Catalytic olefin block copolymers with controlled block sequence distribution and at least one low crystallinity hard block

FIELD OF THE INVENTION

0001This invention relates to catalytic olefin block copolymers with a controlled block sequence distribution and at least one low crystallinity hard block.

BACKGROUND OF THE INVENTION

0002Block copolymers comprise sequences ("blocks") of monomer units, covalently bound to sequences of unlike type. The blocks can be connected in a variety of ways, such as A-B in diblock and A-B-A triblock structures, where A represents one block and B represents a different block. In a multi-block copolymer, A and B can be connected in a number of different ways and be repeated multiply. It may further comprise additional blocks of different type. Multi-block copolymers can be either linear multi-block or multi-block star polymers (in which all blocks bond to the same atom or chemical moiety).

0003A linear block copolymer is created when two or more polymer molecules of different chemical composition are covalently bonded in an end-to-end fashion. While a wide variety of block copolymer architectures are possible, most block copolymers involve the covalent bonding of hard plastic blocks, which are substantially crystalline or glassy, to elastomeric blocks forming thermoplastic elastomers. Other block copolymers, such as rubber-rubber (elastomer-elastomer), glass-glass, and glass-crystalline block copolymers, are also possible and may have commercial importance.

0004One method to make block copolymers is to produce a "living polymer". Unlike typical Ziegler-Natta polymerization processes, living polymerization processes involve only initiation and propagation steps and essentially lack chain terminating side reactions. This permits the synthesis of predetermined and well-controlled structures desired in a block copolymer. A polymer created in a "living" system can have a narrow or extremely narrow distribution of molecular weight and be essentially monodisperse (i.e., the molecular weight distribution is essentially one). Living catalyst systems are characterized by an initiation rate which is on the order of or exceeds the propagation rate, and the absence of termination or transfer reactions. In addition, these catalyst systems are characterized by the presence of a single type of active site. To produce a high yield of block copolymer in a polymerization process, the catalyst must exhibit living characteristics to a substantial extent.

0005Butadiene-isoprene block copolymers have been synthesized via anionic polymerization using the sequential monomer addition technique. In sequential addition, a certain amount of one of the monomers is contacted with the catalyst. Once a first such monomer has reacted to substantial extinction forming the first block, a certain amount of the second monomer or monomer species is introduced and allowed to react to form the second block. The process may be repeated using the same or other anionically polymerizable monomers. However, ethylene and other α-olefins, such as propylene, butene, and 1-octene are not directly block polymerizable by anionic techniques.

0006Recently, a method has been described for a process of catalytically making block copolymers with a controlled sequence distribution in publication <patcit id="pcit0001" dnum="WO2007035485A"><text>WO2007/035485</text></patcit>. As discussed in this publication, it has long been known that polymers containing a block-type structure often have superior properties compared to random copolymers and blends. For example, triblock copolymers of styrene and butadiene (SBS) and hydrogenated versions of the same (SEBS) have an excellent combination of heat resistance and elasticity. Other block copolymers are also known in the art. Generally, block copolymers known as thermoplastic elastomers (TPE) have desirable properties due to the presence of "soft" or elastomeric block segments connecting "hard", either crystallizable or glassy, blocks in the same polymer. At temperatures up to the melt temperature or glass transition temperature of the hard segments, the polymers demonstrate elastomeric character. At higher temperatures, the polymers become flowable, exhibiting thermoplastic behavior. Known methods of preparing block copolymers include anionic polymerization and controlled free radical polymerization. Unfortunately, these methods of preparing block copolymers require sequential monomer addition with polymerization to relative completeness and the types of monomers that can be usefully employed in such methods are limited. For example, in the anionic polymerization of styrene and butadiene to form a SBS type block copolymer, each polymer chain requires a stoichiometric amount of initiator and the resulting polymers have extremely narrow molecular weight distribution, Mw/Mn, preferably from 1.0 to 1.3. That is, the polymer block lengths are substantially identical. Additionally, anionic and free-radical processes are relatively slow, resulting in poor process economics, and not readily adapted to polymerization of α-olefins. <nplcit id="ncit0001" npl-type="s"><text>Gouvané et al., Colloid and Polymer Science, vol. 283, no. 9, pages 994 - 1006</text></nplcit> describes a technique to characterize mono-molecular micelles in random ethylene-propylene copolymers. A nanostructure is described with monomolecular micelles, wherein the outer core of the micelles is either ethylene-rich or propylene-rich. Samples with ethylene content 0.75 were analysed.

0007<patcit id="pcit0002" dnum="US20060211819A"><text>US,A,2006 0211819</text></patcit> discloses polymer blends from interpolymers of ethylene/alpha-olfeins.

0008It would be desirable to produce block copolymers catalytically, that is, in a process wherein more than one polymer molecule is produced for each catalyst or initiator molecule. In addition, it would be highly desirable to produce copolymers having properties resembling block copolymers from olefin monomers such as ethylene, propylene, and higher alphaolefins that are generally unsuited for use in anionic or free-radical polymerizations. In certain of these polymers, it is highly desirable that some or all of the polymer blocks comprise amorphous polymers such as a copolymer of ethylene and a comonomer, especially amorphous random copolymers comprising ethylene and an α-olefin having 3 or more carbon atoms. Finally, it would be desirable to prepare pseudo-block or block copolymers wherein a substantial fraction of the polymer molecules are of a controlled block number, especially diblocks or triblocks, but wherein the block lengths are a most probable distribution, rather than identical or nearly identical block lengths.

0009It would be useful to produce additional such block copolymers which are based on ethylene and α-olefins and have at least one low crystallinity hard block.

SUMMARY OF INVENTION

0010The present invention provides an ethylene/a-olefin block interpolymer comprising two or more homogeneous blocks comprising differing chemical or physical properties selected from variable comonomer content, crystallinity, density, tacticity and region-error, wherein the ethylene/a-olefin block interpolymer comprises a hard segment and a soft segment, and: <ol id="ol0001" compact="compact" ol-style=""><li>(a) has a Mw/Mn from 1.7 to 3.5;</li><li>(b) has an ethylene content in the hard segment in the range of from 60 wt% to 95 wt% based on total monomer content in the hard segment;</li><li>(c) <ul id="ul0001" list-style="none" compact="compact"><li>(i-a) has a hard segment in an amount of at least 40%, at least one melting point, Tm, in degrees Celsius and an amount of ethylene in weight percent, wt% C₂, wherein the numerical values of Tm and wt% C₂ correspond to the relationship: 90 °C ≥ Tm ≥ 4.1276(wt% C₂) - 244.76; or</li><li>(i-b) has a hard segment in an amount of at least 40%, at least one melting point, Tm, in degrees Celsius and an amount of ethylene in weight percent, wt% C₂, wherein the numerical values of Tm and wt% C₂ correspond to the relationship: 0 °C ≥ Tm ≥ 3.4405(wt% C₂) - 218.99; or</li><li>(ii) has a hard segment composition of less than 40%, at least one melting point, Tm, in degrees Celsius and an amount of ethylene in weight percent, wt% C₂, wherein the numerical values of Tm and wt% C₂ correspond to the relationship: 80 °C ≥ Tm ≤ 4.1276(wt% C₂) - 264.95; or</li><li>(iii) is characterized by an average block index greater than zero and up to 1.0 and a molecular weight distribution, M_w/M_n, greater than 1.3; or</li><li>(iv) has a molecular fraction which elutes between 0°C and 130°C when fractionated using low temperature Temperature Rising Elution Fractionation (TREF), characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/a-olefin block interpolymer; or</li><li>(v) has a relationship between ethylene content in wt% and log molecular weight such that a line plotted of ethylene content vs log molecular weight as measured by GPC-IR has an absolute slope, m, of equal to or less than 4; and,</li></ul></li><li>(d) has a turbidity in a 1.0 wt% solution of the ethylene/a-olefin block interpolymer in oil or a 1.5 wt% solution in dodecane that is less than 1.5 NTU and a DSC enthalpy (J/g) at greater than 55 °C of less than J/g.</li></ol>

0011The invention is further defined in the dependent claims.

0012In an embodiment, the ethylene/a-olefin block interpolymer: has a hard segment in an amount of at least 40%, at least one melting point, Tm, in degrees Celsius and an amount of ethylene in weight percent, wt% C₂, wherein the numerical values of Tm and wt% C₂ correspond to the relationship: <maths id="math0001" num=""><math display="block"><mn>0</mn><mspace width="1ex" /><mi>°C</mi><mo>≥</mo><mi>Tm</mi><mo>≥</mo><mn>3.4405</mn><mfenced separators=""><mi>wt</mi><mi>%</mi><msub><mrow><mspace width="1ex" /><mi mathvariant="normal">C</mi></mrow><mn>2</mn></msub></mfenced><mo>−</mo><mn>218.99</mn></math><img file="EP2170993B1_D0001.tif" /></maths>

0013In one embodiment, the ethylene/a-olefin block interpolymer has (a) at least one molecular fraction which elutes between 0°C and 130°C when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and up to 1 and a molecular weight distribution, Mw/Mn, greater than 1.3 or (b) an average block index greater than zero and up to 1.0 and a molecular weight distribution, Mw/Mn, greater than 1.3.

0014In one embodiment, the α-olefin used in the ethylene/a-olefin block interpolymer is styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1,5-hexadiene, or a combination thereof.

0015In another embodiment, the ethylene/a-olefin block interpolymer has a melt index in the range of 0.1 to 2000 g/10 minutes, 2 to 1500 g/10 minutes, 2 to 1000 g/10 minutes or 2 to 500 g/10 minutes measured according to ASTM D-1238, Condition 190°C/2.16 kg.

0016Additional aspects of the invention and characteristics and properties of various embodiments of the invention will become apparent with the following description.

DETAILED DESCRIPTION OF THE INVENTION

General Definitions

0017"Polymer" means a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term "polymer" embraces the terms "homopolymer," "copolymer," "terpolymer" as well as "interpolymer."

0018"Interpolymer" means a polymer prepared by the polymerization of at least two different types of monomers. The generic term "interpolymer" includes the term "copolymer" (which is usually employed to refer to a polymer prepared from two different monomers) as well as the term "terpolymer" (which is usually employed to refer to a polymer prepared from three different types of monomers). It also encompasses polymers made by polymerizing four or more types of monomers.

0019The term "ethylene/α-olefin interpolymer" generally refers to polymers comprising ethylene and an α-olefin having 3 or more carbon atoms. Preferably, ethylene comprises the majority mole fraction of the whole polymer, i.e., ethylene comprises at least 50 mole percent of the whole polymer. More preferably ethylene comprises at least 60 mole percent, at least 70 mole percent, or at least 80 mole percent, with the substantial remainder of the whole polymer comprising at least one other comonomer that is preferably an α-olefin having 3 or more carbon atoms. For many ethylene/propylene copolymers, the preferred composition comprises an ethylene content in the range of from 55 wt% to 75 wt%, preferably in the range of from 60 wt% to 73 wt%, based on the weight of the polymer. In some embodiments, the ethylene/α-olefin block interpolymers do not include those produced in low yields or in a minor amount or as a by-product of a chemical process. While the ethylene/a-olefin block interpolymers can be blended with one or more polymers, the as-produced ethylene/a-olefin block interpolymers are substantially pure and often comprise a major component of the reaction product of a polymerization process.

