阅读说明：本技术 通过在并联方法中采用vtp和hmp催化剂体系制备具有增强弹性的聚合物组合物的方法 (Process for preparing a polymer composition with enhanced elasticity by employing a VTP and HMP catalyst system in a parallel process ) 是由 F·C·里克斯 J·A·M·卡尼奇 R·科尔布 于 2019-08-15 设计创作，主要内容包括：这里提供了制备具有增强弹性的共混聚合物组合物的方法。本发明方法包括以下步骤：使用VTP催化剂体系制备第一聚合物组合物,使用HMP催化剂体系制备第二聚合物组合物和将所述第一聚合物组合物和所述第二聚合物组合物结合以制备共混聚合物组合物。本发明方法包括将通过不同催化剂体系制备的聚合物组合物共混/结合。一种这样的催化剂体系包括(i)包含VTP催化剂化合物(这里也称作“VTP催化剂”)和一种或多种活化剂的乙烯基-封端聚合物(VTP)催化剂体系。另一种催化剂体系包括包含HMP催化剂化合物(这里也称作“HMP催化剂”)和一种或多种活化剂的高分子量聚合物(HMP)催化剂体系。这些不同的催化剂体系的活化剂可以完全或部分地相同或不同。(Provided herein are methods of making blended polymer compositions having enhanced elasticity. The method comprises the following steps: the method includes the steps of preparing a first polymer composition using a VTP catalyst system, preparing a second polymer composition using a HMP catalyst system, and combining the first polymer composition and the second polymer composition to produce a blended polymer composition. The process of the present invention comprises blending/combining polymer compositions prepared by different catalyst systems. One such catalyst system includes (i) a vinyl-terminated polymer (VTP) catalyst system comprising a VTP catalyst compound (also referred to herein as a "VTP catalyst") and one or more activators. Another catalyst system includes a high molecular weight polymer (HMP) catalyst system comprising an HMP catalyst compound (also referred to herein as an "HMP catalyst") and one or more activators. The activators of these different catalyst systems may be completely or partially the same or different.)

1. A process for preparing a blended polymer composition having enhanced elasticity comprising the steps of:

(a) providing a first polymer composition, wherein the first polymer composition is a VTP composition prepared with a VTP catalyst compound;

(b) providing a second polymer composition, wherein the second polymer composition is a HMP composition prepared with a HMP catalyst compound;

(c) combining the first polymer composition and the second polymer composition; and

(d) recovering the polymer blend composition;

wherein the HMP composition has a weight average molecular weight greater than the weight average molecular weight of the VTP composition; and

wherein the VTP catalyst compound is represented by the formula:

wherein:

(1) j is a divalent bridging group containing C, Si or both;

(2) m is a group 4 transition metal;

(3) each X is independently a monovalent anionic ligand, or two X's join to form a chelating ligand, a diene ligand, or an alkylidene ligand; and

(4)R²-R⁷each of which is independently hydrogen, C₁-C₅₀Substituted or unsubstituted hydrocarbyl or C₁-C₅₀A substituted or unsubstituted halogenated hydrocarbon group, with the proviso that R⁴And R⁵、R⁵And R⁶And R⁶And R⁷Any one or more of the pairs may optionally be bonded together to form a saturated or partially saturated cyclic or fused ring structure.

2. The method of claim 1, wherein the VTP composition is (a) ethylene; (b) one or more alpha-olefins or cyclic olefins; and (c) a copolymer of a diene.

3. The process of claim 2 wherein the diene is 5-ethylidene-2-norbornene.

4. The process of claims 2-3 wherein the one or more alpha-olefins or cyclic olefins are selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, or combinations thereof.

5. The process of claim 4 wherein the one or more alpha-olefins or cyclic olefins is propylene.

6. The process of any preceding claim, wherein the total ethylene content of the VTP composition is about 20 to 100 wt%, the total alpha-olefin or cyclic olefin content of the VTP composition is about 20 to 80 wt%, and the total diene content of the VTP composition is about less than or equal to about 20 wt%, based on the VTP composition.

VTP is a copolymer of (ethylene) x (propylene) y (diene) z, wherein x is 20-80 wt%, y is 80-20 wt%, z is 0-20 wt% and x + y + z is 100 wt%.

8. The process of any preceding claim, wherein the HMP composition comprises ethylene, one or more olefins, cyclic olefins, and dienes.

9. The method of any preceding claim, wherein the first polymer composition and the second polymer composition are blended in solution to form the blended polymer composition.

10. The process of any preceding claim, wherein said first polymer composition and/or said second polymer composition is prepared at a temperature of from about 75 ℃ to about 250 ℃.

11. The process of any preceding claim, wherein said blended polymer composition has an elasticity measured by the tangent of the phase angle of from about 0.650rad/s to about 0.975 rad/s.

12. The process of any preceding claim, wherein each R of the VTP catalyst compound³Is hydrogen; each R⁴Independently is C₁-C₁₀An alkyl group; each R²And R⁷Independently is hydrogen or C₁-C₁₀Alkyl radical, each R⁵And R⁶Independently of each other is hydrogen, C₁-C₅₀Substituted or unsubstituted hydrocarbyl or C₁-C₅₀Substituted or unsubstituted halogenated hydrocarbon groups; r⁴And R⁵，R⁵And R⁶And/or R⁶And R⁷May optionally be bonded together to form a ring structure; and J is represented by formula Ra₂J 'represents, wherein J' is C or Si, and each Ra is independently C₁-C₂₀Substituted or unsubstituted hydrocarbyl, provided that two Ra can be bonded together to form a saturated or partially saturated cyclic or fused ring structure incorporating J'.

13. The method of any of the preceding claimsWherein is of the formula Ra₂Two Ra of J 'are bonded together to form a saturated or partially saturated cyclic or fused ring structure incorporating J'.

14. The process of any preceding claim, wherein, within the VTP catalyst compound, J is selected from: cyclopentylmethylenesilylene, cyclotetramethylenesilylene and cyclotrimethylenylsilylene.

15. The process of any preceding claim, wherein, within the VTP catalyst compound, R²Independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl and isomers thereof; and further wherein R⁴Independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl and isomers thereof.

16. The process of any preceding claim, wherein the VTP catalyst compound comprises cyclotetramethylenesilylene-bis (4, 7-trimethylinden-1-yl) hafnium dimethyl.

17. The method of any preceding claim, wherein the VTP composition has one or more of the following properties:

(a) a weight average molecular weight of about 5,000g/mol to about 500,000 g/mol;

(b) a weight average molecular weight (Mw)/number average molecular weight (Mn) of greater than about 2.5;

(c) g' (vis average) of less than about 0.95;

(d) a storage modulus equal to a loss modulus at 100 ℃ at less than about 4 rad/s;

(e) a storage modulus not equal to the loss modulus at 100 ℃ in the range of about 0.1rad/s to 128 rad/s;

(f) if ML (1+4, 125 ℃) is greater than or equal to about 10, then cMLA is greater than about 300; and

(g) at 0.245rad/s at 100 ℃, the tan (delta) is less than about 1.

18. The process of any preceding claim, wherein the polymer blend composition has one or more of the following properties:

(a) g, δ at 100,000Pa is less than about 48 °;

(b) a storage modulus equal to the loss modulus at 100 ℃ at less than about 0.9 rad/s;

(c) tan (delta) of less than about 1.2 at 0.245rad/s at 100 ℃; and

(d) at 125 ℃ at 0.245rad/s, the tan (. delta.) is less than about 1.6.

