use of aluminoxane as a co-catalyst. I'm wearing it. Alminoxane is expensive, and a large amount of aluminoxane is associated with it. Required to activate the Tarosen catalyst. Outline of the invention An object of the present invention is that the cross-linking group is activated with at least two bulky groups. Producing polyolefin elastomers using crosslinked metallocenes as catalyst compositions Liquid phase polymerization method for, i.e. solution or slurry conditions and batch or continuous Is to provide a way to do it. Another object of the present invention is to provide EODEs such as high molecular weight EPs and EPDMs. To provide, the above-mentioned polymerization method of olefins is provided. Yet another object of the invention is activation by a particular type of cation-forming cocatalyst. Catalytically active composition containing metallocene procatalyst To provide things. Further objects of the present invention include high molecular weight, high Mooney viscosity, low polydispersity index, and low gazing. Polyolefin elastomers that have both a lath transition temperature and low hysteresis Includes providing and then providing a variety of products manufactured. Elastomers are provided in maintaining these and other objectives of the invention. Ethylene, at least one other α-olefin and preferably less Liquid phase polymerization method of at least one diene monomer (this method is under liquid phase polymerization conditions) The monomer is (a) a metallocene procatalyst, preferably at least two bulky A catalyst containing a cross-linking group having a group and (b) a co-catalyst, preferably described below. Contains products obtained in combination with such cation-forming cocatalysts A step of contacting a catalytically effective amount of the catalytic composition) is provided. The polyolefin elastomer obtained by the method of the present invention is novel in itself. Known Polyolefin Elastomers that contain a corresponding amount of the same olefins Higher molecular weight (M) than their same properties in_w), High Mooney viscosity (12 ML at 5 ° C₁₊₄), Low polydispersity index (M)_w/ M_n), Low glass transition temperature (T_g) And low hysteresis (tan δ). These d Lastmers are then compared to the same product made from known elastomers Gives favorable properties to the manufactured product. The term "metallocene" as used herein. And "metallocene procatalyst" is transition metal M, less Ligand X from at least one non-cyclopentadienyl and zero or one he A compound having a terrorist atom-containing ligand Y (the above-mentioned ligand is coordinated to M and is numbered. It should be understood that it refers to (corresponding to its valence). Such compounds , To polymerize olefins to obtain polyolefin homopolymers and copolymers Useful aids in activating them to provide metallocene catalysts that can be used in Polymerization method using catalyst and / or one or more metallocene catalysts Is Among other things, listed in the following U.S. Patents: U.S. Pat. No. 4,752,597, No. 4,892,851, No. 4,931,417, No. 4,931,517 No. 4, No. 4,933,403, No. 5,001,205, No. 5,017, No. 714, No. 5,026,798, No. 5,034,549, No. 5,0 No. 36,034, No. 5,055,438, No. 5,064,802, No. No. 5,086,134, No. 5,087,677, No. 5,126,301 , No. 5,126,303, No. 5,132,262, No. 5,132,3 No. 80, No. 5,132,381, No. 5,145,819, No. 5,15 No. 3,157, No. 5,155,080, No. 5,225,501, No. 5 , 227,478, 5,229,478, 5,241,025, No. 5,243,002, No. 5,278,119, No. 5,278,26 No. 5, No. 5,281,679, No. 5,296,434, No. 5,304 , 614, 5,308,817, 5,324,800, 5,5, No. 328,969, No. 5,329,031, No. 5,330,948, No. No. 5,331,057, No. 5,349,032, No. 5,372,980 No. 5,374,753, 5,385,877, 5,391, No. 629, No. 5,391,789, No. 5,399,636, No. 5,4 01,817, 5,406,013, 5,416,177, No. 5,416,178, No. 5,416,228, No. 5,427,991 , No. 5,439,994, No. 5,441,920, No. 5,442,0 No. 20, No. 5,449,651, No. 5,453,410, No. 5,45 No. 5,365, No. 5,455,366, No. 5,459,117, No. 5 , 466,649, 5,470,811, 5,470,927, No. 5,477,895, No. 5,491,205 and No. 5,491, No. 207 (incorporated herein by reference to the contents of these patents). Brief description of drawings FIG. 1 shows within the scope of the present invention (Example 21) and outside the scope of the present invention (Comparative Example 30). Stability of metallocene procatalysts activated by both cation-forming cocatalysts The graph comparison shows that the stability of the catalyst is that of the consumed monomers over time. Shown as a quantity. Description of preferred embodiments The polymerization method in the present invention activates a metallocene procatalyst using an appropriate co-catalyst. The catalyst composition obtained by the above is used. Metallocene procatalysts are preferably of the following general formula: (Cp¹R¹_m) R³_n(Cp²R²_p) MX_q (I) (Cp¹R¹_m) R³_nY_rMX_s (II) One metallocene compound or a mixture of one or both metallocene compounds It is a thing (in the formula, the ligand (Cp)¹R¹_m) Cp¹And ligand (Cp²R²_p) Cp²Are the same or different cyclopentadienyl rings, R¹And R²Are German Halogen, a hydrocarbyl containing up to about 20 carbon atoms Calvir, hydrocarbyl-substituted organic metalloids or halocarbyl-substituted organic metaloids It is a Lloyd group, m is 0 to 5, p is 0 to 5, and the above-mentioned cyclope associated with each other. Two Rs on adjacent carbon atoms of the ntagenyl ring¹And (or) R²Substituent They may be bonded together to form a ring containing 4 to about 20 carbon atoms. R³Is a cross-linking group, n is 0 or 1, and Y contains a heteroatom coordinated to M. It is a ligand, M is a transition metal with a valence of 3-6, and each X is a non-cyclopentane. A tadienyl ligand that independently contains halogen or up to about 20 carbon atoms. Contains hydrocarbyl, oxyhydrocarbyl, halocarbyl, hydrocarbi Le Substituted Organic Metalloid, Oxyhydrocarbyl Substituted Organic Metalloid or Haroca It is a rubil-substituted organic metalloid group, where q is equal to the valence of M minus 2 and r is Has a value of n, where s is equal to the valence of M minus 1 when r is 0, and when r is 1. Equal to the valence of M minus 2). Methods for making