0020The terms "pseudo-block copolymer" or "block copolymer" refer to a copolymer comprising two or more blocks or segments of differing chemical or physical property. the two or more block comprise differing chemical or physical properties selected from variable comonomer content, crystallinity, density, tacticity, and regio-error. Non-adjacent blocks are not necessarily of identical chemical composition, but may vary in one or more of the foregoing respects, from the composition of all other blocks or regions.

0021The pseudo-block copolymers typically comprise various amounts of "hard" and "soft" segments. "Hard" segments refer to blocks of polymerized units in which ethylene is present in an amount in the range of from 60 wt% to 95 wt%, and preferably in the range of from 70 wt% to 85 wt%, based on the weight of the polymer. "Soft" segments, on the other hand, refer to blocks of polymerized units in which the comonomer content (content of monomers other than ethylene) is in the range of from 30 wt% to 80 wt%, preferably in the range of from 35 wt% to 80 wt%, based on the weight of the polymer.

0022The soft segments can often be present in a block interpolymer from 1 weight percent to 99 weight percent of the total weight of the block interpolymer, preferably from 5 weight percent to 95 weight percent, from 10 weight percent to 90 weight percent, from 15 weight percent to 85 weight percent, from 20 weight percent to 80 weight percent, from 25 weight percent to 75 weight percent, from 30 weight percent to 70 weight percent, from 35 weight percent to 65 weight percent, from 40 weight percent to 60 weight percent, or from 45 weight percent to 55 weight percent of the total weight of the block interpolymer. Conversely, the hard segments can be present in similar ranges. The polymer is said to have a hard segment majority when the amount of hard segment present is greater than 40 % and a soft segment majority when the amount of hard segment is less than 60 %. The soft segment weight percentage and the hard segment weight percentage can be calculated based on data obtained from differential scanning calorimetry (DSC) or NMR. Such methods and calculations are disclosed in <patcit id="pcit0003" dnum="US20060199930A"><text>US Patent Application Publication Number 2006-0199930</text></patcit>.

0023The term "crystalline" if employed, refers to a polymer that possesses a first order transition or crystalline melting point (Tm) as determined by differential scanning calorimetry (DSC) or equivalent technique. The term may be used interchangeably with the term "semicrystalline". The term "amorphous" refers to a polymer lacking a crystalline melting point as determined by differential scanning calorimetry (DSC) or equivalent technique.

0024Ethylene/α-olefin block interpolymers containing low crystallinity hard blocks are polymers that have hard blocks that have melting points that are less than 100°C. These polymers differ from high melting point block copolymers in that their primary use is for compatibilization of polymer blend components and/or improving the solubility of polymers in solvents and oils. Applications include oil viscosity modifiers, thermoplastic olefin impact modifiers and compatibilizers, elastomer cross-linking and heat sealing polymers. Applications such as these require polymers with a low but broad range of temperatures for thermosetting and heat sealing operations.

0025Processes useful for making the polymers have been described in <patcit id="pcit0004" dnum="WO2007035485A"><text>WO2007/035485</text></patcit>. In particular, the polymers may be made by a process comprising contacting an addition polymerizable monomer or mixture of monomers under addition polymerization conditions with a composition comprising at least one addition polymerization catalyst, a cocatalyst and a chain shuttling agent, said process being characterized by formation of at least some of the growing polymer chains under differentiated process conditions in two or more reactors operating under steady state polymerization conditions or in two or more zones of a reactor operating under plug flow polymerization conditions. Chain terminating agents such as hydrogen may be used if desired to control reactor viscosity or polymer molecular weight.

0026The block copolymers of the invention are characterized by unique distributions of polymer polydispersity (PDI or Mw/Mn) and block length distribution, with two or three, preferably two different block compositions. This is due, in a preferred embodiment, to the effect of the use of one or more shuttling agents in combination with a high activity metal complex based polymerization catalyst in two or more polymerization reactors or zones operating under differing polymerization conditions. More specifically, the block copolymers of the invention desirably possess PDI from 1.7 to 2.9, preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to 2.1. The block copolymers may also possess PDI of less than 1.8.

0027In the following description, all numbers disclosed herein are approximate values, regardless whether the word "about" or "approximate" is used in connection therewith. They may vary by 1 percent, 2 percent, 5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical range with a lower limit, R^L and an upper limit, R^U, is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R=R^L+k*(R^U-R^L), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,..., 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent. Moreover, any numerical range defined by two R numbers as defined in the above is also specifically disclosed.

0028Disclosed herein is an ethylene/a-olefin block interpolymer comprising two or more substantially homogeneous blocks comprising differing chemical or physical properties, wherein the ethylene/a-olefin interpolymer comprises a hard segment and a soft segment, and: <ol id="ol0002" compact="compact" ol-style=""><li>(a) has a Mw/Mn from 1.7 to 3.5;</li><li>(b) has an ethylene content in the hard segment in the range of from 60 wt% to 95 wt% based on based on total monomer content in hard segment;</li><li>(c) <ul id="ul0002" list-style="none" compact="compact"><li>(i-a) has a hard segment in an amount of at least 40%, at least one melting point, Tm, in degrees Celsius and an amount of ethylene in weight percent, wt% C₂, wherein the numerical values of Tm and wt% C₂ correspond to the relationship: <maths id="math0002" num=""><math display="block"><mn>90</mn><mspace width="1ex" /><mo>°</mo><mi mathvariant="normal">C</mi><mo>≥</mo><mi>Tm</mi><mo>≥</mo><mn>4.1276</mn><mfenced separators=""><mi>wt</mi><mi>%</mi><msub><mrow><mspace width="1ex" /><mi mathvariant="normal">C</mi></mrow><mn>2</mn></msub></mfenced><mo>−</mo><mn>244.76</mn><mo>;</mo></math><img file="EP2170993B1_D0002.tif" /></maths> or</li><li>(i-b) has a hard segment in an amount of at least 40%, at least one melting point, Tm, in degrees Celsius and an amount of ethylene in weight percent, wt% C₂, wherein the numerical values of Tm and wt% C₂ correspond to the relationship: <maths id="math0003" num=""><math display="block"><mn>0</mn><mspace width="1ex" /><mi>°C</mi><mo>≥</mo><mi>Tm</mi><mo>≥</mo><mn>3.4405</mn><mfenced separators=""><mi>wt</mi><mi>%</mi><msub><mrow><mspace width="1ex" /><mi mathvariant="normal">C</mi></mrow><mn>2</mn></msub></mfenced><mo>−</mo><mn>218.99</mn><mo>;</mo></math><img file="EP2170993B1_D0003.tif" /></maths> or</li><li>(ii) has a hard segment composition of less than 40%, at least one melting point, Tm, in degrees Celsius and an amount of ethylene in weight percent, wt% C₂, wherein the numerical values of Tm and wt% C₂ correspond to the relationship: <maths id="math0004" num=""><math display="block"><mn>80</mn><mspace width="1ex" /><mo>°</mo><mi mathvariant="normal">C</mi><mo>≥</mo><mi>Tm</mi><mo>≥</mo><mn>4.1276</mn><mfenced separators=""><mi>wt</mi><mi>%</mi><msub><mrow><mspace width="1ex" /><mi mathvariant="normal">C</mi></mrow><mn>2</mn></msub></mfenced><mo>−</mo><mn>264.95</mn><mo>;</mo></math><img file="EP2170993B1_D0004.tif" /></maths> or</li><li>(iii) is characterized by an average block index greater than zero and up to about 1.0 and a molecular weight distribution, M_w/M_n, greater than 1.3; or</li><li>(iv) has a molecular fraction which elutes between 0°C and 130°C when fractionated using low temperature TREF, characterized in that the fraction has a molar comonomer content of at least 5 percent higher than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the ethylene/a-olefin interpolymer; or</li><li>(v) has a relationship between ethylene content in wt% and log molecular weight such that a line plotted of ethylene content vs log molecular weight as measured by GPC-IR has an absolute slope, m, of equal to or less than 4; and</li></ul></li><li>(d) has a turbidity in a 1.0 wt% solution of the ethylene/a-olefin block interpolymer in oil or a 1.5 wt% solution in dodecane that is less than 1.5 NTU and a DSC enthalpy (J/g) at greater than 55 °C of less than 2 J/g.</li></ol>

0029In an embodiment, the ethylene/α-olefin block interpolymer has a hard segment in an amount of at least 40%, at least one melting point, Tm, in degrees Celsius and an amount of ethylene in weight percent, wt% C₂, wherein the numerical values of Tm and wt% C₂ correspond to the relationship: <maths id="math0005" num=""><math display="block"><mn>0</mn><mspace width="1ex" /><mi>°C</mi><mo>≥</mo><mi>Tm</mi><mo>≥</mo><mn>3.4405</mn><mfenced separators=""><mi>wt</mi><mi>%</mi><msub><mrow><mspace width="1ex" /><mi mathvariant="normal">C</mi></mrow><mn>2</mn></msub></mfenced><mo>−</mo><mn>212.42.</mn></math><img file="EP2170993B1_D0005.tif" /></maths>

Ethylene/α-Olefin Block Interpolymers

0030The ethylene/α-olefin block interpolymers underlying embodiments of the invention (also referred to as "inventive interpolymer" or "inventive polymer") comprise ethylene and one or more copolymerizable α-olefin comonomers in polymerized form, characterized by segments of two or more polymerized monomer units differing in chemical or physical properties as noted herein above (block interpolymer). These pseudo-block copolymers comprise two or more substantially homogeneous intramolecular segments or blocks comprising differing chemical or physical properties as noted herein above, said intramolecular segments characterized by possessing a most probable molecular weight distribution

0031In one embodiment, the ethylene/α-olefin block interpolymers have a molecular fraction which elutes between 0 °C and 130 °C when fractionated using Temperature Rising Elution Fractionation ("TREF"), characterized in that said fraction has a molar comonomer content at least 5 percent higher, more preferably at least 10 percent higher, than that of a comparable random ethylene interpolymer fraction eluting between the same temperatures, wherein the comparable random ethylene interpolymer contains the same comonomer(s), and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the block interpolymer. Preferably, the Mw/Mn of the comparable random interpolymer is also within 10 percent of that of the block interpolymer and/or the comparable random interpolymer has a total comonomer content within 10 weight percent of that of the block interpolymer.