19. The process of any preceding claim, wherein the HMP catalyst compound is represented by the formula:

wherein:

(1) j is a divalent bridging group containing C, Si or both;

(2) m is a group 4 metal;

(3) each X is independently a monovalent anionic ligand, or two Xs are joined and bonded to a metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and

(4) each R'¹、R”²、R”³、R”⁴、R”⁵、R”⁶、R”⁷、R”⁸、R”⁹And R "¹⁰Independently of each other is hydrogen, C₁-C₅₀A hydrocarbyl, substituted hydrocarbyl, halocarbyl or substituted halocarbyl group, with the proviso that R "¹And R "²、R”³And R "⁴、R”⁵And R "⁶、R”⁶And R "⁷、R”⁸And R "⁹And R "⁹And R "¹⁰Any one or more of the pairs may optionally be bonded together to form a saturated or partially saturated cyclic or fused ring structure. In certain aspects, the bridging group J is represented by R₂C、R*₂Si、R*₂CCR*₂、R*C＝CR*、R*₂CSiR*₂Or R₂SiSiR*₂Wherein each R is independently hydrogen or C₁-C₂₀And optionally, two or more adjacent R may be joined to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent.

20. A polymer prepared by the process of any preceding claim.

21. An article comprising the polymer of claim 20.

Technical Field

The present disclosure relates to polymer compositions having enhanced elasticity, and more particularly to methods of making such compositions as follows: vinyl Terminated Polymer (VTP) and high molecular weight polymer (HMP) catalyst systems and blending of these polymer compositions are employed in a parallel process.

Background

Polymer compositions with high molecular weight distribution and high mooney viscosity are useful for dense weatherseals and sponge applications (sponge application). It is well known that long chain branching of a polymer affects the viscosity of the polymer melt. For example, an increase in the number of long chain branches in the polymer increases the elasticity of the polymer composition due to an increase in the time required for the polymer branches to relax during flow (van Ruyyembeke et al, Soft Matter 2014, 10, 4762 and references therein). Long chain branching further affects polymer processing, such as compounding and extrudability. At low shear rates, there is a high melt viscosity that is useful for compounding of polymers with various agents. Also, at low shear rates, high viscosity is useful for product stability during extrusion, for example when blowing bubbles or extruded hoses of polyethylene film or stabilized foam cells. On the other hand, the advantage of low viscosity at higher shear rates is related to extrusion (shear thinning), which increases polymer throughput.

To produce polyolefins having long chain branching ("LCB polyolefins") and polymer compositions comprising such polyolefins, dienes may be added to the polymerization process (Nele, m. et al, macromol. theory, simul.2003, 12, 582 and references therein). When each olefin of the diene is incorporated into a separate chain, long chain branches are formed. This process can lead to higher order branches on the branches, but has the following disadvantages when the level of branching becomes too high: asymptotically approaching the point of formation of insoluble gels (Guzman, j.d. et al, AiChE 2010, 56, 1325). This process can compromise reactor operability, particularly in solution polymerization processes, and can also negatively impact product appearance and provide a failure point for product testing.

Alternatively, the polymer chains may be coupled such that the olefin has reactive groups along its backbone. For example, vanadium-based processes for preparing ethylene propylene diene monomer ("EPDM") polymer compositions contain high levels of branching, the origin of which has been suggested to be due to lewis acids in systems that couple ENB (5-ethylidene-2-norbornene) from separate polymer chains (Ravishankar, PS, Rubber Chemistry and Technology 2012, 85(3)327 and references therein). Lewis bases, such as ammonia, have been reported to reduce the concentration of lewis acids, and thus the level of branching, by forming acid-base pairs. The disadvantage of this system is that, similar to the diene system, an insoluble high molecular weight gel is formed due to the very large network formed by the crosslinking.

A strategy to produce LCB polyolefins and avoid in-reactor gels is to employ macromonomers. Useful macromers are polymer chains containing one polymerizable group, such as a vinyl end group. During polymerization, they are copolymerized with other monomers to form LCB structures (Soares, J.B.P.; McKenna, T.F.L.polyofin Reaction Engineering, Wiley VCH 2012). The molecular weight of the macromer must be greater than the entanglement Molecular Weight (MW) to see a significant rheological effect. This can vary from 2000g/mol for polyethylene or syndiotactic polypropylene to 7000g/mol for atactic or isotactic PP. These are much higher than the MW of the monomers (e.g., ethylene, propylene) in the system. Thus, the molar concentration of the macromer is much lower than the other monomers in the system, and the level of incorporation is low. As a result, LCB due to macromer incorporation can be difficult to detect by spectroscopy when rheological signals of LCB are present.

In addition, it has been reported that two catalysts work together to produce long chain branched polyolefins. For example, Dekmezian reports the use of Cp₂ZrCl₂MAO from ethylene and butene and Me₂Si(tBuN)((Me₄Cp)TiCl₂Macromonomers are prepared to incorporate a portion thereof into ethylene/butene copolymers (Dekmezian et al, Macromolecules2002, 33, 9586). Walter reports the use of (Me) by rheological measurements₅Cp)₂ZrCl₂And rac-Me₂Si(2-Me，4-PhInd)₂ZrCl₂Homopolymerization and copolymerization of ethylene was carried out to prepare long-chain branched polymers (Walter et al, Polymer Bulletin 2001, 46, 205). Recently, Coates and colleagues have prepared poly (ethylene-co-propylene) macromonomers using fluorinated phenoxyiminato titanium catalysts (Coates Macromolecules 2008, 41, 559). Coats these macromonomers are subsequently homopolymerized using nickel catalysts and copolymerized with propylene using pyridyl-aminohafnium catalysts (coats Macromolecules 2015, 48, 7489).

In addition, single catalyst systems for the preparation of long chain branched polyolefins have been reported for both solution and supported catalysts. For example, supported metallocene-polyethylene catalysts are reported to produce long chain branched polyethylene in slurry or gas phase processes (Yang et al, Macromolecules2010, 43, 8366). In use (C)₆F₅)₃B modified MAO activated Me₂Si(Me₄Cp)(tBuN)TiMe₂This phenomenon is also observed in the solutions of ethylene-propylene copolymers produced (Wang et al, Polymer 2004, 45, 5497). Similarly, racemic-Me activated with MAO when at low propylene concentrations₂Si(2-Me，4-PhInd)₂ZrCl₂LCB formation of polypropylene has been observed as a catalyst (Weng et al, Macromolecules2002, 35, 3838).

For EPDM applications, High molecular weight EPDM with Long chain branching has been prepared using constrained geometry catalysts (Li Pi Shan et al, Development of High monomer Viscisity, Homogeneous Long-chain Branched EPDM, Fall 2013ACS Rubber Division Meeting). However, high molecular weight polymer compositions (including high molecular weight EPDM) cannot be prepared with metallocene catalysts. While it is possible to prepare high molecular weight EPDM in one reactor using a mixed catalyst/bimodal process, there is the problem of poisons selectively affecting one catalyst rather than another complex process control. Thus, there remains a need for a process for preparing polymer compositions having high molecular weight distribution and enhanced elasticity while providing good reactor performance using metallocene catalysts.