these and other useful metallocene procatalysts are publicly available in the industry. It is knowledge and does not form part of the present invention. The metallocene procatalyst (I) is in aluminoxane or preferably It can be activated using the cation-forming cocatalyst described below. Meta If the Rosenpro catalyst is entirely of formula (II), use the above cation-forming cocatalyst. Is activated. However, the metallocene procatalyst is of formula (I). If the co-catalyst is all aluminoxane, then the ligand (Cp)¹R¹_m) Is the ligand (C p²R²_p) Must be different from the cross-linking group R³Has at least two bulky groups It must be contained and the value of n must be 1. These cross-linked meta Among the rosens, the cross-linking group R³Is the structure:<img file="JP2000507635A_D0008.tif" /> (In the formula, bulky group R⁴And R⁵Independently, up to about 20, preferably 6 ~ Approximately 12 carbon atoms and 0 to 3 oxygen, sulfur, tertiary nitrogen, boron or phosphorus A cyclohydrocarbyl group containing such a heteroatom, or containing the same group, And especially, cycloalkyl, heterocycloalkyl, cycloalkenyl, Haitai Locycloalkenyl, aryl, heteroaryl, alkaline, alkylhete Loaryl, aralkyl, heteroaralkyl, etc.), where M is titanium, di Luconium or hafnium, q is 2, and each X is a halogen. preferable. Within this preferred group of crosslinked metallocenes, ligands (Cp)¹R¹_m) Is an unsubstituted cyclo It is pentadienyl and is a ligand (Cp)²R²_p) Is indenyl or fluorenyl And M is zirconium and R⁴And R⁵Each of them is phenyl Cross-linked metallocenes in which each X ligand is chlorine are even more preferred. One of these Layer-preferable metallocenes correspond to the above-mentioned known metallocene compounds (1) to (4). .. Yet another preferred crosslinked metallore that can be used in the polymerization method of the present invention. For Sen (I), Diphenylmethylene (indenyl) (fluorenyl) zirconium dichlorite Do, Diphenylmethylene (cyclopentadienyl) (4,5,6,7-tetrahydro Loindenyl) Zirconium dichloride, Diphenylmethylene (cyclopentadienyl) (2-methylindenyl) zill Conium dichloride, Diphenylmethylene (2,4-dimethylcyclopentadienyl) (3', 5' -Dimethylcyclopentadienyl) zirconium dichloride, Diphenylmethylene (2-methyl-4-tert-butylcyclopentadieni) Le) (3'-tert-butyl-5'-methylcyclopentadienyl) zirconi Umjikuroride, Dixysilylmethylene (2,3,5-trimethylcyclopentadienyl) (2' , 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, Dixysilylmethylene (2,4-dimethylcyclopentadienyl) (3', 5' -Dimethylcyclopentadienyl) zirconium dichloride, Dixysilylmethylene (2-methyl-4-tert-butylcyclopentadieni) Le) (3'-tert-butyl-5-methylcyclopentadienyl) zirconiu Music Ride, Dixysilylmethylene (cyclopentadienyl) (fluorenyl) zirconium Dichloride, Di-o-trilmethylene (cyclopentadienyl) (3,4-dimethylcyclo Pentazienyl) Zirconium dichloride, Di-o-trilmethylene (cyclopentadienyl) (3,4-dimethylcyclo Pentazienyl) Zirconium dichloride, Di-o-trilmethylene (cyclopentadienyl) (3,4-dimethylcyclo Pentazienyl) Zirconium dichloride, Di-o-trilmethylene (cyclopentadienyl) (indenyl) zirconiu Music Ride, Dibenzylmethylene (Cyclopentadienyl) (Tetramethylcyclopentadi) Enil) Zirconium dichloride, Dibenzylmethylene (Cyclopentadienyl) (Indenyl) Zirconium Di Chloride, Dibenzylmethylene (cyclopentadienyl) (fluorenyl) zirconium Dichloride, Dicyclohexylmethylene (cyclopentadienyl) (indenyl) zirconi Umjikuroride, Dicyclohexyl (cyclopentadienyl) (fluorenyl) zirconium di Chloride, Dicyclohexylmethylene (2-methylcyclopentadienyl) (fluoreni) Le) Zirconium dichloride, Diphenylsilyl (2,4-dimethylcyclopentadienyl) (3', 5'- Dimethylcyclopentadienyl) zirconium dichloride, Diphenylsilyl (2,4-dimethylcyclopentadienyl) (3', 5'- Dimethylcyclopentadienyl) zirconium dichloride, Diphenylsilyl (2,3,5-trimethylcyclopentadienyl) (2,4 , 5-trimethylcyclopentadienyl) zirconium dichloride, Tetraphenyl disilyl (cyclopentadienyl) (indenyl) zirconiu Music Ride, Tetraphenyldisilyl (3-methylcyclopentadienyl) (Indenyl) Zirconium dichloride, Tetraphenyldisilyl (cyclopentadienyl) (fluorenyl) zirconi Umjikuroride, Di-o-tolylsilyl (cyclopentadienyl) (trimethylcyclopentadienyl) Enil) Zirconium dichloride, Di-o-tolylsilyl (cyclopentadienyl) (tetramethylcyclopenta) Dienyl) Zirconium dichloride, Di-o-tolylsilyl (cyclopentadienyl) (3,4-diethylcyclope) Ntagenil) Zirconium dichloride, Di-o-trilsilyl (cyclopentadienyl) (triethylcyclopentadi) Enil) Zirconium dichloride, Dibenzylsilyl (cyclopentadienyl) (fluorenyl) zirconium di Chloride, Dibenzylsilyl (cyclopentadienyl) (2,7-di-t-butyl-full) Olenyl) Zirconium dichloride, and Dicyclohexylsilyl (cyclopentadienyl) (fluorenyl) zirconi Umjikuroride, Is included. In the preferred metallocene procatalyst of formula (II), both n and r are 1 , M has a valence of 4, X is a halogen, and s is 2. Main departure Such a preferred mechanism that can be activated by a bright cation-forming cocatalyst. Examples of Tarosenprocatalyst (II) are: Dimethylsilyl (Tetramethylcyclopentadienyl) (Cyclohexylami) D) Zirconium dichloride; Didimethylsilyl (3,4-dimethylcyclopentadienyl) (cyclohexyl) Amide) Hafnium dichloride; Dimethylsilyl (tetramethylcyclopentadienyl) (butyramide) tita Nium dichloride; Dimethylsilyl (3,4-di-t-butylcyclopentadienyl) (cyclodo) Decylamide) Titanium dichloride; Dimethylsilyl (2,5-dimethylcyclopentadienyl) (cyclododecyl) Amide) Titanium dichloride; Di-n-propylsilyl (2,5-dimethylcyclopentadienyl) (pn) -Butyl-Phenylamide) Titanium Dichloride; Di-isopropylsilyl (2-indenyl) (cyclohexylamide) zirco Niumji halide; Diphenylsilyl (Tetra-n-propylcyclopentadienyl) (isopro Pyramide) Zirconium dihalide; and Dimethylmethylene (2-methyl-5-t-butylcyclopentadienyl) (di Methylamide) Zirconium dihalide. A co-catalyst used with the preferred crosslinked metallocene procatalyst of formula (I), i.e. active Sexing agents are known to activate metallocene procatalysts, as mentioned earlier. It may be any aluminoxane that exists. Alkyl aluminum tree like MAO For more details on aluminoxane cocatalysts, including suns, see, for example, the United States. See Patent No. 5,227,478. In general, cross-linked metallocene procatalysts