0032In some embodiments, the pseudo-block copolymers possess a PDI fitting a Schultz-Flory distribution rather than a Poisson distribution. The copolymers are further characterized as having a polydisperse distribution of block sizes and possessing a most probable distribution of block lengths. Preferred block copolymers are those containing 2 or more blocks or segments including terminal blocks.

0033Comonomer content may be measured using any suitable technique, with techniques based on nuclear magnetic resonance ("NMR") spectroscopy preferred. Moreover, for polymers or blends of polymers having relatively broad TREF curves, the polymer desirably is first fractionated using TREF into fractions each having an eluted temperature range of 10 °C or less. That is, each eluted fraction has a collection temperature window of 10 °C or less. Using this technique, said block interpolymers have at least one such fraction having a higher molar comonomer content than a corresponding fraction of the comparable interpolymer.

0034In one aspect, the inventive polymer is an olefin interpolymer comprising ethylene and one or more copolymerizable α-olefin comonomers in polymerized form, characterized by a number of blocks (i.e., at least two blocks) or segments of two or more polymerized monomer units differing in chemical or physical properties (blocked interpolymer), said block interpolymer having a peak (but not just a molecular fraction) which elutes between 0 °C and 130 °C (but without collecting and/or isolating individual fractions), characterized in that said peak, has a comonomer content estimated by infra-red spectroscopy when expanded using a full width/half maximum (FWHM) area calculation, has an average molar comonomer content at least 5 percent higher, more preferably at least 10 percent higher, than that of a comparable random ethylene interpolymer peak at the same elution temperature and expanded using a full width/half maximum (FWHM) area calculation, wherein said comparable random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10 percent of that of the blocked interpolymer. Preferably, the Mw/Mn of the comparable interpolymer is also within 10 percent of that of the blocked interpolymer and/or the comparable interpolymer has a total comonomer content within 10 weight percent of that of the blocked interpolymer. The full width/half maximum (FWHM) calculation is based on the ratio of methyl to methylene response area [CH₃/CH₂] from the ATREF infra-red detector, wherein the tallest (highest) peak is identified from the base line, and then the FWHM area is determined. For a distribution measured using an ATREF peak, the FWHM area is defined as the area under the curve between T₁ and T₂, where T₁ and T₂ are points determined, to the left and right of the ATREF peak, by dividing the peak height by two, and then drawing a line horizontal to the base line, that intersects the left and right portions of the ATREF curve. A calibration curve for comonomer content is made using random ethylene/a-olefin copolymers, plotting comonomer content from NMR versus FWHM area ratio of the TREF peak. For this infra-red method, the calibration curve is generated for the same comonomer type of interest. The comonomer content of TREF peak of the inventive polymer can be determined by referencing this calibration curve using its FWHM methyl:methylene area ratio [CH₃/CH₂] of the TREF peak.

ATREF Peak Comonomer Composition Measurement by Infra-Red Detector

0035The comonomer composition of the TREF peak can be measured using an IR4 infra-red detector available from Polymer Char, Valencia, Spain (<u>http://www.polymerchar.com/</u>).

0036The "composition mode" of the detector is equipped with a measurement sensor (CH₂) and composition sensor (CH₃) that are fixed narrow band infra-red filters in the region of 2800-3000 cm^-1. The measurement sensor detects the methylene (CH₂) carbons on the polymer (which directly relates to the polymer concentration in solution) while the composition sensor detects the methyl (CH₃) groups of the polymer. The mathematical ratio of the composition signal (CH₃) divided by the measurement signal (CH₂) is sensitive to the comonomer content of the measured polymer in solution and its response is calibrated with known ethylene alpha-olefin copolymer standards.

0037The detector when used with an ATREF instrument provides both a concentration (CH₂) and composition (CH₃) signal response of the eluted polymer during the TREF process. A polymer specific calibration can be created by measuring the area ratio of the CH₃ to CH₂ for polymers with known comonomer content (preferably measured by NMR). The comonomer content of an ATREF peak of a polymer can be estimated by applying the reference calibration of the ratio of the areas for the individual CH₃ and CH₂ response (i.e. area ratio CH₃/CH₂ versus comonomer content).

0038The area of the peaks can be calculated using a full width/half maximum (FWHM) calculation after applying the appropriate baselines to integrate the individual signal responses from the TREF chromatogram. The full width/half maximum calculation is based on the ratio of methyl to methylene response area [CH₃/CH₂] from the ATREF infra-red detector, wherein the tallest (highest) peak is identified from the base line, and then the FWHM area is determined. For a distribution measured using an ATREF peak, the FWHM area is defined as the area under the curve between T1 and T2, where T1 and T2 are points determined, to the left and right of the ATREF peak, by dividing the peak height by two, and then drawing a line horizontal to the base line, that intersects the left and right portions of the ATREF curve.

0039The application of infra-red spectroscopy to measure the comonomer content of polymers in this ATREF-infra-red method is, in principle, similar to that of GPC/FTIR systems as described in the following references: <nplcit id="ncit0002" npl-type="s"><text>Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley; "Development of gel-permeation chromatography-Fourier transform infrared spectroscopy for characterization of ethylene-based polyolefin copolymers". Polymeric Materials Science and Engineering (1991), 65, 98-100</text></nplcit>.; and <nplcit id="ncit0003" npl-type="s"><text>Deslauriers, P.J.; Rohlfing, D.C.; Shieh, E.T.; "Quantifying short chain branching microstructures in ethylene-1-olefin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTIR)", Polymer (2002), 43, 59-170</text></nplcit>.

0040In other embodiments, the inventive ethylene/a-olefin block interpolymer is characterized by an average block index, ABI, which is greater than zero and up to 1.0 and a molecular weight distribution, M_w/M_n, greater than 1.3. The average block index, ABI, is the weight average of the block index ("BI") for each of the polymer fractions obtained in preparative TREF from 20°C and 110°C, with an increment of 5°C : <maths id="math0006" num=""><math display="block"><mi mathvariant="italic">ABI</mi><mo>=</mo><mstyle displaystyle="true"><mo>∑</mo><mfenced separators=""><msub><mi>w</mi><mi>i</mi></msub><msub><mi mathvariant="italic">BI</mi><mi>i</mi></msub></mfenced></mstyle></math><img file="EP2170993B1_D0006.tif" /></maths> where BI_i is the block index for the i^th fraction of the inventive ethylene/a-olefin interpolymer obtained in preparative TREF, and w_i is the weight percentage of the i^th fraction.

0041For each polymer fraction, BI is defined by one of the two following equations (both of which give the same BI value): <maths id="math0007" num=""><math display="block"><mi mathvariant="italic">BI</mi><mo>=</mo><mfrac><mrow><mn>1</mn><mo>/</mo><msub><mi>T</mi><mi>X</mi></msub><mo>−</mo><mn>1</mn><mo>/</mo><msub><mi>T</mi><mi mathvariant="italic">XO</mi></msub></mrow><mrow><mn>1</mn><mo>/</mo><msub><mi>T</mi><mi>A</mi></msub><mo>−</mo><mn>1</mn><mo>/</mo><msub><mi>T</mi><mi mathvariant="italic">AB</mi></msub></mrow></mfrac><mspace width="1ex" /><mi>or</mi><mspace width="1ex" /><mi mathvariant="italic">BI</mi><mo>=</mo><mo>−</mo><mfrac><mrow><mi mathvariant="italic">Ln</mi><msub><mi>P</mi><mi>X</mi></msub><mo>−</mo><mi mathvariant="italic">Ln</mi><msub><mi>P</mi><mi mathvariant="italic">XO</mi></msub></mrow><mrow><mi mathvariant="italic">Ln</mi><msub><mi>P</mi><mi>A</mi></msub><mo>−</mo><mi mathvariant="italic">Ln</mi><msub><mi>P</mi><mi mathvariant="italic">AB</mi></msub></mrow></mfrac></math><img file="EP2170993B1_D0007.tif" /></maths> where T_X is the preparative ATREF elution temperature for the i^th fraction (preferably expressed in Kelvin), P_X is the ethylene mole fraction for the i^th fraction, which can be measured by NMR or IR as described above. P_AB is the ethylene mole fraction of the whole ethylene/α-olefin interpolymer (before fractionation), which also can be measured by NMR or IR. T_A and P_A are the ATREF elution temperature and the ethylene mole fraction for pure "hard segments" (which refer to the crystalline segments of the interpolymer). As a first order approximation, the T_A and P_A values are set to those for high density polyethylene homopolymer, if the actual values for the "hard segments" are not available. For calculations performed herein, T_A is 372°K, P_A is 1.

0042T_AB is the ATREF temperature for a random copolymer of the same composition and having an ethylene mole fraction of P_AB. T_AB can be calculated from the following equation: <maths id="math0008" num=""><math display="block"><msub><mi>Ln P</mi><mi>AB</mi></msub><mo>=</mo><mi mathvariant="normal">α</mi><mo>/</mo><msub><mi mathvariant="normal">T</mi><mi>AB</mi></msub><mo>+</mo><mi mathvariant="normal">β</mi></math><img file="EP2170993B1_D0008.tif" /></maths> where α and β are two constants which can be determined by calibration using a number of known random ethylene copolymers. It should be noted that α and β may vary from instrument to instrument. Moreover, one would need to create their own calibration curve with the polymer composition of interest and also in a similar molecular weight range as the fractions. There is a slight molecular weight effect. If the calibration curve is obtained from similar molecular weight ranges, such effect would be essentially negligible. In some embodiments, random ethylene copolymers satisfy the following relationship: <maths id="math0009" num=""><math display="block"><mi>Ln P</mi><mo>=</mo><mo>−</mo><mn>237.83</mn><mo>/</mo><msub><mi mathvariant="normal">T</mi><mi>ATREF</mi></msub><mo>+</mo><mn>0.639</mn></math><img file="EP2170993B1_D0009.tif" /></maths>

0043T_XO is the ATREF temperature for a random copolymer of the same composition and having an ethylene mole fraction of P_X. T_XO can be calculated from LnP_X = α/T_XO + β. Conversely, P_XO is the ethylene mole fraction for a random copolymer of the same composition and having an ATREF temperature of T_X, which can be calculated from Ln P_XO = α/T_X + β.

0044Once the block index (BI) for each preparative TREF fraction is obtained, the weight average block index, ABI, for the whole polymer can be calculated. In some embodiments, ABI is greater than zero but less than 0.3 or from 0.1 to 0.3. In other embodiments, ABI is greater than 0.3 and up to 1.0. Preferably, ABI should be in the range of from 0.4 to 0.7, from 0.5 to 0.7, or from 0.6 to 0.9. In some embodiments, ABI is in the range of from 0.3 to 0.9, from 0.3 to 0.8, or from 0.3 to 0.7, from 0.3 to 0.6, from 0.3 to 0.5, or from 0.3 to 0.4. In other embodiments, ABI is in the range of from 0.4 to 1.0, from 0.5 to 1.0, or from 0.6 to 1.0, from 0.7 to 1.0, from 0.8 to 1.0, or from 0.9 to 1.0.