Disclosure of Invention

Disclosed herein is a method of making a blended polymer composition having enhanced elasticity, comprising the steps of: providing a first polymer composition, wherein the first polymer composition is a VTP composition prepared with a VTP catalyst compound; providing a second polymer composition, wherein the second polymer composition is a HMP composition prepared with a HMP catalyst compound; combining the first polymer composition and the second polymer composition; and recovering the polymer blend composition; wherein the HMP composition has a weight average molecular weight greater than the weight average molecular weight of the VTP composition; and wherein the VTP catalyst compound is represented by the formula:

wherein:

(1) j is a divalent bridging group containing C, Si or both;

(2) m is a group 4 transition metal;

(3) each X is independently a monovalent anionic ligand, or two X's join to form a chelating ligand, a diene ligand, or an alkylidene ligand; and

(4)R²-R⁷each of which is independently hydrogen, C₁-C₅₀Substituted or unsubstituted hydrocarbyl or C₁-C₅₀Substituted or unsubstituted halocarbyl (halocarbyl), with the proviso that R is⁴And R⁵、R⁵And R⁶And R⁶And R⁷Any one or more of the pairs may optionally be bonded together to form a saturated or partially saturated cyclic or fused ring structure.

Drawings

FIG. 1 shows the complex viscosity vs frequency for examples 1-4.

FIG. 2 shows Tan (. delta.) vs. frequencies for examples 1-4.

Fig. 3 is a Van Gurp Palmen plot of the phase angle (δ) vs complex viscosity (G ″) of examples 1-4.

FIG. 4 shows the complex viscosity vs frequency for examples 5-10.

FIG. 5 shows Tan (. delta.) vs. frequencies for examples 5-10.

Fig. 6 is a Van Gurp Palmen plot of phase angle (δ) vs complex viscosity (G ″) for examples 5-10.

FIG. 7 shows the complex viscosity vs frequency for blends 1-3 and comparative 1.

FIG. 8 shows Tan (. delta.) vs. frequency for blends 1-3 and comparative 1.

Fig. 9 is a Van Gurp Palmen plot of phase angle (δ) vs complex viscosity (G ″) for blends 1-3 and comparative 1.

FIG. 10 shows the complex viscosity vs frequency for blends 4-6 and comparative 2.

FIG. 11 shows Tan (. delta.) vs. frequency for blends 4-6 and comparative 2.

Fig. 12 is a Van Gurp Palmen plot of phase angle (δ) vs complex viscosity (G ″) for blends 4-6 and comparative 2.

Description of the preferred embodiments

Various specific embodiments, versions and examples are described herein, including exemplary embodiments and definitions employed for understanding the claimed invention. While the following detailed description gives certain preferred embodiments, those skilled in the art will appreciate that these embodiments are exemplary only, and that the invention can be practiced in other ways. For determining infringement, the scope of the invention will refer to any one or more of the appended claims, including their equivalents, and elements or limitations that are equivalent to those that are recited. Any reference to the "invention" may refer to one or more, but not necessarily all, of the inventions defined by the claims.

The terms "activator" and "cocatalyst" as used herein refer to one or more compounds that can activate a catalyst compound by converting a neutral catalyst compound into a catalytically active catalyst compound cation.

The term "alkyl" refers to a linear, branched, or cyclic group of carbon and hydrogen.

The term "allyl chain end" is represented by CH as shown in the formula₂CH-CH₂Represents:

wherein M represents a polymer chain. The 3-alkyl chain end, also referred to as a "3-alkylvinyl end" or "3-alkylvinyl terminus" is represented by the formula:

a 3-alkylvinyl end group,

wherein ". cndot. cndot." represents a polyolefin chain, R^bAre alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like. R^bCan be significantly larger, e.g. C_1-50、C_1-100Or greater, provided that R is^bIs a shorter alkyl chain than the polyolefin chain.

The term "anionic ligand" refers to a negatively charged ligand that donates one or more electron pairs to a metal ion.

The term "catalyst compound" may be used interchangeably with the terms "catalyst", "catalyst precursor", "transition metal compound", "transition metal complex" and "procatalyst".

The term "catalyst system" refers to a system that incorporates a catalyst, or a catalyst precursor/activator pair, and optionally a co-activator, and optionally a support material, which polymerize monomers into polymers. When the catalyst system is described as comprising a neutral stable form of a component, the ionic form of the component is the form that reacts with the monomer to produce a polymer. As used herein, when the term "catalyst system" is used to describe such precursor/activator pairs prior to activation, it refers to the catalyst that is not activated ("procatalyst" or "procatalyst") along with an activator and optionally a cocatalyst. As used herein, when the term catalyst system is used to describe such a pairing after activation, it refers to the activated catalyst and an activator or other charge-balancing moiety.

The term "continuous" refers to a system that operates without interruption or stoppage for at least a period of time. For example, the term "continuous process" refers to a process for producing a polymer in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

The terms "elastomer" or "elastomer composition" are used interchangeably and refer to any polymer or polymer composition (e.g., 5 polymer blends) that meets the ASTM D1566 definition. Elastomers include mixed blends of polymers, such as melt-mixed and/or reactor blends of polymers. The term "elastomer" may be used interchangeably with the term "rubber" and refers to any composition comprising at least one elastomer.

The terms "ethylene polymer" or "ethylene copolymer" are used interchangeably and refer to a polymer or copolymer comprising at least 50 mole% of ethylene-derived units. Ethylene refers to alpha-olefins.

The term "high molecular weight polymer or" HMP "refers to a polymer, typically a copolymer, having an Mw of 50,000g/mol or greater and prepared by the HMP catalyst system described herein. The term "HMP-VTP" is used herein to denote a subgroup of HMPs comprising one or more units derived from a vinyl-terminated polymer (VTP) as defined below and described in more detail herein.

The term "HMP catalyst" refers to a catalyst compound capable of producing the high molecular weight (Mw greater than 50,000g/mol) copolymers (HMP) described herein. The term "HMP catalyst" is not intended to limit such catalysts alone; rather, the label is provided as a convenient means of distinguishing the HMP catalysts and HMP catalyst systems described herein from other catalysts and catalyst systems (e.g., VTP catalyst systems or catalyst systems).

The term "hydrocarbyl" refers to a group containing hydrogen atoms and up to 50 carbon atoms and which may be linear, branched, or cyclic, and when cyclic, may be aromatic or non-aromatic. Also, as used herein, the terms "hydrocarbyl", and "hydrocarbyl group" are used interchangeably throughout the specification. Likewise, the terms "group," "group," and "substituent" (when referring to a subgroup of compounds) may also be used interchangeably.

The term "metallocene catalyst" refers to an organometallic compound having at least one pi-bonded cyclopentadienyl (Cp) moiety (or substituted cyclopentadienyl moiety such as indenyl or fluorenyl), more typically two pi-bonded cyclopentadienyl moieties or substituted cyclopentadienyl moieties. This includes other pi-bonded moieties such as indenyl or fluorenyl groups or derivatives thereof. The term "substituted" when used with respect to a metallocene catalyst means that a hydrogen radical has been replaced with a hydrocarbyl radical, a heteroatom or a heteroatom-containing group. For example, methylcyclopentadiene is a Cp group substituted with a methyl group.

The term "Mn" refers to the number average molecular weight. The term "Mw" refers to the weight average molecular weight. The term "Mz" refers to the z-average molecular weight. The term "wt%" refers to weight percent. The term "mol%" means mol%. As used herein, the terms "molecular weight distribution", "MWD", "polydispersity" or "PDI" are used interchangeably and refer to Mw divided by Mn, (Mw/Mn). Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol.