have a transition. Expressed by metal transfer content, about 0.0001 to about 0.02 mmol / liter, Preferably from about 0.0002 to about 0.015 mmol / liter, more preferably Is present in the reactor in an amount of about 0.0002 to about 0.01 mmol / liter. Rukoto can. Corresponding to these amounts of transition metals, aluminoxane cocatalysts are about 0.01 to about 100 mmol / liter, preferably about 0.02 to about 75 millimo Le / liter, more preferably about 0.025 to about 50 mmol / liter Can be used in. Cross-linked metallocene procatalyst and aluminoxane co-catalyst Optimal levels of are selected specific pro-catalysts and co-catalysts as well as other variations of the polymerization method. It will of course be recognized that it depends to some extent on the factors that move it. Proper activation of metallocene procatalysts when using alminoxane cocatalysts Trimethylaluminum to reduce the amount of aluminoxane needed for Nium, triethylaluminum, tri (n-propyl) aluminum, trii Sopropylaluminum, tri (n-butyl) aluminum, triisobutyla It is advantageous to include trialkylaluminum such as luminium etc. obtain. In general, any trialkylaluminum can be used with respect to metallocene procatalysts. It can be used in a molar ratio of about 1 to about 1000, preferably about 2 to about 500. To. However, preferably, a cationic co-catalyst having the composition described below is used. Used to activate Tarosenpro catalysts (I) and (II). This preference The co-catalyst is not only the above-mentioned preferable cross-linked metallocene, but also with or without cross-linking. Partial replacement of aluminoxane for any metallocene procatalyst Or it can be used as a complete replacement, and the present invention relates to this as well. It is. More specifically, the cationic co-catalyst of the present invention is used as the first component. Independently water at least one X ligand in the metallocene procatalyst to all of them Carbohydryl groups containing elementary atoms or up to 20 carbon atoms or 20 Metals that can be exchanged for oxycarbohydryl groups containing up to carbon atoms And (or) metalloid-containing compounds, at least one electron as the second component Neutral metals with at least one aryl group with child-attractive substituents and ( Or) a metalloid-containing compound, and at least one electron request as a third component Anionic metals with at least one aryl group with an attractive substituent and (Or) Contains metalloid-containing compounds. Activation of the metallocene procatalyst can be done simultaneously or at any time interval. By sequentially combining metallocenes with the above components of the cation-forming cocatalyst Can be achieved. In-situ activity of procatalysts for the reasons described below Chemicalization, i.e., activation in the polymerization reactor in the presence of the monomer is preferred. But However, in other ways, for example, the metallocene procatalyst is reacted with the first component of the co-catalyst. The product of this reaction is then placed in an olefin monomer or an olefin monomer. Combined simultaneously or sequentially with the second and third components of the co-catalyst in the absence of It is also within the scope of the present invention to thereby achieve activation of the procatalyst. Generally, the molar ratio of the first component of the cocatalyst to the metallocene procatalyst is 1 to about 500. , Preferably about 2 to about 500, as opposed to metallocene procatalysts The molar ratio of the second and third components of the co-catalyst to be independently is about 0.5 to about 10, which is preferred. It can be changed from about 0.8 to about 5. Contains a metal or metalloid to obtain a cationic co-catalyst in the present invention The first component is advantageously the general formula AlR⁴R⁵R⁶(In the formula, R⁴, R⁵And R⁶Is it Hydrocarbyl groups (eg, alkyl) each independently containing up to about 20 carbon atoms ) Or an oxyhydrocarbyl group (eg, alkoxy) or hydrogen, but with R⁴, R⁵And R⁶Is an aluminum compound (where two or less of the groups can be hydrogen) obtain. Suitable aluminum compounds include trimethylaluminum and triethyla. Luminim, tri (n-propyl) aluminum, triisopropyl aluminum , Tri (n-butyl) aluminum, tri (n-propyl) aluminum, tri Isobutylaluminum, tri (n-hexyl) aluminum, tri (n-oct) Chill) Aluminum, dimethylaluminum hydrogenated, diethylaluminium hydrogenated , Diisopropylaluminum hydride, di (n-propyl) aluminium hydrogenated Diisobutylaluminum hydride, di (n-butyl) hydrogenated Minium, dimethylaluminum ethoxydo, di (n-propyl) aluminum Ethoxide, diisobutylaluminum ethoxide, di (n-butyl) aluminum Ummethoxydo, etc. are included. Among the above aluminum compounds, Trialchi Lualuminums are preferred, among which triethylaluminium and triethylaluminum are preferred. Liisobutylaluminum is more preferred. Used as the first component of co-catalyst Additional representative compounds that can be used are alkali metals, organometallics, alkaline earths, etc. Organometallics and organometallic halides (eg Grignard reagents), the like Hydrocarbyl complexes of metals such as boron, zinc, gallium, germanium, arsenic It is a hydrocarbyl complex of organic metalloids such as element, tellurium, mercury, and lead. A second component useful for obtaining a preferred cocatalyst is tris (pentafluorof). Enil) borane, tris (methoxyphenyl) borane, tris (trifluorome) Chil-phenyl) borane, tris (3,5-di [trifluoromethyl] phenyl ) Borane, Tris (Tetrafluoroxylyl) Borane, Tris (Tetrafluoro) -o- Trill) Includes boranes such as boranes. Among the above boranes, Tris (pentafluorophenyl) borane and tris (3,5-di [triflu] Oromethyl] phenyl) borane is preferred. Other useful second components include the above compounds Includes aluminum homologues. A specific third component that can be used in a preferred cocatalyst is lithium. Tetrakis (pentafluorophenyl) borate, lithium tetrakis (trif) Luolomethylphenyl) borate, lithium tetrakis (3,5-di [triflu] Oromethyl] Phenyl) Borate, Sodium Tetrakis (Pentafluorofe) Nyl) borate, potassium tetrakis (pentafluorophenyl) borate, ma Gnesium Tetrakis (Pentafluorophenyl) Borate, Titanium Tetra Kiss (pentafluorophenyl) borate, tin tetrakis (pentafluorofe) Includes borates such as nyl) borate, etc. Among the above borates, lithium Mutetrakis (pentafluorophenyl) borate and lithium tetrakis ( Alkali metal boron such as 3,5-di [trifluoromethyl] phenyl) borate Acid salts are preferred. Another useful third component is the aluminate homologue of the above compound. included. The activated metallocene catalyst composition is prepared in advance and then introduced to the polymerization reactor. You can enter. However, the preferred cation-forming cocatalyst described above is used. When used, the co-catalyst component is used on the spot, i.e. in the presence of the monomer. It is highly preferred to activate the environment catalyst. Is such activation on the spot? There are some advantages. Metallocene procatalysts in which each X ligand is a halogen are fairly stable compounds No special handling or storage requirements are required. However, one or more Metallocenes whose X ligand is a hydrogen atom or a hydrocarbyl group are oxygen and water. Very susceptible to deterioration when exposed to light and / or heat. Prepare in advance If so, store these metallocenes in a way that eliminates all of these conditions. You have to be careful. This is extremely unstable metallocene This is especially true for hydrides. For this reason, in the presence of monomers It is preferable to activate the metallocene procatalyst in the polymerization reactor with a preferred co-catalyst. I. Activation of the procatalyst in this way forms a catalytically inert degradation product. Avoid or greatly reduce the possibility of In-situ activation of metallocene procatalysts still has other significant advantages. Su That is, according to in-situ activation, for example, reactive sweeping of polar impurities. Aluminiu in co-catalyst through (reactive scavenging) The flexibility to adjust the treatment conditions in the polymerization reactor can be obtained by adjusting the amount of the polymer component. Pre-generated metallocene hydrides, hydrocarbyls or oxyhydrs With locals, as if to represent the complications of the polymerization method, Scavengers will need to be supplied separately. Also, olefin monomas When activated in the presence of-, it was activated before it was introduced into the polymerization reactor. It was observed here that it produced significantly higher initial polymerization activity than the same catalyst. .. Α-Oref suitable for use in the production of elastomers in the present invention Inns contain 3 to about 20 carbon atoms, propylene, 1-butene, 3-meth. Chilbutene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-o Kuten, 1-decene, 1-dodecene and styrene, α-methylstyrene, etc. Α-olefins containing vinyl aromatic monomers, with propylene being particularly preferred. Is. The diene monomer (s) used as desired is conjugated. It may be unconjugated or non-conjugated. Butadiene and isoprene are used as conjugated monomers. , 2,3-Dimethylbutadiene and cyclopentadiene are included. Examples of suitable non-conjugated diene are 1,4-hexadiene, 1,5-hexadiene. , 1,6-heptadiene and 1,7-octadien. , 4-Methyl-1,5-hexadiene, 5-methyl-1,4-hexadiene , 3,7-dimethyl-1,6-, octadiene, 3,7-dimethyl-1,7-o Like mixed isomers of kutadiene and dihydromilsen with dihydroosimene Branched chain acyclic dienes, 1,4-cyclohexadiene, 1,5-cyclooctadi Dienes and unsubstituted and substituted ring-type diene such as 1,5-cyclododecadiene , And tetrahydroindene, methyltetrahydroindene, dicyclopenta Diene, bicyclo- (2,2,1) -hepta-2,6-diene-like polycyclic diene Ens, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene , 5-Propenil-2-Norbornene, 5-Isopropyriden-2-Norbornene , 5-Butenyl-2-norbornene, 5- (4-cyclopentenyl) -2-No Lubornen, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-no Alkenyl, alkylidene, sik, such as rubornen and norbornadiene Includes loalkenyl and cycloalkylidene norbornenes. EODE Of the diene typically used to make, the preferred ones are 1,4-hexes. Sazien, 5-Etylidene-2-Norbornene, 5-Viniliden-2-Norbornene Nen, 5-methylene-2-norbornene and dicyclopentadiene. Among them, 5-ethylidene-2-norbornene, 1,4-hexadiene and Dicyclopentadiene is more preferred. Even if it occurs in the product elastomer, it causes almost no branching. Such as 1,4-hexadiene, ethylidene-2-norbornene, disic Dienes such as lopentadiene, 1-methylcyclopentadiene, indene, etc. When using, it is possible to include a branching diene in the monomer mixture. It can be advantageous for the properties of the product elastomer. So-called branching diene Types include 1,5-hexadiene, 1,7-octadien or 4-methyl-1, Cyclopentadi, a branched or non-branched acyclic diene such as 5-hexadiene En, 3-methyl-1,4-cyclopentadiene, vinylcyclohexene or Substituted or unsubstituted cyclic dienes such as norbornadiene, 5-methylene-2- Norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene Alkenyl substitution norbornene such as nen or 5-butenyl-2-norbornene Conjugated, such as butadiene, isoprene or 2,3-dimethylbutadiene Acyclic dienes, and dialkenyl aromatic diene such as divinylbenzene Is included. Preferred elastomeric ethylene-α-olefin copolymers and EODE Classes are up to about 90% by weight, preferably about 30 to about 85% by weight, more preferably It can contain about 35 to about 80% by weight of ethylene, and the rest is α-olefin. (1 or more) and optionally diene monomers (1 or more) To. When diene monomer (1 or more) is used, about 0.1 to about 3 0% by weight, preferably about 1 to about 25% by weight, more preferably about 1 to about 20% by weight Can be included in EODE at the% level. The polymerization of the above-mentioned monomers using the catalyst of the present invention is a liquid in a continuous or batch manner. It is carried out in phase, i.e. by the solution method or the slurry method. These methods are generally about At temperatures in the range of -20 ° C to about 300 ° C, preferably in the range of about 0 ° C to about 200 ° C. It is performed at a pressure of about 5 to about 2000 psig. To a diluting solvent that can