0045Another characteristic of the inventive ethylene/a-olefin block interpolymer is that the inventive ethylene/a-olefin block interpolymer comprises at least one polymer fraction which can be obtained by preparative TREF, wherein the fraction has a block index greater than 0.1 and up to 1.0 and a molecular weight distribution, M_w/M_n, greater than 1.3. In some embodiments, the polymer fraction has a block index greater than 0.6 and up to 1.0, greater than 0.7 and up to 1.0, greater than 0.8 and up to 1.0, or greater than 0.9 and up to 1.0. In other embodiments, the polymer fraction has a block index greater than 0.1 and up to 1.0, greater than 0.2 and up to 1.0, greater than 0.3 and up to 1.0, greater than 0.4 and up to 1.0, or greater than 0.4 and up to 1.0. In still other embodiments, the polymer fraction has a block index greater than 0.1 and up to 0.5, greater than 0.2 and up to 0.5, greater than 0.3 and up to 0.5, or greater than 0.4 and up to 0.5. In yet other embodiments, the polymer fraction has a block index greater than 0.2 and up to 0.9, greater than 0.3 and up to 0.8, greater than 0.4 and up to 0.7, or greater than 0.5 and up to 0.6.

0046For copolymers of ethylene and an α-olefin, the inventive polymers preferably possess (1) a PDI of at least 1.3, more preferably at least 1.5, at least 1.7, or at least 2.0, and most preferably at least 2.6, up to a maximum value of 5.0, more preferably up to a maximum of 3.5, and especially up to a maximum of 2.7; (2) a heat of fusion of 80 J/g or less; (3) an ethylene content of at least 50 weight percent; (4) a glass transition temperature, T_g, of less than -25°C, more preferably less than -30°C, and/or (5) one and only one T_m.

0047Additionally, the ethylene/a-olefin block interpolymers can have a melt index, I₂, from 0.01 to 2000 g/10 minutes, preferably from 0.01 to 1000 g/10 minutes, more preferably from 0.01 to 500 g/10 minutes, and especially from 0.01 to 100 g/10 minutes. In certain embodiments, the ethylene/α-olefin block interpolymers have a melt index, I₂, from 0.01 to 10 g/10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes, from 1 to 6 g/10 minutes or from 0.3 to 10 g/10 minutes. In certain embodiments, the melt index for the ethylene/a-olefin block interpolymers is 1g/10 minutes, 3 g/10 minutes or 5 g/10 minutes.

0048The polymers can have molecular weights, M_w, from 1,000 g/mole to 5,000,000 g/mole, preferably from 1000 g/mole to 1,000,000, more preferably from 10,000 g/mole to 500,000 g/mole, and especially from 10,000 g/mole to 300,000 g/mole. The density of the inventive polymers can be from 0.80 to 0.99 g/cm³ and preferably for ethylene containing polymers from 0.85 g/cm³ to 0.97 g/cm³. In certain embodiments, the density of the ethylene/a-olefin block polymers ranges from 0.860 to 0.925 g/cm³ or 0.867 to 0.910 g/cm³.

0049In some embodiments, the ethylene/α-olefin block interpolymers additionally have a Tm in the range of from -25 °C to 100 °C, preferably from 30 °C to 80 °C, and more preferably from 35 °C to 75 °C . In some embodiments, they may also have a Tm in the range of from 15 °C to 50 °C, from 30 °C to 45 °C or from 35 °C to 40°C. In some embodiments, the interpolymers have a Tm that is less than that of a comparable random copolymer with same weight percent comonomer within 10%. In addition, in some embodiments the end of melting occurs at less than 100 °C, preferably in the range of from 85 °C to 95 °C.

0050The ethylene/α-olefin block interpolymers may also comprise additives and adjuvants. Suitable additives include fillers, such as organic or inorganic particles, including clays, talc, titanium dioxide, zeolites, powdered metals, organic or inorganic fibers, nano-sized particles, clays, and so forth; tackifiers, oil extenders, including paraffinic or napthelenic oils; and other natural and synthetic polymers, including other polymers according to embodiments of the invention. Additionally, minor amounts of a different polymer may be used as a carrier for any of the additives. An example of such a polymer would be polyethylene, for example AFFINITY® resins (The Dow Chemical Company) or EXACT® resins (ExxonMobil Chemical Company.

0051Representative catalysts and chain shuttling agent are as follows. Chemical structures follow each description.

0052<b>Catalyst (A1)</b> is [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium dimethyl, prepared according to the teachings of <patcit id="pcit0005" dnum="WO0340195A"><text>WO 03/40195</text></patcit> and <patcit id="pcit0006" dnum="WO0424740A"><text>WO 04/24740</text></patcit>. <chemistry id="chem0001" num="0001"><img file="EP2170993B1_D0010.tif" /></chemistry>

0053<b>Catalyst (A2)</b> is [N-(2,6-di(1-methylethyl)phenyl)amido)(2-methylphenyl)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafnium dimethyl, prepared according to the teachings of <patcit id="pcit0007" dnum="WO0340195A"><text>WO 03/40195</text></patcit> and <patcit id="pcit0008" dnum="WO0424740A"><text>WO 04/24740</text></patcit>. <chemistry id="chem0002" num="0002"><img file="EP2170993B1_D0011.tif" /></chemistry>

0054<b>Catalyst (A3)</b> is bis[N,N'''-(2,4,6-tri(methylphenyl)amido)ethylenediamine]hafnium dibenzyl. <chemistry id="chem0003" num="0003"><img file="EP2170993B1_D0012.tif" /></chemistry>

0055<b>Catalyst (A4)</b> is bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diyl zirconium (IV) dibenzyl, prepared substantially according to the teachings of <patcit id="pcit0009" dnum="US20040010103A"><text>US-A-2004/0010103</text></patcit>. <chemistry id="chem0004" num="0004"><img file="EP2170993B1_D0013.tif" /></chemistry>

0056<b>Catalyst</b> (<b>A5</b>) is (bis-(1-methylethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl. <chemistry id="chem0005" num="0005"><img file="EP2170993B1_D0014.tif" /></chemistry>

0057The preparation of catalyst (A5) is conducted as follows.

a) Preparation of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)inline

00583,5-Di-t-butylsalicylaldehyde (3.00 g) is added to 10 mL of isopropylamine. The solution rapidly turns bright yellow. After stirring at ambient temperature for 3 hours, volatiles are removed under vacuum to yield a bright yellow, crystalline solid (97 percent yield).

b) Preparation of (bis-(1-methylethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino) zirconium dibenzyl

0059A solution of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)imine (605 mg, 2.2 mmol) in 5 mL toluene is slowly added to a solution of Zr(CH₂Ph)₄ (500 mg, 1.1 mmol) in 50 mL toluene. The resulting dark yellow solution is stirred for 30 min. Solvent is removed under reduced pressure to yield the desired product as a reddish-brown solid.

0060<b>Catalyst</b> (<b>A6</b>) is bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino) zirconium dibenzyl <chemistry id="chem0006" num="0006"><img file="EP2170993B1_D0015.tif" /></chemistry>

0061The preparation of catalyst (A6) is conducted as follows.

a) Preparation of (1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine

00622-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol (90 mL), and di-t-butylsalicaldehyde (10.00 g, 42.67 mmol) is added. The reaction mixture is stirred for three hours and then cooled to -25 °C for 12 hrs. The resulting yellow solid precipitate is collected by filtration and washed with cold methanol (2 x 15 mL), and then dried under reduced pressure. The yield is 11.17 g of a yellow solid. ¹H NMR is consistent with the desired product as a mixture of isomers.

b) Preparation of bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl) immino)zirconium dibenzyl

0063A solution of (1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine (7.63 g, 23.2 mmol) in 200 mL toluene is slowly added to a solution of Zr(CH₂Ph)₄ (5.28 g, 11.6 mmol) in 600 mL toluene. The resulting dark yellow solution is stirred for 1 hour at 25 °C. The solution is diluted further with 680 mL toluene to give a solution having a concentration of 0.00783 M.

0064<b>Catalyst</b> (<b>A7</b>) is (t-butylamido)dimethyl(3-N-pyrro1yl-1,2,3,3a,7a-η-inden-1-yl)silanetitanium dimethyl prepared substantially according to the techniques of <patcit id="pcit0010" dnum="USP6268444B"><text>USP 6,268,444</text></patcit>: <chemistry id="chem0007" num="0007"><img file="EP2170993B1_D0016.tif" /></chemistry>

0065<b>Catalyst</b> (<b>A8</b>) is (t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,7a-η-inden-1-yl)silanetitanium dimethyl prepared substantially according to the teachings of <patcit id="pcit0011" dnum="US2003004286A"><text>US-A-2003/004286</text></patcit>: <chemistry id="chem0008" num="0008"><img file="EP2170993B1_D0017.tif" /></chemistry>

0066<b>Catalyst</b> (<b>A9</b>) is (t-butylamido)di(4-metby1phenyl)(2-metbyl-1,2,3,3a,8a-n-s-indacen-1-yl)silanetitanium dimethyl prepared substantially according to the teachings of <patcit id="pcit0012" dnum="US2003004286A"><text>US-A-2003/004286</text></patcit>: <chemistry id="chem0009" num="0009"><img file="EP2170993B1_D0018.tif" /></chemistry>

0067<b>Catalyst</b> (<b>A10</b>) is bis(dimethyldisiloxane)(indene-1-yl)zirconium dichloride available from Sigma-Aldrich: <chemistry id="chem0010" num="0010"><img file="EP2170993B1_D0019.tif" /></chemistry>

0068<b>Shuttling Agents</b> The shuttling agents employable include diethylzinc, di(i-butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum, triethylgallium, i-butylaluminum bis(dimethyl(t-butyl)siloxane), i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum, i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis(2,6-di-t-butylphenoxide, n-octylaluminum di(ethyl(1-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminum bis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminum bis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminum bis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), and ethylzinc (t-butoxide).

0069The inventive interpolymers may comprise alternating blocks of differing comonomer content (including homopolymer blocks). The inventive interpolymers may also comprise a distribution in block size of polymer blocks of differing density or comonomer content, which is a Schultz-Flory type of distribution.

0070The ethylene/a-olefin block interpolymers underlying embodiments of the invention are preferably interpolymers of ethylene with at least one C₃-C₂₀ α-olefin. Copolymers of ethylene and a C₃-C₂₀ α-olefin are especially preferred. The interpolymers may further comprise C₄-C₁₈ diolefin and/or alkenylbenzene. Suitable unsaturated comonomers useful for polymerizing with ethylene include, for example, ethylenically unsaturated monomers, conjugated or nonconjugated dienes, polyenes, and alkenylbenzenes. Examples of such comonomers include C₃-C₂₀ α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, and 1-decene. Propylene and non-conjugated dienes are preferred. Other suitable monomers include styrene, halo- or alkyl-substituted styrenes, vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics (e.g., cyclopentene, cyclohexene and cyclooctene).