The fractions were determined by high temperature gel permeation chromatography (polymerChar GPC-IR) equipped with a multichannel band-filter based Infrared detector IR5(a multiple-channel band-filter based Infrared detector IR5), an 18-angle light scattering detector and a viscometerDistribution and fraction (moment) of the sub-quantities (Mw, Mn, Mw/Mn, etc.), comonomer content (C)₂、C₃、C₆Etc.) and long chain branching (g'). Three Agilent PLGel 10 μm Mixed-B LS columns were used to provide polymer separations. Aldrich reagent grade 1,2, 4-Trichlorobenzene (TCB) containing 300ppm of the antioxidant Butylated Hydroxytoluene (BHT) was used as the mobile phase. The TCB mixture was filtered through a 0.1 μm Teflon filter and degassed with an in-line degasser before entering the GPC instrument. The nominal flow rate was 1.0mL/min and the nominal injection volume was 200. mu.L. The oven maintained at 145 ℃ was charged with the entire system including transfer lines, columns and detectors. A given amount of polymer sample was weighed and sealed in a standard vial, to which was added 80 μ L of the flow marker (heptane). After loading the vial into the autosampler, the polymer was automatically dissolved in the instrument with 8mL of added TCB solvent. The polymer was dissolved at 160 ℃ while shaking continuously for about 1 hour (for most PE samples) or continuously for about 2 hours (for PP samples). The TCB density used for concentration calculations was 1.463g/ml at room temperature and 1.284g/ml at 145 ℃. The sample solution concentration is 0.2-2.0mg/ml, with lower concentrations being used for higher molecular weight samples.

The concentration of each point in the chromatogram (c) was calculated from the baseline-subtracted IR5 broadband signal intensity (I) using the following equation:

c＝βI,

where β is the mass constant determined with PE or PP standards. Mass recovery was calculated from the ratio of the integrated area of the concentration chromatogram to the elution volume and the injection mass was equal to the pre-determined concentration multiplied by the injection loop volume.

Routine molecular weight (IR MW) was determined by combining the universal calibration relationship with column calibration performed with a series of 700-10M monodisperse Polystyrene (PS) standards. The MW at each elution volume was calculated using the following equation.

Wherein the variable having the subscript "PS" represents polystyrene, and notThose variables with subscripts represent the test samples. In this process, a_PS0.67 and K_PS0.000175 and a and K were established by ExxonMobil and were disclosed in literature (T.Sun, P.Brant, R.R.Chance and W.W.Graessley, Macromolecules, Vol.34, No. 19, p.6812-6820, (2001)). In particular, a/K is 0.695/0.000579 for PE and 0.705/0.0002288 for PP.

Comonomer composition consisting of CH corresponding to calibration with a series of PE and PP homo/copolymer standards₂And CH₃The ratio of the IR5 detector intensities of the channels was determined, the nominal values of the standard samples were determined beforehand by NMR or FTIR.

The LS detector is an 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point of the chromatogram was determined by analyzing the LS output using a Zimm model of static Light Scattering (M.B. Huglin, Light Scattering from Polymer Solutions, Academic Press, 1971):

wherein Δ R (θ) is the excess rayleigh scattering intensity measured at the scattering angle θ; c is the polymer concentration determined from IR5 analysis; a. the₂Is a second virial coefficient; p (θ) is the form factor of the monodisperse random coil; and K_oIs the optical constant of the system:

wherein N is_AIs an avogalois value; dn/dc is the refractive index increment of the system. The refractive index n is 1.500 for TCB at 145 ℃ and λ 665 nm.

Specific viscosity was measured using a high temperature Agilent (or Viscotek Corporation) viscometer having four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors. One sensor measures the total pressure drop across the detector and the other sensor, located between the two sides of the bridge, measures the pressure difference. The specific viscosity η s of the solution flowing through the viscometer is calculated from their output values. The intrinsic viscosity [ η ] at each point in the chromatogram is calculated by the following equation:

[η]＝ηs/c,

where c is concentration and is measured from the IR5 broadband channel output. The viscosity MW at each point is calculated by the following equation:

the branching index (g' VIS) was calculated as follows from the output of the GPC-IR5-LS-VIS method. Average intrinsic viscosity [ eta ] of sample]_avgThe following calculations were made:

where the sum is taken from all chromatogram slices i between the integration limits. The branching index g' vis is defined as:

mv is the viscosity average molecular weight based on the molecular weight determined by LS analysis. K/a is used for the reference linear polymer, which is usually PE with a certain amount of short chain branching.

For GPC analysis, the concentration is in g/cm³Molecular weight is expressed in g/mole and intrinsic viscosity is expressed in dL/g unless otherwise indicated.

As used herein, the terms "mooney viscosity" or "ML" are used interchangeably and refer to the measured or reported mooney viscosity of a polymer or polymer composition. Mooney viscosity as used herein is measured as ML (1+4) in Mooney units at 125 ℃ according to ASTM D-1646. Square samples were placed on both sides of the rotor. The inner cavity is filled by pneumatically lowering the upper platen. The upper and lower platens were electrically heated and controlled at 125 ℃. The torque to rotate the rotor at 2rpm was measured with a sensor. After the platens were closed, the samples were preheated for 1 minute. The motor was then started and the torque was recorded for 4 minutes. The results are reported as ML (1+4)125 ℃, where M is the mooney viscosity value, L represents the large rotor, 1 is the preheat time (in minutes), 4 is the sample run time (in minutes) after motor start-up, and 125 ℃ is the test temperature.

When the rubber has relaxed after the rotor has stopped, the mooney relaxation area is obtained from the mooney viscosity measurement. MLRA is the integrated area under the mooney curve from 1 to 100 seconds. The mooney relaxation area depends on the mooney viscosity of the polymer, and increases with increasing mooney viscosity. To eliminate the dependence on polymer mooney viscosity, a corrected MLRA (cmlra) parameter was used, where the MLRA of the polymer was normalized to the 80 mooney viscosity benchmark. The formula for cMLA is provided below:

cMLRA＝MLRA(80/ML)^1.44

wherein MLRA and ML are the Mooney relaxation area and Mooney viscosity of the polymer sample measured at 125 ℃.

The parameter cMLRA can be considered as an energy storage term, which indicates that longer or branched polymer chains store more energy and will take longer to relax after the applied strain is removed. The cMLRA value of the bimodal or branched polymers is generally higher than that of the linear polymers or mixtures thereof.

However, mooney viscosity values greater than about 100 are generally not measurable under these conditions. In this case, mooney measurements were performed using the following non-standard small rotor.

With a non-standard rotor design, having a mooney scale variation allows the same equipment on the mooney machine to be used for higher mooney polymers. This rotor is called MST-Mooney Small Thin. When MST is measured at ([email protected] ℃ C.) and ML is measured at ([email protected] ℃ C.), one MST point is about the 5ML point.

ASTM D1646-99 specifies the dimensions of the rotor to be used inside the Mooney machine cavity. This standard allows large and small rotors that differ only in diameter. They are referred to as ML (Mooney Large) and MS (Mooney Small). However, EPDM can be made at such high MW that the torque limits of mooney machines may be exceeded by the specified rotors using these standards. In these cases, tests were performed using MST rotors of smaller diameter and thinner. Typically, when MST rotors are used, the tests will also be performed at different times and temperatures. The preheat time was changed from the standard 1 minute to 5 minutes and the test was run at 200 deg.C (instead of the standard 125 deg.C). Thus, the value will be reported as MST (5+4), 200 ℃. It should be noted that at the end of the 4 minute run time, the mooney readings were still the same as the standard conditions. The Mooney Small Thin Relaxation Area (MSTRA) is obtained from the mooney small thin viscosity measurement when the rubber has relaxed after the rotor stops. MSTRA is the integrated area under the Mooney curve from 1 to 100 seconds.