be used Like butanes, pentanes, hexanes, heptanes, octanes, etc. Linear and branched hydrocarbons, cyclopentane, cyclohexane, cyclohepta , Methylcyclopentane, methylcyclohexane, methylcycloheptane, etc. Cyclic and alicyclic hydrocarbons such as and toluene, xylene, etc. Includes Lucil-substituted aromatic compounds. A typical batch solution polymerization method involves first using a hydrocarbon solvent such as cyclohexane. This can be done by introducing it into a stirring tank reactor. Next, ethylene, α- Olefin (eg, propylene) and diene (if used) (one or more) Is sprayed into the liquid phase with a monomer feed material containing (multiple types). Next, the required amount of co-catalyst Hydrocarbon solution, followed by a metallocene pro-catalyzed hydrocarbon solution in the liquid phase of the reactor. Add. The rate of polymerization is controlled by the concentration of the catalyst. Reactor temperature is cold Controlled by a rejection coil, etc., the initial total pressure in the reactor is a gaseous monomer ( It is maintained by flowing a certain amount of one or more species). Gas in the reactor (1 type By keeping the flow rate of (or more than one) faster than the rate of polymerization, the reactor The conditions inside should approach steady-state conditions. Elastomer product containing ethylene A significant amount of ethylene vs. α-olefins in the metallocene catalysts and reactors used. Determined by the ratio. The latter is the relative rate of supply of these monomers into the reactor. It is controlled by adjusting. Polymerization and catalyst inactivation followed by After agglomeration of the elastomer, the elastomer is recovered by any suitable means. , Can be further processed if desired. In the slurry polymerization method, ethylene, α-olefin (one or more), Diene (s) and components of the catalyst composition used as desired A suspension of a solid granular polymer is formed in the hydrocarbon diluent to which the above is added. Slurry polymerization proceeds in much the same way as solution polymerization. Preferred polyolefin elas that can be obtained by the polymerization method in the present invention. Stormers have a high molecular weight (M), which is different from known polyolefin elastomers._w), High Mooney Viscosity (ML₁₊₄), Low polydispersity index (M)_w/ M_n), Low glass Transition temperature (T_g) And low hysteresis (tan δ) Have a combination. The novel polyolefin elast of the present invention before curing Mar is about 200,000 to about 2,000,000, preferably about 275,00 0 to about 1,750,000, more preferably about 300,000 to about 1,500 , 000 M_w, About 10 to about 200, preferably about 15 to about 175, even more preferred ML at 125 ° C of about 20 to about 150₁₊₄, About 1.25 ~ about 10, preferred Or about 1.5 to about 8.5, more preferably about 2.0 to about 7.5 M_w/ M_n,about T less than -25, preferably less than about -30, more preferably less than -35_g(° C ) And about 0.3 to about 7, preferably about 0.35 to about 6, more preferably about 0. It has 4 to about 5 tan δ. These advantageous properties can be useful in a variety of products. That's right Therefore, the elastomer according to the present invention is compatible with elastomers such as EPDMs. One or more known hydrocarbon polymers, such as Poly (α-olefin) homopolymers and copolymers, polystyrene, ethylene / Cycloolefin copolymer, butyl rubber, polyisoprene, polybutadiene, etc. A polymer blend containing the above can be prepared. The elastomer in the present invention , Hoses, pipe materials, V-belts, conveyor belts, toothed belts (timing) Belts) and power transmission belts including industrial flat belts, air springs, roof wipes Material, windbreak (gap closure), girder pipe (bushing, bearing), shaking table, bridge bearing Jacketing for pads, soles, heels, wires or cables Included in any of a wide range of rubber articles such as (jacketing), etc. Can be done. The elastomer of the present invention also exists as a viscosity modifier for lubricating oils. For. To facilitate the production of polymer blends, the elastomers of the present invention are carbonized by other means. Provided as an oil-enhanced (spread) polymer before mixing with the hydrogen polymer Can be done. The elastomer of the present invention is used after the polymer is recovered from the polymerization reactor. The amount of oil can be increased (spread) by the well-known method of adding oil. The oil is typically about 5 to about 1 oil per 100 parts by weight of elastomer. You can choose from naphthenic or paraffinic oils in an amount of 50 parts by weight You can. Alternatively, blending of elastomers and other hydrocarbon polymers You can also add some or all of the oil during the production. The elastomer of the present invention is one of a number of common formulation ingredients, such as one. Or for vulcanization containing more vulcanizers, accelerators, activators, retarders, etc. Can be formulated in a known manner using a hardener package. Other normal arrangement Combined ingredients include ozone degradation agents, antioxidants, plasticizer oils and softeners, Includes fillers, strengthening pigments and carbon black. Example: The following examples are examples of the present invention (Examples 1 to 27) and known polymerization methods. Examples of examples of catalysts and elastomers (Comparative Examples 1-48) are included. these Procatalysts, MAO co-catalysts, cation-forming co-catalyst components used in the example of , The solvents and monomers are: 1. Bis (cyclopentadienyl) zirconium dichloride [Cp₂ZrCl₂] 2. Diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconi Umjichloride [Ph₂C (Cp-9-Flu) ZrCl₂] 3. Diphenylsilyl (cyclopentadienyl) (fluorenyl) zirconiu Musico Ride [Ph₂Si (Cp-9-Flu) ZrCl₂] 4. Diphenylmethylene (cyclopentadienyl) (indenyl) zirconiu Musico Ride [Ph₂C (Cp-9'-Ind) ZrCl₂] 5. Diphenylsilyl (cyclopentadienyl) (indenyl) zirconium Dichloride [Ph₂Si (Cp-9'-Ind) ZrCl₂] 6. Dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconiu Music Ride [Me₂C (Cp-9-Flu) ZrCl₂] 7. Racemic-dimethylsilylbis (2-methylindenyl) zirconium di Chloride [rac-Me₂Si (2-Me-Ind)₂ZrCl₂] 8. Dimethylsilylbis (Cyclopentadienyl) Zirconium Dichloride [Me₂Si (Cp)₂ZrCl₂] 9. Dimethylsilylbis (fluorenyl) zirconium dichloride [Me₂Si (Flu)₂ZrCl₂] 10. Racemic-Ethylene Bis (Indenyl) Zirconium Dichloride [Rac-Et (Ind)₂ZrCl₂] 11. Racemic-Dimethylsilylbis (Indenyl) Zirconium Dichloride [Rac-Me₂Si (Ind)₂ZrCl₂] 12. Racemic-Ethylene Bis (Indenyl) Hafnium Dichloride [Rac-Et (Ind)₂HfCl₂] 13. Racemic-Dimethylsilylbis (Indenyl) Hafnium Dichloride [Rac-Me₂Si (Ind)₂HfCl₂] 14. Dimethylsilyl (tetramethylcyclopentadienyl) (t-butylami) De) Titanium dichrolide [Me₂Si (Cp^*) (NBu^t) TiCl₂] 15. Tris (pentafluorophenyl) borane [B (C₆F₅)₃] 16. Trityl Tetrakis (Pentafluorophenyl) Borate [Ph₃CB (C)₆F₅)₄] 17. Dimethylanilinium tetrakis (pentafluorophenyl) borate [HNMe₂PhB (C₆F₅)₄] 18. Lithium Tetrakis (Pentafluorophenyl) Borate [LiB (C)₆F₅)₄] 19. Methylaluminoxane [MAO] 20. Triisobutylaluminum [Al (Buⁱ)₃], 25 weight in hexane % Al, 0.86M Al The hexane solvent was purified on 3Å molecular sieves. Toluene solvent is molten natriu Distilled from flatulence and degassed with dry deoxygenated argon. Both are highly Pure grade monomers, ethylene and propylene, are molecular sieves and It was purified by passing it over an oxygen scavenging catalyst. Diene monomer 5- Ethylidene-2-norbornene [ENB], dicyclopentadiene [DCPD] , 5-Vinyl-2-Norbornene [VNB] and 1,7-Octadiene [OD ] Is deinhibited on activated alumina and 4Å molecular sieves Stored on. The properties of the elastomer were determined using the following method. Weight average molecular weight (M_w), Molar mass distribution (M_n) And (M_w/ M_n) Molecular weight of elastomer (M_wAnd M_n) Is Waters RA401 Refractive Index Meter and Waters Styragel HT column (10E 5 Å, 10E Waters GPC 1 with 4 Å, 10E3 Å and 10E6 Å) Measured in ordichlorobenzene at 130 ° C on 50C gel permeation chromatography I decided. Molecular weight is American Polymer Standards Polystyrene standard from Corp. (narrow molecular weight distribution, M_n9300 ~ 2. 1x10⁶) Was calculated from the calibrated elution time. Mooney viscosity (ML at 125 ° C)₁₊₄) Mooney viscosity of elastomers (ML at 125 ° C)₁₊₄) Is ASTM standard D1 According to 646 Monsanto Mooney Viscometer Measured on a Dell MV2000. Glass transition temperature (T_g) Glass transition temperature of elastomers (T_g) Is molded at 150 ° C for 15 minutes, Next, run for 20 to 25 mg of the polymer annealed at room temperature for 24 hours. It was measured by measuring the amount of heat. T_gIs a Perkin Elmer DS Sample heating curve recorded in C7 differential scanning calorimetry (heating rate of 20 ° C / min) Report as the midpoint of the glass transition above (from -100 ° C to 180 ° C). Hysterichs (Tan δ) Elastomer Hysteresis (tan δ: ASTM Standard D945) Monsanto Rubber Process Analyzer model Calculated using RPA2000, frequency of 0.25 rad / sec and 1 ° arc vortex Report as the average of 10 measurements taken at 150 ° C only (14%). Ethylene: propylene ratio and diene content Ethylene: propylene ratio and diene content of elastomers are ASTM standards Perkin-Elmer Infrared Spectrometer Model According to D3900 Infrared spectroscopy of thin polymer film on Paragon 1000 PC I asked for it. General solution polymerization method (using MAO co-catalyst) A Weigh the metallocene procatalyst into a hypovial. It was mixed vigorously under Lugon with a suitable aliquot of MAO solution. Gain The catalyst solution was aged for 30 minutes before use. In one polymerization operation 0.056 grams (100 micromoles) of diphenylmethylene (cyclopentane) Dienyl) (Fluorenyl) Zirconium Dichloride [Ph₂C (Cp-9- Flu) ZrCl₂] Was reacted with 40.0 ml of MAO solution. This is Zr = A catalytic solution with an Al / Zr ratio of 2.0 mM and 1250 was produced. Then in a 2 liter glass reactor 1500 ml hexane, 1.2 ml Al (Buⁱ)₃(Equivalent to 1.0 mmol Al), a suitable aliquot of diene and 50 psi each of ethylene and propylene (quality measured on a rotor meter) Volume flow rate ratio) was charged and thermally equilibrated. The catalytic solution was then injected into the reactor. Maintain reactor pressure at 50 psi Ethylene and propylene were supplied as needed. 100 ml of acidified metano Polymerization was stopped using all (1 volume% concentrated HCl) and the obtained polymer was condensed. After that, it was mill-dried. General solution polymerization method (using a cation-forming cocatalyst) B 1500 ml hexane, 1.2 ml in a 2 liter glass reactor Al (Buⁱ)₃(1.0 mmol Al), an appropriate amount of diene aliquot and 50 psi each of ethylene and propylene (quality measured on a rotor meter) Volume flow rate ratio) was charged and thermally equilibrated. Catalyst, Ph₂C (Cp-9-Flu ) ZrCl₂1.0 ml (0.056 g, in 10 ml toluene) of 10 mM solution of Inject 100 micromoles into the reactor and Al (Bu) for 2 minutesⁱ)₃Reacted with .. The remaining components of the co-catalyst (eg, B (C) in 10 ml of toluene₆F₅)₃(0.102 g, 100 micromoles) and LiB (C)₆F₅)₄(0.152g, 100m Ichromol) 10 mM solution 1.0 ml) was injected into the reactor. Ethylene and And propylene was supplied to 50 psi as needed to maintain reactor pressure. Stop the polymerization with 100 ml of acidified methanol (1 volume% concentrated HCl) and The resulting polymer was condensed and then mill-dried. The polymer product was analyzed by IR spectroscopy to determine the E: P ratio and diene content. I asked. Also, for most samples, the molecular weight (M)_w), Thermal transfer (DSC), Mooney viscosities at tan δ and 125 ° C were determined. The specific polymerization conditions and physical properties of the obtained polymer for each example will be described later. It is summarized in Tables 1-6. Comparative Example 1-19 Using the above solution polymerization method A, several MAO activities in which the cross-linking group lacks bulky groups EP and EPDM-type elastomers using chemical cross-linked metallocene catalysts Was prototyped. The conditions of each polymerization and the characteristics of the obtained polymer are shown below in Table 1. To summarize. Table 1: Comparative examples 1 to 19 A. Polymerization conditions and results<img file="JP2000507635A_D0009.tif" /> Table 