0071While ethylene/α-olefin interpolymers are preferred polymers, other ethylene/olefin polymers may also be used. Olefins as used herein refer to a family of unsaturated hydrocarbon-based compounds with at least one carbon-carbon double bond. Depending on the selection of catalysts, any olefin may be used in embodiments of the invention. Preferably, suitable olefins are C₃-C₂₀ aliphatic and aromatic compounds containing vinylic unsaturation, as well as cyclic compounds, such as cyclobutene, cyclopentene, dicyclopentadiene, and norbornene, including norbornene substituted in the 5 and 6 position with C₁-C₂₀ hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures of such olefins as well as mixtures of such olefins with C₄-C₄₀ diolefin compounds.

0072Examples of olefin monomers include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene, vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene, cyclohexene, dicyclopentadiene, cyclooctene, C₄-C₄₀ dienes, including 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, and other C₄-C₄₀ α-olefins. In certain embodiments, the α-olefin is propylene, 1-butene, 1-pentene,1-hexene, 1-octene or a combination thereof. Although any hydrocarbon containing a vinyl group potentially may be used in embodiments of the invention, practical issues such as monomer availability, cost, and the ability to conveniently remove unreacted monomer from the resulting polymer may become more problematic as the molecular weight of the monomer becomes too high.

0073The polymerization processes described herein are well suited for the production of olefin polymers comprising monovinylidene aromatic monomers including styrene, o-methyl styrene, p-methyl styrene, and t-btylstyrene. In particular, interpolymers comprising ethylene and styrene can be prepared by following the teachings herein. Optionally, copolymers comprising ethylene, styrene and a C₃-C₂₀ alpha olefin, optionally comprising a C₄-C₂₀ diene, having improved properties can be prepared.

0074Suitable non-conjugated diene monomers can be a straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms. Examples of suitable non-conjugated dienes include straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene and dihydroocinene, single ring alicyclic dienes, such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene. Of the dienes typically used to prepare EPDMs, the particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB), and dicyclopentadiene (DCPD). The especially preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

0075One class of desirable polymers that can be made in accordance with embodiments of the invention are elastomeric interpolymers of ethylene, a C₃-C₂₀ α-olefin, especially propylene, and optionally one or more diene monomers. Preferred α-olefins for use in this embodiment of the present invention are designated by the formula CH₂=CHR*, where R* is a linear or branched alkyl group of from 1 to 12 carbon atoms. Examples of suitable α-olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. A particularly preferred α-olefin is propylene. The propylene based polymers are generally referred to in the art as EP or EPDM polymers. Suitable dienes for use in preparing such polymers, especially multi-block EPDM type polymers include conjugated or non-conjugated, straight or branched chain-, cyclic- or polycyclic- dienes comprising from 4 to 20 carbons. Preferred dienes include 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferred diene is 5-ethylidene-2-norbornene.

0076Because the diene containing polymers comprise alternating segments or blocks containing greater or lesser quantities of the diene (including none) and α-olefin (including none), the total quantity of diene and α-olefin may be reduced without loss of subsequent polymer properties. That is, because the diene and α-olefin monomers are preferentially incorporated into one type of block of the polymer rather than uniformly or randomly throughout the polymer, they are more efficiently utilized and subsequently the crosslink density of the polymer can be better controlled. Such crosslinkable elastomers and the cured products have advantaged properties, including higher tensile strength and better elastic recovery.

0077In some embodiments, the inventive interpolymers made with two catalysts incorporating differing quantities of comonomer have a weight ratio of blocks formed thereby from 95:5 to 5:95. The polymers desirably have an ethylene content of from 20 to 90 percent, a diene content of from 0.1 to 10 percent, and an α-olefin content of from 10 to 80 percent, based on the total weight of the polymer. Further preferably, the pseudo-block polymers have an ethylene content of from 60 to 90 percent, a diene content of from 0.1 to 10 percent, and an α-olefin content of from 10 to 40 percent, based on the total weight of the polymer. Preferred polymers are high molecular weight polymers, having a weight average molecular weight (Mw) from 10,000 to about 2,500,000, preferably from 20,000 to 500,000, more preferably from 20,000 to 350,000, and a polydispersity less than 3.5, more preferably less than 3.0, and a Mooney viscosity (ML (1+4) 125°C) from 1 to 250. More preferably, such polymers have an ethylene content from 65 to 75 percent, a diene content from 0 to 6 percent, and an α-olefin content from 20 to 35 percent.

0078The ethylene/a-olefin block interpolymers can be functionalized by incorporating at least one functional group in its polymer structure. Exemplary functional groups may include, for example, ethylenically unsaturated mono- and di-functional carboxylic acids, ethylenically unsaturated mono- and di-functional carboxylic acid anhydrides, salts thereof and esters thereof. Such functional groups may be grafted to an ethylene/α-olefin interpolymer, or it may be copolymerized with ethylene and an optional additional comonomer to form an interpolymer of ethylene, the functional comonomer and optionally other comonomer(s). Means for grafting functional groups onto polyethylene are described for example in <patcit id="pcit0013" dnum="US4762890A"><text>U.S. Patent Nos. 4,762,890</text></patcit>, <patcit id="pcit0014" dnum="US4927888A"><text>4,927,888</text></patcit>, and <patcit id="pcit0015" dnum="US4950541A"><text>4,950,541</text></patcit>. One particularly useful functional group is malic anhydride.

0079The amount of the functional group present in the functional interpolymer can vary. The functional group can typically be present in a copolymer-type functionalized interpolymer in an amount of at least 1.0 weight percent, preferably at least 5 weight percent, and more preferably at least 7 weight percent. The functional group will typically be present in a copolymer-type functionalized interpolymer in an amount less than 40 weight percent, preferably less than 30 weight percent, and more preferably less than 25 weight percent.

0080The ethylene/α-olefin block interpolymers of the present invention may be used in a number of applications, a set of examples of which are given below. The interpolymers may be used an impact modifier for polypropylene; a compatibilizer for random ethylene/alpha olefin copolymers or termonomers and polypropylene; and, the interpolymers may be used as a peroxide crosslinked elastomer with either ethylene/alpha olefin copolymers or ethylene/alpha olefin/nonconjugated diene termonomers. Additionally, the lower melting point allows for manufacture in standard thermoset applications. Such applications include: conveyor belting; V-belting; crosslinked foams, including, but not limited to, midsole foams in footwear, foamed mats, wet suits, extruded sponge profiles, dual hardness sponge/solid coextruded profiles, single ply roofing, and windshield wipers.

0081For an ethylene/alpha olefin/nonconjugated diene termonomer composition, sulfur or phenolic cured versions of elastomeric compositions may be produced. Similar applications may be used as described for peroxide crosslinked elastomers.

0082The ethylene/a-olefin block interpolymers of the present invention may also be used in oil extended gel compounds in thermoplastic or thermoset applications.

0083In addition, the ethylene/a-olefin interpolymers of the present invention may be used in noise, vibration and harshness (NVH) control related applications.

0084The following examples are presented to exemplify embodiments of the invention but are not intended to limit the invention to the specific embodiments set forth. Unless indicated to the contrary, all parts and percentages are by weight. All numerical values are approximate. When numerical ranges are given, it should be understood that embodiments outside the stated ranges may still fall within the scope of the invention. Specific details described in each example should not be construed as necessary features of the invention.

EXAMPLES

Testing Methods

0085In the examples that follow, the following analytical techniques are employed:

GPC-IR Method

Gel Permeation Chromatography (GPC)

0086The gel permeation chromatographic system is either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220 instrument. The column and carousel compartments are operated at 150 °C. Four Polymer Laboratories 20 µm (20-micron) Mixed-A columns are used. The solvent is 1,2,4 trichlorobenzene. The samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent containing 200 ppm of butylated hydroxytoluene (BHT). Samples are prepared by agitating lightly for 2 hours at 160°C. The injection volume used is 200 microliters and the flow rate is 1.0 ml/minute.

0087Calibration of the GPC column set is performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000, arranged in 6 "cocktail" mixtures with at least a decade of separation between individual molecular weights. The standards are purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards are prepared at 0.025 grams in 50 milliliters of solvent for molecular weights equal to or greater than 1,000,000, and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80°C with gentle agitation for 30 minutes. The narrow standards mixtures are run first and in order of decreasing highest molecular weight component to minimize degradation. The polystyrene standard peak molecular weights are converted to polyethylene molecular weights using the following equation (as described in <nplcit id="ncit0004" npl-type="s"><text>Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968</text></nplcit>)): M_polyethylene = 0.431(M_polystyrene).

0088Polyetheylene equivalent molecular weight calculations are performed using Viscotek TriSEC software Version 3.0.

Molecular Weight-Comonomer Composition Measurement by Infra-Red Detector

0089The comonomer composition throughout the GPC curve can be measured using an IR4 infra-red detector that is available from Polymer Char, Valencia, Spain (<u>http://www.polymerchar.com/</u>).

0090The "composition mode" of the detector is equipped with a measurement sensor (CH₂) and composition sensor (CH₃) that are fixed narrow band infra-red filters in the region of 2800-3000 cm^-1. The measurement sensor detects the methylene (CH₂) carbons on the polymer (which directly relates to the polymer concentration in solution) while the composition sensor detects the methyl (CH₃) groups of the polymer. The mathematical ratio of the composition signal (CH₃) divided by the measurement signal (CH₂) is sensitive to the comonomer content of the measured polymer in solution and its response is calibrated with known ethylene alpha-olefin copolymer standards.

0091The detector when used with a GPC instrument provides both a concentration (CH₂) and composition (CH₃) signal response of the eluted polymer during the GPC process. A polymer specific calibration can be created by measuring the area ratio of the CH₃ to CH₂ for polymers with known comonomer content (preferably measured by NMR). The comonomer distribution of a polymer can be estimated by applying a reference calibration of the ratio of the areas for the individual CH₃ and CH₂ response (i.e. area ratio CH₃/CH₂ versus comonomer content).

0092By taking the ratio of the CH₃/CH₂ response at each elution volume, the response to the polymer's composition is measured. After applying the appropriate reference calibration, the composition response can be used to estimate the comonomer amount at each elution volume. Integration of the entire GPC profile provides the average comonomer content of the polymer while the slope of the line from the comonomer versus molecular weight provides an indication of the uniformity of the comonomer distribution. When integrating the GPC chromatograph for composition determination, the integration region should be set to be greater than 5 weight percent of the polymer on either end of the chromatogram.

0093The application of infra-red spectroscopy to measure the comonomer content of polymers in this system is similar in principle to GPC/FTIR systems as described in the following references:

0094<nplcit id="ncit0005" npl-type="s"><text>Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley; "Development of gel-permeation chromatography-Fourier transform infrared spectroscopy for characterization of ethylene-based polyolefin copolymers", Polymeric Materials Science and Engineering (1991), 65, 98-100</text></nplcit>.