The MST rotor should be prepared as follows: the diameter of the rotor should be 30.48 + -0.03 mm and the thickness should be 2.8 + -0.03 mm (the top of the serrations) and the diameter of the shaft should be 11mm or less. The rotor should have serrated faces and edges with square grooves 0.8mm wide and 0.25-0.38mm deep cut on the 1.6mm center. The serrations consist of two sets of grooves at right angles to each other (forming a square cross-hatch). The rotor should be centered in the mold cavity so that the centerline of the turntable coincides with the mold cavity centerline to within a tolerance of + -0.25 mm. Spacers or shims may be used to raise the shaft to the midpoint.

The term "olefin" refers to a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this disclosure, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, the monomer units in the copolymer are derived from ethylene in the polymerization reaction and the derived units are present at 35 wt% to 55 wt% based on the weight of the copolymer. The alpha-olefin comprises up to 2000 monomer units of an alpha-olefinic macromonomer.

The olefin content was measured by NMR spectroscopy. Using ODCB/C₆D₆Samples were prepared at 130 ℃ and 140 ℃ from a solution prepared from approximately 20mg of polymer and 1mL of solvent mixture.

ODCB (ortho-dichlorobenzene) and benzene-d on a 5mm or 10mm probe with a field strength of at least 500MHz₆(C₆D₆) In the mixture (9:1) at 120 ℃ with a flip angle of 30 °, a delay of 15s and 512 transients¹NMR of H solution. The signal was integrated and percent ENB weight reported.

The calculation of ENB and double bonds was performed as follows:

I_Primaryintegration of the main ENB species at 5.2-5.4ppm

I_{Of secondary importance}Integral of secondary ENB species at 4.6-5.12ppm

I_eth＝(–CH₂Integration at 0-3 ppm)

Total ═ ENB + EP)

Total wt ═ ENB 120+ EP 14)

Peak assignment	Strength of matter	Branched/1000 carbons
			Vinylidene (5.55-5.31ppm)	IVinylidene radicalVinylidene group/2	Vinylidene 1000 per total
Trisubstituted (5.30-5.12ppm)	ITrisubstituted1-trisubstituted	I trisubstitution 1000/Total
			Vinyl (5.09-4.95ppm)	IVinyl radicalVinyl radical/2	Monovinyl 1000/total
Vinylidene (4.84-4.69ppm)	IVinylidene radicalVinyl group/2	Ivinylidene 1000/total

The trisubstitution may have an overlap with the primary ENB.

The term "polymer" refers to a compound having two or more identical or different monomer units. The term "homopolymer" refers to a polymer comprising the same monomer units. The term "copolymer" refers to a polymer having two or more monomer units that are different from each other. The term "terpolymer" refers to a polymer having three monomer units that differ from each other. Thus, the definition of copolymer as used herein includes terpolymers and the like.

The term "polymerization catalyst system" refers to a catalyst system that can polymerize monomers into polymers.

The terms "propylene polymer" or "propylene copolymer" are used interchangeably and refer to a polymer or copolymer comprising at least 50 mole% of propylene derived units. Additional polymers may be defined in a similar manner, as described herein.

The term "ring structure" refers to atoms bonded together in one or more cyclic arrangements.

The term "rubber" is meant to conform to the ASTM D1566 definition: any polymer or combination of polymers that is capable of recovering from large deformations and that can, or has been modified to a material in which it is substantially insoluble (but can swell in) boiling solvents.

Using those from Alpha TechnologiesThe 1000 rubber processing analyzer performs small angle vibratory shear (SAOS) measurements. A sample of approximately 4.5g weight was mounted on the ATDBetween the parallel plates. The test temperature is 100 ℃ or 125 ℃, the applied strain is 14% and the frequency is 0.1rad/s to 200 rad/s. The complex modulus (G), complex viscosity (η), and phase angle (δ) were measured at each frequency. The phase angle at G ═ 100,000Pa was calculated from a cubic fit of the data. The crossover point (when the storage and loss moduli are equal and δ is 45 °) is calculated from a linear interpolation of the δ vs frequency data.

The term "scavenger" refers to a compound that is typically added to promote oligomerization or polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. Co-activators (not scavengers) may also be used in combination with the activator to form an active catalyst. In some embodiments, the co-activator may be premixed with the transition metal compound to form an alkylated transition metal compound.

The term "transition metal compound" refers to a catalyst compound that is neutral, e.g., a procatalyst, or that is a charged species with a counterion, e.g., in an activated catalyst system.

The term "vinyl chain end" or "vinyl terminus" refers to the vinyl group at the end of the polymer and can be located on any one or more of the ends of the polymer. The vinyl chain ends may be "allyl chain ends" or "3-alkyl chain ends". References to vinyl-terminated "macromers" are not intended to limit the size (e.g., Mw or Mn) of the VTP alone, nor the necessary use of the VTP, but merely for convenience, as a "monomer" to be incorporated into another polymer, such as HMP, in view of the possible processing of the VTP.

The terms "vinyl-terminated polymer," "vinyl-terminated macromer" or "VTP" (plural VTP) are used interchangeably and refer to a polymer having a specified percentage (e.g., greater than 40%) of vinyl chain ends, relative to total polymer chain end unsaturation, that can be suitably used as a macromer.

The term "VTP catalyst" refers to a catalyst compound capable of preparing the VTP and VTP compositions described herein. The VTP catalyst is capable of producing polymers having greater than 60% vinyl chain ends (preferably greater than 70%, preferably greater than 80%, preferably greater than 85%, preferably greater than 90%, preferably greater than 95%, preferably greater than 98%) relative to total polymer chain end unsaturation. As with the HMP catalyst, the term "VTP catalyst" is not solely intended to limit the type of catalyst. Rather, labels are provided as a convenient means of distinguishing the VTP catalysts and catalyst systems described herein from other catalysts and catalyst systems (e.g., HMP catalysts or catalyst systems).

The weight% of ethylene (C2) and 5-ethylidene-2-norbornene (ENB) were determined by infrared spectroscopy of polymer films according to ASTM methods D3900 and D6047, respectively.

As used herein, the new numbering scheme for groups of the periodic Table of the elements is the new notation given in Chemical and Engineering News,63(5),27 (1985). Thus, a "group 4 metal" is an element selected from group 4 of the periodic table, such as Zr, Ti and Hf.

Process for making polymer blend compositions

The process of the present invention comprises blending/combining polymer compositions prepared by different catalyst systems. One such catalyst system includes (i) a vinyl-terminated polymer (VTP) catalyst system comprising a VTP catalyst compound (also referred to herein as a "VTP catalyst") and one or more activators. Another catalyst system includes a high molecular weight polymer (HMP) catalyst system comprising an HMP catalyst compound (also referred to herein as an "HMP catalyst") and one or more activators. The activators of these different catalyst systems may be completely or partially the same or different.