1A (continued) <img file="JP2000507635A_D0010.tif" />* Added to reduce the ratio of MAO / Zr and MAO / Hf. Table 1 (continued) B. Polymer properties<img file="JP2000507635A_D0011.tif" /> Table 1B (continued) Comparison<img file="JP2000507635A_D0012.tif" /> As these data show, zirconium-based metallocene catalysts Comparative Examples 1 to 3 and 7 to 9 exemplifying the use of the above produced polymers with low Mooney viscosities. Comparative Examples 4-6 exemplifying the use of hafnium-based metallocene catalysts and 10-12 showed unacceptably low activity. Used in Comparative Examples 1 to 13 All of the catalysts showed relatively low activity against propylene. Comparative Examples 13 ~ 18 Produced only ternary copolymers, not ternary copolymers. Diene introduction This is because the ban on diene was observed. Comparative Example 19 showed low catalytic activity. The resulting elastomer had a low Mooney viscosity. Examples 1 to 3 Using the above solution polymerization method A, MAO-activation in which the cross-linking group has two bulky groups Elastomers were produced using crosslinked metallocene catalysts. Conditions of each polymerization and The properties of the obtained elastomer are summarized in Table 2. Table 2: Examples 1 to 3 A. Polymerization conditions<img file="JP2000507635A_D0013.tif" /> Table 2: A. (continued), B. Polymerization results <img file="JP2000507635A_D0014.tif" />* Added to reduce the MAO / Zr ratio. Table 2 (continued): B. Polymerization results and polymer properties <img file="JP2000507635A_D0015.tif" /> Table 2 B. (continued) Implementation Example tan δ comment 1 High MAO / Zr required for good results without measurement 2 High MAO / Zr required for good results without measurement 3 High MAO / Zr required for good results without measurement In these examples, the yield was high and a good E: P ratio was consistently achieved. Ta. In Examples 2 and 3, the diene was successfully introduced into the polymer and EPDM. An elastomer was obtained. All elastomers showed good properties. Example 1 ~ 3 is also typical of MAO for metallocenes needed for good results It shows a high ratio. Examples 4-9 The polymerization methods used in these examples are used in Examples 1-3. Certain properties of EPDM-type elastomers that can be similar to the above method, Especially those Mooney viscosities, M_w, M_w/ M_nAnd for branching to tan δ values Intended to show the beneficial effects of using additional diene monomers as agents To do. Table 3 summarizes the conditions of each polymerization and the properties of the obtained polymer. .. Table 3: Examples 4-9 A. Polymerization conditions<img file="JP2000507635A_D0016.tif" /> Table 3: A. (continued) <img file="JP2000507635A_D0017.tif" /> Table 3 (continued) B. Polymerization results and polymer properties<img file="JP2000507635A_D0018.tif" /> Table 3: B. (continued) <img file="JP2000507635A_D0019.tif" /> Table 3: B. (continued) Example comment 4 High MAO / Zr required for good results 5 High MAO / Zr required for good results 6 High MAO / Zr required for good results 7 High MAO / Zr required for good results 8 High MAO / Zr required for good results 9 High MAO / Zr required for good results Use a MAO / metallocene ratio that is twice the MAO / metallocene ratio of Examples 8 and 9. Examples 4-7 used show much higher yield and activity than Examples 8 and 9. And this is also a very high MAO to achieve optimal processing results. It shows that it is necessary to use the Tarosen ratio. Are Examples 5-9 branches? Elastomer of Example 4 that does not contain diene for branching when diene for branching is introduced Compared to the Mooney viscosity of each elastomer, M_w, M_w/ M_nAnd (measurement (If done) Indicates that the tan δ value has improved. Comparative Examples 20 to 23: Examples 10 to 19 Using the above solution polymerization method B, the cross-linking group has two bulky groups, which is the category of the present invention. Both within the enclosure (Examples 10-19) and outside the scope of the invention (Comparative Examples 20-23) EPDM elastomers for metallocene catalysts activated by cation-forming cocatalysts Used for manufacturing. The conditions of each polymerization and the characteristics of the obtained polymer are shown. Summarized in 4. Table 4: Comparative Examples 20-23 and Examples 10-19 A. Polymerization conditions <img file="JP2000507635A_D0020.tif" /> Table 4: A. (continued) <img file="JP2000507635A_D0021.tif" />* B = B (C)₆F₅)₃, Ph₃C = Ph₃CB (C)₆F₅)₄, HNMe₂Ph = (HNMe₂Ph) B (C₆F₅)₄, LiB = LiB (C₆F₅)₄ Table 4 (continued) B. Polymerization results and polymer properties<img file="JP2000507635A_D0022.tif" /> Table 4: B. (continued) <img file="JP2000507635A_D0023.tif" /> Table 4: B. (continued) Comparative example / Example comment 20 life is short 21 Very high initial activity but short lifespan 22 Very high initial activity but short lifespan. With gel formation 23 No activity 10 Better than those produced using MAO catalysts 11 Better than those produced using MAO catalysts 12 Better than those produced using MAO catalysts 13 Better than those produced using MAO catalysts 14 Better than those produced using MAO catalysts 15 Better than those produced using MAO catalysts 16 Mooney viscosity is too high to measure 17 Mooney viscosity is too high to measure 18 Mooney viscosity is too high to measure 19 Mooney viscosity is too high to measure As these data show, the catalysts used in Comparative Examples 20-23 Short lifespan, little or total activity after rapid onset of high activity in the early stages It did not occur (the catalyst of Comparative Example 23 showed no activity). These results In contrast to the case where the cationic co-catalyst according to the present invention is used. Examples 10-19 show consistently good activity over the entire duration of the polymerization, as a result? It was shown that the stability is much higher than that of the cationic co-catalyst of the comparative example. .. This result shows that the boron-containing compound of the cationic co-catalyst of the present invention was compared