0095<nplcit id="ncit0006" npl-type="s"><text> Deslauriers, P.J.; Rohlfing, D.C.; Shieh, E.T.; "Quantifying short chain branching microstructures in ethylene-1-olefin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTIR)", Polymer (2002), 43, 59-170</text></nplcit>.

DSC Standard Method

0096Differential Scanning Calorimetry results are determined using a TAI model Q1000 DSC equipped with an RCS cooling accessory and an autosampler. A nitrogen purge gas flow of 50 ml/min is used. The sample is pressed into a thin film and melted in the press at about 175°C and then air-cooled to room temperature (25°C). 3-10 mg of material is then cut into a 6 mm diameter disk, accurately weighed, placed in a light aluminum pan (ca 50 mg), and then crimped shut. The thermal behavior of the sample is investigated with the following temperature profile. The sample is rapidly heated to 180°C and held isothermal for 3 minutes in order to remove any previous thermal history. The sample is then cooled to - 40°C at 10°C/min cooling rate and held at -40°C for 3 minutes. The sample is then heated to 150 °C at 10°C/min. heating rate. The cooling and second heating curves are recorded.

0097The DSC melting peak is measured as the maximum in heat flow rate (W/g) with respect to the linear baseline drawn between -30°C and end of melting. The heat of fusion is measured as the area under the melting curve between -30°C and the end of melting using a linear baseline.

Density

0098Samples for density measurement are prepared according to ASTM D 1928. Measurements are made within one hour of sample pressing using ASTM D792, Method B.

Melt Index

0099Melt index, or I₂, is measured in accordance with ASTM D 1238, Condition 190°C/2.16 kg. Melt index, or I₁₀ is also measured in accordance with ASTM D 1238, Condition 190°C/10 kg.

Mooney Viscosity

0100Mooney viscosity is measured in accordance with ASTM D1646-06 at 125°C, ML 1+4 (MU)).

ATREF

0101Analytical temperature rising elution fractionation (ATREF) analysis is conducted according to the method described in <patcit id="pcit0016" dnum="USP4798081A"><text>USP 4,798,081</text></patcit> and <nplcit id="ncit0007" npl-type="s"><text>Wilde, L.; Ryle, T.R.; Knobeloch, D.C.; Peat, I.R.; Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. Sci., 20, 441-455 (1982</text></nplcit>). The composition to be analyzed is dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel shot) by slowly reducing the temperature to 20°C at a cooling rate of 0.1°C/min. The column is equipped with an infrared detector. An ATREF chromatogram curve is then generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 to 120°C at a rate of 1.5°C/min.

¹³C NMR Analysis

0102The samples are prepared by adding approximately 3g of a 50/50 mixture of tetrachloroethane-d²/orthodichlorobenzene to 0.4 g sample in a 10 mm NMR tube. The samples are dissolved and homogenized by heating the tube and its contents to 150°C. The data are collected using a JEOL Eclipse™ 400MHz spectrometer or a Varian Unity Plus™ 400MHz spectrometer, corresponding to a ¹³C resonance frequency of 100.5 MHz. The data are acquired using 4000 transients per data file with a 6 second pulse repetition delay. To achieve minimum signal-to-noise for quantitative analysis, multiple data files are added together. The spectral width is 25,000 Hz with a minimum file size of 32K data points. The samples are analyzed at 130 °C in a 10 mm broad band probe. The comonomer incorporation is determined using Randall's triad method (<nplcit id="ncit0008" npl-type="s"><text>Randall, J.C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989</text></nplcit>)).

Additional Method for ¹³C NMR analysis

0103The following generally describes an NMR methodology to determine the composition, sequence distribution and ratio of amorphous and semi-crystalline blocks of an ethylene-propylene olefin block copolymer with ethylene/propylene segment/block compositions that differ by less than 25-30 wt% ethylene by using the relationship between NMR integrals and comonomer concentration.

0104For a diblock copolymer with both blocks made by a specific catalyst, the NMR integrals fit the following equation: <maths id="math0010" num=""><math display="block"><mi mathvariant="normal">I</mi><mo>=</mo><mi mathvariant="normal">P</mi><mo>*</mo><mi mathvariant="normal">f</mi><mfenced separators=""><mi mathvariant="normal">E</mi><mn>1</mn></mfenced><mo>+</mo><mfenced separators=""><mn>1</mn><mo>−</mo><mi mathvariant="normal">P</mi></mfenced><mo>*</mo><mi mathvariant="normal">f</mi><mfenced separators=""><mi mathvariant="normal">E</mi><mn>2</mn></mfenced></math><img file="EP2170993B1_D0020.tif" /></maths> Where <ul id="ul0003" list-style="none" compact="compact"><li>I is the integral for a selected peak of copolymer</li><li>P is the weight fraction of the first block</li><li>E1 is the concentration of ethylene in first block</li><li>E2 is the concentration of ethylene in second block</li><li>f(E1) is the integral contribution from the first block</li><li>f(E2) is the integral contribution from the second block</li></ul>

0105As there are more than 3 integrals and only three unknowns (P, E1 and E2), an optimized solution of P, E1 and E2 can be obtained from normalized NMR integrals.

0106In the second step, assign an initial value to E1 corresponding to the value expected from the process parameters and calculate corresponding integrals with equations.

0107In the third step, assign an initial value to E2 corresponding to the value expected from the process parameters and calculate corresponding integrals with equations.

0108In the fourth step, assign an initial value to P corresponding to the value expected from the process parameters and the equation, I=P*f(E1)+(1-P)*f(E2), is used to get simulated integrals.

0109Lastly, the calculated residual errors between raw normalized and simulated integrals are minimized to minimize the sum of the residual errors to get P, E1 and E2 .

Polymer Fractionation by TREF

0110Large-scale TREF fractionation is carried by dissolving 15-20 g of polymer in 2 liters of 1,2,4-trichlorobenzene (TCB)by stirring for 4 hours at 160°C. The polymer solution is forced by 15 psig (100 kPa) nitrogen onto a 3 inch by 4 foot (7.6 cm x 12 cm) steel column packed with a 60:40 (v:v) mix of 30-40 mesh (600-425 µm) spherical, technical quality glass beads (available from Potters Industries, HC 30 Box 20, Brownwood, TX, 76801) and stainless steel, 0.028" (0.7mm) diameter cut wire shot (available from Pellets, Inc. 63 Industrial Drive, North Tonawanda, NY, 14120). The column is immersed in a thermally controlled oil jacket, set initially to 160 °C. The column is first cooled ballistically to 125 °C, then slow cooled to 20 °C at 0.04 °C per minute and held for one hour. Fresh TCB is introduced at about 65 ml/min while the temperature is increased at 0.167 °C per minute.

0111Approximately 2000 ml portions of eluant from the preparative TREF column are collected in a 16 station, heated fraction collector. The polymer is concentrated in each fraction using a rotary evaporator until about 50 to 100 ml of the polymer solution remains. The concentrated solutions are allowed to stand overnight before adding excess methanol, filtering, and rinsing (approx. 300-500 ml of methanol including the final rinse). The filtration step is performed on a 3 position vacuum assisted filtering station using 5.0 µm polytetrafluoroethylene coated filter paper (available from Osmonics Inc., Cat# Z50WP04750). The filtrated fractions are dried overnight in a vacuum oven at 60 °C and weighed on an analytical balance before further testing.

Turbidity

0112Turbidity of the oil or solvent solutions were measured using a HACH RATIO Turbidimeter Model 18900 using the 0-20 NTU resolution scale (+/- 0.1 NTU).

Catalysts

0113The term "overnight", if used, refers to a time of approximately 16-18 hours, the term "room temperature", refers to a temperature of 20-25 °C, and the term "mixed alkanes" refers to a commercially obtained mixture of C_6-9 aliphatic hydrocarbons available under the trade designation Isopar E®, from ExxonMobil Chemical Company. In the event the name of a compound herein does not conform to the structural representation thereof, the structural representation shall control. The synthesis of all metal complexes and the preparation of all screening experiments are carried out in a dry nitrogen atmosphere using dry box techniques. All solvents used are HPLC grade and are dried before their use.

0114<b>MMAO</b> refers to modified methylalumoxane, a triisobutylaluminum modified methylalumoxane available commercially from Akzo-Nobel Corporation.

0115<b>Cocatalyst 1</b> A mixture of methyldi(C_14-18 alkyl)ammonium salts of tetrakis(pentafluorophenyl)borate (here-in-after armeenium borate), prepared by reaction of a long chain trialkylamine (Armeen™ M2HT, available from Akzo-Nobel, Inc.), HCl and Li[B(C₆F₅)₄], substantially as disclosed in <patcit id="pcit0017" dnum="USP59199883B"><text>USP 5,919,9883</text></patcit>, Ex. 2.

0116<b>Cocatalyst 2</b> Mixed C_14-18 alkyldimethylammonium salt of bis(tris(pentafluorophenyl)-alumane)-2-undecylimidazolide, prepared according to <patcit id="pcit0018" dnum="USP6395671B"><text>USP 6,395,671</text></patcit>, Ex. 16.

Examples 1-4, Comparative Example A

0117Ethylene/propylene copolymers are prepared using two continuous stirred tank reactors (CSTR) connected in series. Each reactor is hydraulically full and set to operate at steady state conditions. The shuttling agent (SA1) is added to the first reactor along with catalyst A-1, Cocatalyst 1, a scavenger (triisobutylaluminum modified methylalumoxane MMAO, available from Akzo-Nobel, Inc.), and solvent (mixed alkanes (Isopar™ E, available from ExxonMobil Chemicals, Inc.). Operating conditions for the two reactors are provided in Tables 1 and 2. Polymer properties are provided in Table 3.