The first polymer composition and/or the second polymer composition is prepared from a plurality of monomersAt least a portion of (a). The plurality of monomers comprises at least: (1) first C₂-C₂₀An alpha-olefin; (2) a second C different from the first₂-C₂₀An alpha-olefin; and, optionally, (3) one or more dienes. In one aspect, the plurality of monomers comprises: (1) ethylene; (2) second C₃-C₂₀Alpha-olefins such as propylene and/or butene; and (3) one or more dienes.

The blend components may be physically mixed as solids and melt blended in an extruder. More preferably, the blend components are blended in solution. Even more preferably, the blend components are prepared in a parallel solution process in two reactors and blended in-line after discharge from the reactors. The solvent in the process is preferably an alkane or a mixture of alkanes, which may be linear, branched or cyclic. More preferably, the solvent is predominantly isohexane.

VTP catalyst system

As described herein, in certain aspects, a VTP catalyst system includes a catalyst compound and an activator, and optionally a support and/or optionally a co-activator. The VTP catalyst system produces vinyl terminated polymer compositions (VTP compositions) having rheological and molecular weight characteristics consistent with long chain branched polymers.

As described herein, VTP catalyst systems are capable of forming VTPs, i.e., polymers and copolymers having greater than 40% vinyl chain ends relative to total polymer chain end unsaturation. The VTP polymer is made from one or more of ethylene, alpha-olefins, cyclic olefins, and dienes. Preferably, the monomers are ethylene and alpha-olefins such as 1-hexene, 1-butene or propylene. In another preferred embodiment, the monomers are ethylene, propylene and 5-ethylidene-2-norbornene. The polymer preferably has an Mw of 5,000-500,000 g/mol. More preferably, the Mw is 20,000-400,000, even more preferably the Mw is 100,000-300,000 g/mol. The VTP polymer preferably has a g' (vis average)<0.95, more preferably<0.9, even more preferably<0.85. The molecular weight distribution of the polymer is preferably>2.5, more preferably>3, even more preferably>3.5. The polymer preferably has a small angle oscillatory shear rheology of Tan (. delta.), i.e., at 0.245s^-1The ratio of the lower loss modulus to the storage modulus (G '/G') is not more than 1, more preferably Tan (. delta.) not more than 0.9, even more preferably Tan (. delta.) not more than 0.8 at 100 ℃ or 125 ℃. Another characteristic of the VTP polymer is that the shear-thinning ratio (complex viscosity at 0.1 Rad/s)/(complex viscosity at 128 Rad/s) at 100 ℃ or 125 ℃ is preferably > 50, more preferably > 100. The thinning ratio (complex viscosity at 0.1 Rad/s)/(complex viscosity at 128 Rad/s) at 100 ℃ or 125 ℃ is preferably > 50, more preferably > 100. Another characteristic of VTP polymers is the low frequency at which the storage and loss moduli are equal. At 100 ℃ or 125 ℃, in preferred embodiments, at < 4Rad/s, G "/G '═ 1, and in more preferred embodiments, at < 0.1Rad/s, G"/G' ═ 1. In the latter case, the plots of G 'and G' for the VTP versus frequency do not cross between 0.1 and 128 Rad/s. Another characteristic of VTP polymers is that the phase angle is less than 50 °, preferably less than 45 °, even more preferably less than 40 ° when G ═ 100,000Pa at 100 ℃ or 125 ℃. Another feature of VTP polymers is high cMLRA. When ML (1+4, 125 ℃ C.)>10, cMLA is preferred>300, more preferably>400, even more preferably>500。

An activator is used with the VTP catalyst compound.

VTP catalyst compounds

VTP catalyst compounds that may be used in the VTP catalyst systems described herein include metallocenes represented by the following formula:

wherein:

(1) j is a divalent bridging group containing C, Si or both; (2) m is a group 4 transition metal (preferably Hf); (3) each X is independently a monovalent anionic ligand, or two xs are joined and bonded to a metal atom to form a metallocycle ring (a metallocene ring), or two xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and (4) R²、R³、R⁴、R⁵、R⁶And R⁷Each of which is independently hydrogen, C₁-C₅₀SubstitutionOr unsubstituted hydrocarbon radicals, or C₁-C₅₀A substituted or unsubstituted halogenated hydrocarbon group, with the proviso that R⁴And R⁵、R⁵And R⁶And R⁶And R⁷Any one or more of the pairs may optionally be bonded together to form a saturated or partially saturated cyclic or fused ring structure. Such VTP catalyst compounds are also known as bis-indenyl metallocene compounds.

In certain aspects, each X is independently selected from the group consisting of hydrocarbyl groups containing 1-20 carbon atoms, hydride groups (hydrides), amide groups (amides), alkoxy groups (alkoxides), sulfide groups (sulfides), phosphide groups (phosphides), halide groups (halides), dienes, amines, phosphines, ethers, and combinations thereof. Two X may form part of a fused ring or ring system. In particular embodiments, each X is independently selected from halo and C₁-C₅An alkyl group. For example, each X may be chloro, bromo, methyl, ethyl, propyl, butyl or pentyl. In particular embodiments, each X is methyl.

In one aspect, each R²、R³、R⁴、R⁵、R⁶And R⁷Independently selected from the group consisting of: h; CH (CH)₃；CH₂CH₃；CH₂CH₂CH₃；CH₂(CH₂)₂CH₃；CH₂(CH₂)_3-30CH₃；CH₂C(CH₃)₃；CH＝CH₂；CH(CH₃)₂；CH₂CH(CH₃)₂；CH₂CH₂CH(CH₃)₂；C(CH₃)₂CH(CH₃)₂；CH(C(CH₃)₃)CH(CH₃)₂；C(CH₃)₃；CH₂C(CH₃)₃CH₂Si(CH₃)₃；CH₂Ph；C₃H₅,C₄H₇；C₅H₉；C₆H₁₁；C₇H₁₃；C₈H₁₅；C₉H₁₇；CH₂Si(CH₃)₃；CH₂CH＝CH₂；CH₂CH₂CH＝CH₂；CH₂CH₂(CF₂)₇CF₃；CF₃；N(CH₃)₂；N(C₂H₅)₂(ii) a And OC (CH)₃)₃。

In one aspect, each R²、R³、R⁴、R⁵、R⁶And R⁷May be independently selected from hydrogen, or C₁-C₁₀Alkyl (preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or their isomers).

In still other aspects, each R³Is hydrogen; each R⁴Independently is C₁-C₁₀Alkyl (preferably methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or isomers thereof); each R²And R⁷Independently is hydrogen, or C₁-C₁₀Alkyl (preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or isomers thereof); each R⁵And R⁶Independently is hydrogen, or C₁-C₅₀Substituted or unsubstituted hydrocarbon groups (preferably hydrogen, methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl or isomers thereof); and R⁴And R⁵，R⁵And R⁶And/or R⁶And R⁷May optionally be bonded together to form a ring structure.

In one aspect, each R²Independently is C₁-C₃Alkyl groups such as methyl, ethyl, n-propyl, isopropyl or cyclopropyl. R³、R⁵、R⁶And R⁷May be hydrogen, R⁴And R⁷May independently be C₁-C₄Alkyl, preferably methyl, ethyl, propyl, butyl or their isomers.

In addition, each R²、R⁴And R⁷Can independently beMethyl, ethyl or n-propyl, each R⁵And R⁶Independently is C₁-C₁₀Alkyl radicals such as the methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl radical or their isomers, R³Is hydrogen, R⁵And R⁶Joined together to form a 5-membered partially unsaturated ring.