with Comparative Example 20. Consider that using them separately, as in and 23, will give unacceptable results. On the contrary, it is even more surprising. Comparative Examples 24 to 43: Examples 20 to 24 Use substantially the same method as in Comparative Examples 20-23 / Examples 10-19 Within the scope of the present invention (Examples 20 to 24) and outside the scope of the present invention (Comparative Examples 24 to 4). Various metallocene touches activated by both cation-forming cocatalysts in 3) Polymerization was carried out using a medium. The conditions of each polymerization and the results are summarized in Table 5. Table 5: Comparative Examples 24 to 43: Examples 20 to 24 A. Polymerization conditions<img file="JP2000507635A_D0024.tif" /> Table 5: A. (continued) <img file="JP2000507635A_D0025.tif" /> Table 5: A. (continued) Cationic cocatalyst <img file="JP2000507635A_D0026.tif" />* B = B (C)₆F₅)₃, Ph₃C = Ph₃CB (C)₆F₅)₄, HNMe₂Ph = (HNMe₂Ph) B (C₆F₅)₄, LiB = LiB (C₆F₅)₄ Table 5: A. (continued) Cationic cocatalyst <img file="JP2000507635A_D0027.tif" />* B = B (C)₆F₅)₃, Ph₃C = Ph₃CB (C)₆F₅)₄, HNMe₂Ph = (HNMe₂Ph) B (C₆F₅)₄, LiB = LiB (C₆F₅)₄ Table 5: A. (continued) Comparative example / Example comment 24 Life is short 25 no activity 26 Very high initial activity but short lifespan 27 Short life, high initial activity No decrease in activity over 20 hours 28 Life is short 29 Very low activity 30 Very high activity but short lifespan 31 Short life, high initial activity, gelation 21 No decrease in activity over time 32 Life is short 33 No activity 34 Very high initial activity but short lifespan 35 Short life, high initial activity, gelation 22 No decrease in activity over time Table 5: A. (continued) Comparative example / Example comment 36 Life is short 37 No activity 38 Very high initial activity but short lifespan 39 Short life, high initial activity, gelation Slight decrease in activity over 23 hours 40 Life is short 41 No activity 42 Very high initial activity but short lifespan 43 Short life, high initial activity, gelation No decrease in activity over 24 hours Al (Buⁱ)₃+ PhC₃The co-catalyst was activated with a very high initial activity It gives a metallocene catalyst (Comparative Examples 26, 30, 34, 38 and 42), but its The activity activates the metallocene procatalyst using the cationic co-catalyst of the present invention. Short compared to the much more stable catalyst (Examples 20-24) obtained by It has a long life. This difference in the results is visually shown in Attached Figure 1. Figure 1 shows Al (Buⁱ)₃+ Ph₃With a C-activated procatalyst (Comparative Example 30) Al (Buⁱ)₃With a procatalyst activated with + LiB + B (Example 21), This is a comparison of monomer consumption over time. Al (Buⁱ)₃+ Ph₃The catalyst obtained using the C co-catalyst lost its activity within approximately a few minutes. On the other hand, Al (Bu) of the present inventionⁱ)₃The catalyst obtained using the + LiB + B co-catalyst Over the entire 10-minute polymerization time shown in the figure and much longer. Continued to show good activity. Al (Buⁱ)₃+ Ph₃Most of the metallocenes obtained with the C co-catalyst The same type of instability is found in Al (Bu) of Comparative Examples 27, 31, 35 and 39.ⁱ)₂+ H NMe₃Also apparent in metallocenes activated with Ph cocatalyst Therefore, the latter showed a further disadvantage of causing gelation of the polymer. Comparative Examples 44 to 48: Examples 25 to 27 Comparative Examples 44 to 48 are examples using the solution polymerization method A, and are known types of MAO. -An example of an activation catalyst. Examples 25 to 27 are examples using the solution polymerization method B. , Same as used in Comparative Examples using the cation-forming cocatalyst according to the present invention. This is an example of using a catalyst obtained by activating the same pro-catalyst. Polymerization strip Table 6 summarizes the issues, their results and the properties of the product polymer. Table 6: Comparative Examples 44 to 48: Examples 25 to 27 A. Polymerization conditions<img file="JP2000507635A_D0028.tif" /> Table 6: A. (continued) MAO co-catalyst Cationic co-catalyst <img file="JP2000507635A_D0029.tif" />* B = B (C)₆F₅)₃, LiB = LiB (C₆F₅)₄ Table 6 (continued): B. Polymerization results and polymer properties<img file="JP2000507635A_D0030.tif" /> Table 6: B. (continued) <img file="JP2000507635A_D0031.tif" /> Table 6: B. (continued) Comparative example / Example comment 44 High MAO / Zr 45 High MAO / Zr 46 High MAO / Zr, High T_g47 High MAO / Zr, high T_g48 High MAO / Zr, high T_gtwenty five Higher activity than when using MAO, M_w26 OD is very effective 27 More ODs have little further improvement When MAO is used as a co-catalyst (Comparative Examples 44 to 48), an acceptable catalyst It requires a very high MAO / procatalyst ratio to achieve activity. Especially warm At higher degrees (70 ° C), the reactivity of propylene becomes unfavorable and the resulting polymer T_gIs unacceptably high. In contrast to these results, the power of the present invention When a thione-forming cocatalyst is used to activate a procatalyst (Examples 25-2) 7) Yield increases, activity increases, and the resulting polymer M_w, ML₁₊₄And T_gIs Further improvement. In another aspect of the invention, known chain transfer agents such as hydrogen are used during polymerization. Then, the molecular weight of the elastomers described herein is intentionally and substantially reduced. Low molecular weight polymers that can be and may be desirable in certain end-use applications , Even liquid polymers can be produced. Table 7 <img file="JP2000507635A_D0032.tif" />Remarks Polymerization conditions: Ethylene at 1500 ml hexane, 40 ° C, 50 psig: Propile Mass flow ratio 1: 1, triisobutylaluminum = 0.67 mM, [Ph₂C (Cp-9-Flu) ZrCl₂] = [LiB (C)₆F₅)₄] = [B (C)₆F₅)₃] = 6.67 micro M. Polymerization period = 10 minutes. Other conditions are described in General Solution Polymerization Method B on page 27 of this specification. It is listed. b. Propene-free. Table 7 (continued) <img file="JP2000507635A_D0033.tif" />Remarks c: Evaluated by FTIR.