Examples 5-12

0118Examples 5 - 12 are manufactured using a non-adiabatic polymerization system consisting of two recirculating loop reactors configured in series. The shuttling agent (SA1) is added to the first reactor along with catalyst A-1, Cocatalyst 1, a scavenger (triisobutylaluminum modified methylalumoxane MMAO, available from Akzo-Nobel, Inc.), and solvent (mixed alkanes (Isopar™ E, available from ExxonMobil Chemicals, Inc.). Operating conditions for the two reactors are provided in Tables 1 and 2. Polymer properties are provided in Table 3. <tables id="tabl0001" num="0001"><table frame="all"><title>Table 1. Process Conditions First CSTR or Loop Reactor</title><tgroup cols="16"><colspec colnum="1" colname="col1" colwidth="12mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="15mm" /><colspec colnum="4" colname="col4" colwidth="15mm" /><colspec colnum="5" colname="col5" colwidth="15mm" /><colspec colnum="6" colname="col6" colwidth="12mm" /><colspec colnum="7" colname="col7" colwidth="18mm" /><colspec colnum="8" colname="col8" colwidth="18mm" /><colspec colnum="9" colname="col9" colwidth="18mm" /><colspec colnum="10" colname="col10" colwidth="15mm" /><colspec colnum="11" colname="col11" colwidth="18mm" /><colspec colnum="12" colname="col12" colwidth="16mm" /><colspec colnum="13" colname="col13" colwidth="18mm" /><colspec colnum="14" colname="col14" colwidth="14mm" /><colspec colnum="15" colname="col15" colwidth="16mm" /><colspec colnum="16" colname="col16" colwidth="14mm" /><thead><row><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top">Cat. A-1</entry><entry align="center" valign="top">Cat. A-1</entry><entry align="center" valign="top">Cocat.</entry><entry align="center" valign="top">Cocat</entry><entry align="center" valign="top">MMAO</entry><entry align="center" valign="top">MMAO</entry><entry align="center" valign="top">SA1</entry><entry align="center" valign="top">SA1</entry><entry align="center" valign="top" /><entry align="center" valign="top" /></row><row><entry align="center" valign="top" /><entry align="center" valign="top">Solv.</entry><entry align="center" valign="top">C₂H₄¹</entry><entry align="center" valign="top">C₃H₆¹</entry><entry align="center" valign="top">H₂</entry><entry align="center" valign="top">T</entry><entry align="center" valign="top">Conc</entry><entry align="center" valign="top">Flow</entry><entry align="center" valign="top">Conc.</entry><entry align="center" valign="top">flow</entry><entry align="center" valign="top">Conc</entry><entry align="center" valign="top">Flow</entry><entry align="center" valign="top">Conc</entry><entry align="center" valign="top">Flow</entry><entry align="center" valign="top" /><entry align="center" valign="top">R-1</entry></row><row><entry align="center" valign="top">Run</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">sccm²</entry><entry align="center" valign="top">°C</entry><entry align="center" valign="top">mmol/kg</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">mmol/kg</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">mmol/kg</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">mmol/kg</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">Conv.⁴</entry><entry align="center" valign="top">Split⁵</entry></row></thead><tbody><row><entry align="center">A*</entry><entry align="center">22</entry><entry align="center">1.84</entry><entry align="center">0.75</entry><entry align="center">160</entry><entry align="center">107</entry><entry align="center">0.5</entry><entry align="center">0.21</entry><entry align="center">0.252</entry><entry align="center">0.5</entry><entry align="center">2</entry><entry align="center">0.1</entry><entry align="center">-</entry><entry align="center">-</entry><entry align="center" /><entry align="center">61</entry></row><row><entry align="center">1*</entry><entry align="center">22</entry><entry align="center">1.84</entry><entry align="center">0.75</entry><entry align="center">0</entry><entry align="center">105</entry><entry align="center">0.5</entry><entry align="center">0.21</entry><entry align="center">0.25</entry><entry align="center">0.5</entry><entry align="center">-</entry><entry align="center">-</entry><entry align="center">153³</entry><entry align="center">0.142</entry><entry align="center" /><entry align="center">61</entry></row><row><entry align="center">2</entry><entry align="center">25.5</entry><entry align="center">2</entry><entry align="center">1.1</entry><entry align="center">0</entry><entry align="center">105</entry><entry align="center">0.5</entry><entry align="center">0.245</entry><entry align="center">0.286</entry><entry align="center">0.5</entry><entry align="center">-</entry><entry align="center">-</entry><entry align="center">153³</entry><entry align="center">0.12</entry><entry align="center" /><entry align="center">80</entry></row><row><entry align="center">3</entry><entry align="center">25.5</entry><entry align="center">1.92</entry><entry align="center">1.4</entry><entry align="center">0</entry><entry align="center">107</entry><entry align="center">1</entry><entry align="center">0.125</entry><entry align="center">1</entry><entry align="center">0.132</entry><entry align="center">-</entry><entry align="center">-</entry><entry align="center">153³</entry><entry align="center">0.125</entry><entry align="center">88.6</entry><entry align="center">79</entry></row><row><entry align="center">4</entry><entry align="center">25.5</entry><entry align="center">2.1</entry><entry align="center">1.4</entry><entry align="center">0</entry><entry align="center">111</entry><entry align="center">1</entry><entry align="center">0.13</entry><entry align="center">1</entry><entry align="center">0.156</entry><entry align="center">-</entry><entry align="center">-</entry><entry align="center">153³</entry><entry align="center">0.146</entry><entry align="center">69.7</entry><entry align="center">68</entry></row><row><entry align="center">5</entry><entry align="center">173.6</entry><entry align="center">21.7</entry><entry align="center">28.6</entry><entry align="center">0</entry><entry align="center">95</entry><entry align="center">1.68</entry><entry align="center">0.63</entry><entry align="center">5.81</entry><entry align="center">0.27</entry><entry align="center">40.5</entry><entry align="center">0.38</entry><entry align="center">458</entry><entry align="center">0.42</entry><entry align="center">84.2</entry><entry align="center">64</entry></row><row><entry align="center">6</entry><entry align="center">188.6</entry><entry align="center">18.8</entry><entry align="center">18.3</entry><entry align="center">0</entry><entry align="center">104</entry><entry align="center">1.68</entry><entry align="center">0.55</entry><entry align="center">5.81</entry><entry align="center">0.31</entry><entry align="center">40.5</entry><entry align="center">0.42</entry><entry align="center">458</entry><entry align="center">0.31</entry><entry align="center">91.1</entry><entry align="center">64</entry></row><row><entry align="center">7</entry><entry align="center">180.4</entry><entry align="center">17.7</entry><entry align="center">13.4</entry><entry align="center">0</entry><entry align="center">105</entry><entry align="center">1.68</entry><entry align="center">0.55</entry><entry align="center">5.81</entry><entry align="center">0.32</entry><entry align="center">40.5</entry><entry align="center">0.44</entry><entry align="center">458</entry><entry align="center">0.33</entry><entry align="center">89.9</entry><entry align="center">52</entry></row><row><entry align="center">8</entry><entry align="center">180.5</entry><entry align="center">17.6</entry><entry align="center">18.8</entry><entry align="center">0</entry><entry align="center">104</entry><entry align="center">1.68</entry><entry align="center">0.54</entry><entry align="center">5.81</entry><entry align="center">0.31</entry><entry align="center">40.5</entry><entry align="center">0.42</entry><entry align="center">458</entry><entry align="center">0.31</entry><entry align="center">89.7</entry><entry align="center">55</entry></row><row><entry align="center">9</entry><entry align="center">168.4</entry><entry align="center">15.2</entry><entry align="center">19.4</entry><entry align="center">0</entry><entry align="center">103</entry><entry align="center">1.68</entry><entry align="center">0.54</entry><entry align="center">5.81</entry><entry align="center">0.30</entry><entry align="center">40.5</entry><entry align="center">0.42</entry><entry align="center">458</entry><entry align="center">0.30</entry><entry align="center">89.5</entry><entry align="center">53</entry></row><row><entry align="center">10</entry><entry align="center">115.4</entry><entry align="center">8.7</entry><entry align="center">23.7</entry><entry align="center">0</entry><entry align="center">105</entry><entry align="center">1.68</entry><entry align="center">0.47</entry><entry align="center">5.81</entry><entry align="center">0.27</entry><entry align="center">40.5</entry><entry align="center">0.44</entry><entry align="center">458</entry><entry align="center">0.32</entry><entry align="center">87.6</entry><entry align="center">39</entry></row><row><entry align="center">11</entry><entry align="center">180.4</entry><entry align="center">17.5</entry><entry align="center">20.5</entry><entry align="center">0</entry><entry align="center">105</entry><entry align="center">1.68</entry><entry align="center">0.56</entry><entry align="center">5.81</entry><entry align="center">0.24</entry><entry align="center">40.5</entry><entry align="center">0.45</entry><entry align="center">458</entry><entry align="center">0.33</entry><entry align="center">89.9</entry><entry align="center">55</entry></row><row><entry align="center">12</entry><entry align="center">180.5</entry><entry align="center">17.5</entry><entry align="center">20.5</entry><entry align="center">25.6</entry><entry align="center">105</entry><entry align="center">1.68</entry><entry align="center">0.55</entry><entry align="center">5.81</entry><entry align="center">0.24</entry><entry align="center">40.5</entry><entry align="center">0.43</entry><entry align="center">458</entry><entry align="center">0.31</entry><entry align="center">91.3</entry><entry align="center">56</entry></row></tbody></tgroup><tgroup cols="16" rowsep="0"><colspec colnum="1" colname="col1" colwidth="12mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="15mm" /><colspec colnum="4" colname="col4" colwidth="15mm" /><colspec colnum="5" colname="col5" colwidth="15mm" /><colspec colnum="6" colname="col6" colwidth="12mm" /><colspec colnum="7" colname="col7" colwidth="18mm" /><colspec colnum="8" colname="col8" colwidth="18mm" /><colspec colnum="9" colname="col9" colwidth="18mm" /><colspec colnum="10" colname="col10" colwidth="15mm" /><colspec colnum="11" colname="col11" colwidth="18mm" /><colspec colnum="12" colname="col12" colwidth="16mm" /><colspec colnum="13" colname="col13" colwidth="18mm" /><colspec colnum="14" colname="col14" colwidth="14mm" /><colspec colnum="15" colname="col15" colwidth="16mm" /><colspec colnum="16" colname="col16" colwidth="14mm" /><tbody><row><entry namest="col1" nameend="col16" align="justify">*Comparative, not an example of the invention. ¹ Total flow (recycle + fresh, Ex. 5 - 12) ² Standard cm³/min ³ The DEZ solution also contains 1-5 mol percent of MMAO. ⁴ Percent ethylene conversion in reactor. ⁵ Percent of polymer produced in reactor 1.</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><title>Table 2. Process Conditions Second CSTR or Loop Reactor.</title><tgroup cols="15"><colspec colnum="1" colname="col1" colwidth="12mm" /><colspec colnum="2" colname="col2" colwidth="15mm" /><colspec colnum="3" colname="col3" colwidth="15mm" /><colspec colnum="4" colname="col4" colwidth="15mm" /><colspec colnum="5" colname="col5" colwidth="16mm" /><colspec colnum="6" colname="col6" colwidth="13mm" /><colspec colnum="7" colname="col7" colwidth="19mm" /><colspec colnum="8" colname="col8" colwidth="19mm" /><colspec colnum="9" colname="col9" colwidth="19mm" /><colspec colnum="10" colname="col10" colwidth="16mm" /><colspec colnum="11" colname="col11" colwidth="20mm" /><colspec colnum="12" colname="col12" colwidth="17mm" /><colspec colnum="13" colname="col13" colwidth="17mm" /><colspec colnum="14" colname="col14" colwidth="20mm" /><colspec colnum="15" colname="col15" colwidth="14mm" /><thead><row><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top">Cat. A-1</entry><entry align="center" valign="top">Cat. A-1</entry><entry align="center" valign="top">Cocat.</entry><entry align="center" valign="top">Cocat.</entry><entry align="center" valign="top">MMAO</entry><entry align="center" valign="top">MMAO</entry><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top" /></row><row><entry align="center" valign="top" /><entry align="center" valign="top">Solv.</entry><entry align="center" valign="top">C₂H₄</entry><entry align="center" valign="top">C₃H₆</entry><entry align="center" valign="top">H₂</entry><entry align="center" valign="top">T</entry><entry align="center" valign="top">Conc.</entry><entry align="center" valign="top">Flow</entry><entry align="center" valign="top">Conc.</entry><entry align="center" valign="top">Flow</entry><entry align="center" valign="top">Conc</entry><entry align="center" valign="top">Flow</entry><entry align="center" valign="top" /><entry align="center" valign="top" /><entry align="center" valign="top">Rate</entry></row><row><entry align="center" valign="top">Ex.</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">sccm¹</entry><entry align="center" valign="top">°C</entry><entry align="center" valign="top">mmol/kg</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">mmol/kg</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">mmol/Kg</entry><entry align="center" valign="top">kg/hr</entry><entry align="center" valign="top">Conv.²</entry><entry align="center" valign="top">R-2 Split³</entry><entry align="center" valign="top">kg/hr</entry></row></thead><tbody><row><entry align="center">A*</entry><entry align="center">13</entry><entry align="center">0.95</entry><entry align="center">2.7</entry><entry align="center">0</entry><entry align="center" /><entry align="center">0.5</entry><entry align="center">0.08</entry><entry align="center">0.5</entry><entry align="center">0.096</entry><entry align="center">2</entry><entry align="center">0.1</entry><entry align="center" /><entry align="center">39</entry><entry align="center" /></row><row><entry align="center">1*</entry><entry align="center">14</entry><entry align="center">0.88</entry><entry align="center">2.7</entry><entry align="center">0</entry><entry align="center" /><entry align="center">0.5</entry><entry align="center">0.08</entry><entry align="center">0.5</entry><entry align="center">0.096</entry><entry align="center">2</entry><entry align="center">0.1</entry><entry align="center" /><entry align="center">39</entry><entry align="center" /></row><row><entry align="center">2</entry><entry align="center">5</entry><entry align="center">0</entry><entry align="center">1</entry><entry align="center">0</entry><entry align="center" /><entry align="center">0.5</entry><entry align="center">0.08</entry><entry align="center">0.5</entry><entry align="center">0.06</entry><entry align="center">2</entry><entry align="center">0.08</entry><entry align="center" /><entry align="center">20</entry><entry align="center" /></row><row><entry align="center">3</entry><entry align="center">5.5</entry><entry align="center">0.2</entry><entry align="center">1</entry><entry align="center">0</entry><entry align="center">109</entry><entry align="center">1</entry><entry align="center">0.056</entry><entry align="center">1</entry><entry align="center">0.064</entry><entry align="center">3.06</entry><entry align="center">0.08</entry><entry align="center" /><entry align="center">21</entry><entry align="center">3</entry></row><row><entry align="center">4</entry><entry align="center">10.5</entry><entry align="center">0.4</entry><entry align="center">1.75</entry><entry align="center">0</entry><entry align="center">106</entry><entry align="center">1</entry><entry align="center">0.065</entry><entry align="center">1</entry><entry align="center">0.078</entry><entry align="center">2</entry><entry align="center">0.05</entry><entry align="center" /><entry align="center">32</entry><entry align="center">3</entry></row><row><entry align="center">5</entry><entry align="center">44.7</entry><entry align="center">6.1</entry><entry align="center">17.1</entry><entry align="center">0</entry><entry align="center">105</entry><entry align="center">1.68</entry><entry align="center">0.146</entry><entry align="center">5.81</entry><entry align="center">0.063</entry><entry align="center">40.55</entry><entry align="center">0</entry><entry align="center">76.3</entry><entry align="center">36</entry><entry align="center">38</entry></row><row><entry align="center">6</entry><entry align="center">50.6</entry><entry align="center">9.5</entry><entry align="center">27.6</entry><entry align="center">0</entry><entry align="center">105</entry><entry align="center">1.68</entry><entry align="center">0.163</entry><entry align="center">5.81</entry><entry align="center">0.138</entry><entry align="center">40.55</entry><entry align="center">0</entry><entry align="center">73.9</entry><entry align="center">36</entry><entry align="center">39</entry></row><row><entry align="center">7</entry><entry align="center">56.9</entry><entry align="center">10.0</entry><entry align="center">29.7</entry><entry align="center">0</entry><entry align="center">106</entry><entry align="center">1.68</entry><entry align="center">0.189</entry><entry align="center">5.81</entry><entry align="center">0.163</entry><entry align="center">40.55</entry><entry align="center">0</entry><entry align="center">82.5</entry><entry align="center">48</entry><entry align="center">39</entry></row><row><entry align="center">8</entry><entry align="center">56.6</entry><entry align="center">10.0</entry><entry align="center">30.8</entry><entry align="center">0</entry><entry align="center">110</entry><entry align="center">1.68</entry><entry align="center">0.215</entry><entry align="center">5.81</entry><entry align="center">0.185</entry><entry align="center">40.55</entry><entry align="center">0</entry><entry align="center">81.7</entry><entry align="center">45</entry><entry align="center">41</entry></row><row><entry align="center">9</entry><entry align="center">57.2</entry><entry align="center">10.0</entry><entry align="center">30.8</entry><entry align="center">0</entry><entry align="center">109</entry><entry align="center">1.68</entry><entry align="center">0.224</entry><entry align="center">5.81</entry><entry align="center">0.193</entry><entry align="center">40.55</entry><entry align="center">0</entry><entry align="center">83.0</entry><entry align="center">47</entry><entry align="center">41</entry></row><row><entry align="center">10</entry><entry align="center">131.0</entry><entry align="center">19.5</entry><entry align="center">7.5</entry><entry align="center">0</entry><entry align="center">115</entry><entry align="center">1.68</entry><entry align="center">0.421</entry><entry align="center">5.81</entry><entry align="center">0.362</entry><entry align="center">40.55</entry><entry align="center">0</entry><entry align="center">88.1</entry><entry align="center">61</entry><entry align="center">40</entry></row><row><entry align="center">11</entry><entry align="center">54.4</entry><entry align="center">10.3</entry><entry align="center">31.5</entry><entry align="center">0</entry><entry align="center">105</entry><entry align="center">1.68</entry><entry align="center">0.182</entry><entry align="center">5.81</entry><entry align="center">0.156</entry><entry align="center">40.55</entry><entry align="center">0</entry><entry align="center">78.2</entry><entry align="center">45</entry><entry align="center">42</entry></row><row><entry align="center">12</entry><entry align="center">52.6</entry><entry align="center">10.3</entry><entry align="center">31.4</entry><entry align="center">47.2</entry><entry align="center">105</entry><entry align="center">1.68</entry><entry align="center">0.166</entry><entry align="center">5.81</entry><entry align="center">0.142</entry><entry align="center">40.55</entry><entry align="center">0</entry><entry align="center">81.0</entry><entry align="center">44</entry><entry align="center">42</entry></row></tbody></tgroup><tgroup cols="15" rowsep="0"><colspec colnum="1" colname="col1" colwidth="12mm" /><colspec colnum="2" colname="col2" colwidth="15mm" /><colspec colnum="3" colname="col3" colwidth="15mm" /><colspec colnum="4" colname="col4" colwidth="15mm" /><colspec colnum="5" colname="col5" colwidth="16mm" /><colspec colnum="6" colname="col6" colwidth="13mm" /><colspec colnum="7" colname="col7" colwidth="19mm" /><colspec colnum="8" colname="col8" colwidth="19mm" /><colspec colnum="9" colname="col9" colwidth="19mm" /><colspec colnum="10" colname="col10" colwidth="16mm" /><colspec colnum="11" colname="col11" colwidth="20mm" /><colspec colnum="12" colname="col12" colwidth="17mm" /><colspec colnum="13" colname="col13" colwidth="17mm" /><colspec colnum="14" colname="col14" colwidth="20mm" /><colspec colnum="15" colname="col15" colwidth="14mm" /><tbody><row><entry namest="col1" nameend="col15" align="justify">* Comparative, not an example of the invention. ¹ Total feed (carryover + fresh, ex. 5 - 12). ² Percent ethylene conversion in reactor 2. ³ Percent of polymer produced in reactor 2.</entry></row></tbody></tgroup></table></tables><tables id="tabl0003" num="0003"><img file="EP2170993B1_D0021.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP2170993B1_D0022.tif" /></tables>