In one aspect, each R²、R⁴And R⁷Are identical and are selected from C₁-C₃Alkyl radicals such as methyl, ethyl, propyl and their isomers, and R³、R⁵And R⁶Is hydrogen.

In one aspect, the VTP catalyst compound, R⁴Is not aryl (substituted or unsubstituted). Aryl is defined as a single or multiple fused ring group in which at least one ring is aromatic. Substituted aryl is aryl in which a hydrogen has been replaced by a heteroatom or heteroatom-containing group. Examples of substituted and unsubstituted aryl groups include phenyl, benzyl, tolyl, carbazolyl, naphthyl, and the like. Also, in certain aspects, R²、R⁴And R⁷Is not a substituted or unsubstituted aryl group. In even other aspects, R²、R⁴、R⁵、R⁶And R⁷Is not a substituted or unsubstituted aryl group.

J may be represented by formula (1 a):

wherein J 'is a carbon or silicon atom, x is 1,2,3 or 4, preferably 2 or 3, and each R' is independently hydrogen or C₁-C₁₀Hydrocarbyl, preferably hydrogen. Specific examples of the J group wherein J' is silicon include cyclopentylmethylenesilylene, cyclotetramethylenesilylene, cyclotrimethylenylsilylene and the like. Specific examples of the J group wherein J' is carbon include a cyclopropane group, a cyclobutane group, a cyclopentanediyl group, a cyclohexanediyl group, and the like.

In one aspect, J can be represented by the formula (R)^a ₂J ') n, wherein each J' is independentlyStanding on the earth is C or Si, n is 1 or 2, each R^aIndependently is C₁-C₂₀Substituted or unsubstituted hydrocarbyl, provided that two or more R^aOptionally may be joined together to form a saturated or partially saturated or aromatic cyclic or fused ring structure comprising at least one J'. Specific examples of the J group include dimethylsilylene group, diethylsilylene group, isopropylidene group, ethylene group and the like.

For example, the VTP catalyst compound, bis-indenyl metallocene, useful in the process of the present invention may have at least 90% of the racemic isomer and the indenyl may be substituted at the 4-position with C₁-C₁₀Alkyl, hydrogen in position 3, and the bridge being carbon or silicon incorporated into a 4-, 5-or 6-membered ring.

Additionally, the VTP catalyst compound may be cyclotetramethylenesilylene-bis (2,4, 7-trimethylinden-1-yl) hafnium dimethyl, as shown below:

as indicated, the catalyst compounds useful in the process of the present invention may be in racemic or meso form. In one aspect, the catalyst compound is in racemic form. For example, at least 90 wt% of the catalyst compound can be in racemic form, based on the weight of the racemic and meso forms present. More specifically, at least any one of about 92, 93, 94, 95, 96, 97, 98, and 99 wt% of the catalyst compound can be in racemic form. In one aspect, all of the catalyst compounds are in racemic form.

Useful VTP catalyst compounds include metallocene catalysts, such as bridged group 4 transition metal (e.g., hafnium or zirconium, preferably hafnium) metallocene catalyst compounds having two indenyl ligands. Other useful VTP catalyst compounds may include any one or more of the following:

cyclotetramethylenesilyl-bis (2,4, 7-trimethylinden-1-yl) hafnium dimethyl, cyclopentamethylenesilyl-bis (2,4, 7-trimethylinden-1-yl) hafnium dimethyl, cyclotrimethylenesilyl-bis (2,4, 7-trimethylinden-1-yl) hafnium dimethyl, cyclotetramethylenesilyl-bis (2, 4-dimethylinden-1-yl) hafnium dimethyl, cyclopentamethylenesilyl-bis (2, 4-dimethylinden-1-yl) hafnium dimethyl, cyclotrimethylenesilyl-bis (2, 4-dimethylinden-1-yl) hafnium dimethyl, cyclotetramethylenesilyl-bis (4, 7-dimethylinden-1-yl) hafnium, cyclopentamethylenesilylbis (4, 7-dimethylinden-1-yl) hafnium dimethyl, cyclotrimethylenesilylbis (4, 7-dimethylinden-1-yl) hafnium dimethyl, cyclotetramethylenesilyl-bis (2-methyl-4-cyclopropylinden-1-yl) hafnium dimethyl, cyclopentamethylenesilyl-bis (2-methyl-4-cyclopropylinden-1-yl) hafnium dimethyl, cyclotrimethylenesilyl-bis (2-methyl-4-cyclopropylinden-1-yl) hafnium dimethyl, cyclotetramethylenesilyl-bis (2-ethyl-4-cyclopropylinden-1-yl) Group) hafnium, cyclopentamethylenesilylbis (2-ethyl-4-cyclopropylinden-1-yl) hafnium dimethyl, cyclotrimethylenesilylbis (2-ethyl-4-cyclopropylinden-1-yl) hafnium dimethyl, cyclotetramethylenesilyl- (2-methyl-4-tert-butylinden-1-yl) hafnium dimethyl, cyclopentamethylenesilyl-bis (2-methyl-4-tert-butylinden-1-yl) hafnium dimethyl, cyclotrimethylenesilyl-bis (2-methyl-4-tert-butylinden-1-yl) hafnium dimethyl, cyclotetramethylenesilyl-bis (4, 7-diethylinden-1-yl) hafnium, cyclopentylmethylenesilylene-bis (4, 7-diethylinden-1-yl) hafnium dimethyl, cyclotrimethylenesilylene-bis (4, 7-diethylinden-1-yl) hafnium dimethyl, cyclotetramethylenesilylene-bis (2, 4-diethylinden-1-yl) hafnium dimethyl, cyclopentylmethylenesilylene-bis (2, 4-diethylinden-1-yl) hafnium dimethyl, cyclotrimethylsilylene-bis (2, 4-diethylinden-1-yl) hafnium dimethyl, cyclotetramethylsilylene-bis (2-methyl-4, 7-diethylinden-1-yl) hafnium, Cyclopentamethylenesilylene-bis (2-methyl-4, 7-diethylinden-1-yl) hafnium dimethyl, cyclotrimethylsilylene-bis (2-methyl-4, 7-diethylinden-1-yl) hafnium dimethyl, cyclotetramethylsilylene-bis (2-ethyl-4-methylinden-1-yl) hafnium dimethyl, cyclopentylmethylenesilylene-bis (2-ethyl-4-methylinden-1-yl) hafnium dimethyl, cyclotrimethylsilylene-bis (2-ethyl-4-methylinden-1-yl) hafnium dimethyl, cyclotetramethylsilylene-bis (2-methyl-4-isopropylinden-1-yl) hafnium, Cyclopentylmethylenesilylene-bis (2-methyl-4-isopropylinden-1-yl) hafnium dimethyl, cyclotrimethylsilylene-bis (2-methyl-4-isopropylinden-1-yl) hafnium dimethyl, cyclotetramethylsilylene-bis (4,6, 8-trimethyl-1, 2, 3-trihydro-s-indacen-5-yl) hafnium dimethyl, cyclopentylmethylenesilylene-bis (4,6, 8-trimethyl-1, 2, 3-trihydro-s-indacen-5-yl) hafnium dimethyl and cyclotrimethylsilylene-bis (4,6, 8-trimethyl-1, 2, 3-trihydro-s-indacen-5-yl) hafnium.