GPC-IR and Turbidity Measurements

0119Comonomer composition throughout the GPC curve was monitored via GPC-IR. The numerical values of the comonomer content vs molecular weight fractions were plotted and fitted to a line, mx+b. The absolute slope, Iml, and turbidities in oil and dodecane are given in Table 4 below. <tables id="tabl0005" num="0005"><table frame="all"><title>Table 4</title><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="17mm" /><colspec colnum="3" colname="col3" colwidth="10mm" /><colspec colnum="4" colname="col4" colwidth="23mm" /><colspec colnum="5" colname="col5" colwidth="34mm" /><thead><row><entry valign="top">Ex.</entry><entry align="center" valign="top">AH_>55°C</entry><entry align="center" valign="top">|m|</entry><entry align="center" valign="top">Turbidity (oil)</entry><entry align="center" valign="top">Turbidity (dodecane)</entry></row></thead><tbody><row><entry>A*</entry><entry align="center">4.3</entry><entry align="center">7.5</entry><entry align="center">2.8</entry><entry align="center">2.9</entry></row><row><entry>1*</entry><entry align="center">3.6</entry><entry align="center">2.2</entry><entry align="center">1.2</entry><entry align="center">2</entry></row></tbody></tgroup><tgroup cols="5" rowsep="0"><colspec colnum="1" colname="col1" colwidth="10mm" /><colspec colnum="2" colname="col2" colwidth="17mm" /><colspec colnum="3" colname="col3" colwidth="10mm" /><colspec colnum="4" colname="col4" colwidth="23mm" /><colspec colnum="5" colname="col5" colwidth="34mm" /><tbody><row><entry namest="col1" nameend="col5" align="justify">*Comparative, not an example of the invention</entry></row></tbody></tgroup></table></tables>

0120While the invention has been described with respect to a limited number of embodiments, the specific features of one embodiment should not be attributed to other embodiments of the invention. No single embodiment is representative of all aspects of the invention. In some embodiments, the compositions or methods may include numerous compounds or steps not mentioned herein. In other embodiments, the compositions or methods do not include, or are substantially free of, any compounds or steps not enumerated herein. Variations and modifications from the described embodiments exist. Finally, any number disclosed herein should be construed to mean approximate, regardless of whether the word "about" or "approximately" is used in describing the number. The appended claims intend to cover all those modifications and variations as falling within the scope of the invention.