Other useful VTP catalyst compounds are listed and described in U.S. published application 2015/0025209 (now US 9,458,254) in paragraphs [0089] to [0090], which is incorporated herein by reference. Likewise, VTP catalyst compounds may be synthesized via a variety of methods, including according to the procedures described in paragraphs [0096] and [00247] to [00298] of U.S. published application No. 2015/0025209.

The VTP catalyst used in the examples of the invention was Cat2 as shown below:

HMP catalyst system

The HMP catalyst system comprises a catalyst compound and an activator, and optionally, a support and a co-activator. The HMP catalyst systems described herein are capable of producing high molecular weight polymer compositions ("HMP polymer compositions" or "HMP compositions") having a molecular weight greater than 50,000 g/mol. HMP polymers are polymers or blends of polymers composed of one or more olefins, including ethylene, alpha-olefins, cyclic olefins, and dienes. When a diene is present, it is preferably 5-ethylidene-2-norbornene. Preferably, the monomers are ethylene and alpha-olefins such as 1-hexene, 1-butene or propylene. In another preferred embodiment, the monomers are ethylene, propylene and 5-ethylidene-2-norbornene.

HMP catalyst compounds

The HMP catalyst compound useful in the process of the present invention can be any catalyst compound capable of preparing a high Mw copolymer and incorporating ethylene, an α -olefin, and optionally, a cyclic comonomer such as 5-ethylidene-2-norbornene.

Suitable catalyst compounds meeting these criteria include, for example, mono-Cp amino group 4 complexes, bridged fluorenyl-cyclopentadienyl group 4 complexes, Biphenol (BPP) transition metal complexes, pyridylamino transition metal complexes, and/or pyridyldiamido transition metal complexes.

Suitable mono-Cp amino group 4 complexes include compounds of the general structural formula (2):

wherein:

(1) m is a group 4 metal, preferably titanium; (2) l is¹Is a divalent substituted or unsubstituted monocyclic or polycyclic aryl ligand bonded to the M pi-bond; (3) j is a divalent bridging group; (4) z is an element of group 15 or 16 of the periodic Table of the elements, having a coordination number of 3 if from group 15, having a coordination number of 2 if from group 16, and Z is the coordination number of the element Z, such that when Z is an element of group 16, Z is 2 and R'⁵Is absent; (5) r'⁵Is the following group: a hydrocarbyl, substituted hydrocarbyl, halocarbyl or substituted halocarbyl group; (6) l'_wIs a neutral Lewis base, w represents the number of L's bonded to M, wherein w is 0, 1 or 2, and optionally any L' and any X may be bonded to each other; and (7) each of X is independently halo, hydrido, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylhydrocarbyl, substituted silylhydrocarbyl, germylcarbyl (germylcarbyl radial), or substituted germylA hydrocarbyl group; or two xs are joined and bonded to the metal atom to form an ametalytic ring containing from about 3 to about 20 carbon atoms; or two X together may be an alkene, diolefin or aryne ligand. In some embodiments, two xs may independently be halogen, alkoxy, aryloxy (aryloxide), amino, phosphorus, or other monovalent anionic ligands or two xs may also be joined to form an anionic chelating ligand.

Suitably L¹Monocyclic or polycyclic aryl ligands include substituted and unsubstituted cyclopentadienyl, indenyl, fluorenyl, heterocyclopentadienyl, heterophenyl, heteropentalenyl, heterocyclopentacyclopentalenyl, heteroindenyl, heterofluorenyl, heterocyclopentanyl, heterobenzocyclopentindenyl, and the like.

In some embodiments, the mono-Cp amino group 4 complex comprises a compound of the following general structural formula (2 a):

wherein: (1) j is a divalent bridging group containing C, Si or both; (2) m is a group 4 metal (e.g., Hf, Zr, or Ti, with Ti being preferred in certain embodiments); (3) each X is independently a monovalent anionic ligand, or two Xs are joined and bonded to a metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; (4) each R'¹、R'²、R'³、R'⁴And R'⁵Independently of each other is hydrogen, C₁-C₅₀Hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl or substituted halohydrocarbyl provided that R'¹And R'²、R'²And R'³、R'³And R'⁴Any one or more of the pairs may optionally be bonded together to form a saturated or partially saturated cyclic or fused ring structure; and (5) Z is an element of group 15 or 16 of the periodic Table of the elements, if from group 15, hasHas a coordination number of 3, has a coordination number of 2 if from group 16, and Z is the coordination number of element Z. Preferably, Z is N, O, S or P, preferably N, O or P, preferably N. When Z is a group 16 element, Z is 2 and R'⁵Is absent.

In certain embodiments, bridging group J is represented by R₂C、R*₂Si、R*₂CCR*₂、R*C＝CR*、R*₂CSiR*₂Or R₂SiSiR*₂Wherein each R is independently hydrogen or C₁-C₂₀Optionally, two or more adjacent R may be joined to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. In another embodiment, J is a bridging group comprising carbon and/or silicon atoms, e.g. a dialkylsilyl group, preferably J is selected from CH₂、CH₂CH₂、C(CH₃)₂、SiMe₂、SiEt₂、SiPh₂、SiMePh、Ph₂C、(p-(Et)₃SiPh)₂C、Si(CH₂)₃、Si(CH₂)₄And Si (CH)₂)₅。

Alternatively, J may be any of the compounds described for "J" in the VTP catalyst above.

In certain embodiments, each X is selected according to the VTP catalyst compounds described previously herein. That is, each X can be independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, halogens, hydrogen groups, amino groups, alkoxy groups, thio groups, phosphorus groups, halogen groups, dienes, amines, phosphines, ethers, and combinations thereof. Two X may form part of a fused ring or ring system. In particular embodiments, each X is independently selected from halo and C₁-C₅An alkyl group. For example, each X may be chloro, bromo, methyl, ethyl, propyl, butyl or pentyl. In particular embodiments, each X is methyl.

In some embodiments, each R'¹、R'²、R'³、R'⁴And R'⁵Independently selected from the following: h; CH (CH)₃；CH₂CH₃；CH₂CH₂CH₃；CH₂(CH₂)₂CH₃；CH₂(CH₂)_3-30CH₃；CH₂C(CH₃)₃；CH＝CH₂；CH(CH₃)₂；CH₂CH(CH₃)₂；CH₂CH₂CH(CH₃)₂；C(CH₃)₂CH(CH₃)₂；CH(C(CH₃)₃)CH(CH₃)₂；C(CH₃)₃；CH₂Si(CH₃)₃；CH₂Ph；C₄H₇；C₅H₉；C₆H₁₁；C₇H₁₃；C₈H₁₅；C₉H₁₇；C₁₂H₂₃,C₁₀H₁₅,C₆H₅；CH₂Si(CH₃)₃；CH₂CH＝CH₂；CH₂CH₂CH＝CH₂；CH₂CH₂(CF₂)₇CF₃；CF₃；N(CH₃)₂；N(C₂H₅)₂And OC (CH)₃)₃。

In particular embodiments, R'¹、R'²、R'³And R'⁴Each of which is independently C₁-C₁₀Alkyl or hydrogen. For example, R'¹、R'²、R'³And R'⁴Each of which may be methyl or hydrogen. In particular embodiments, R'¹、R'²、R'³And R'⁴Each of which is a methyl group (as in the case of the HMP catalyst compound, according to some embodiments, titanium dimethyldimethylsilylene (tetramethylcyclopentadienyl) (cyclododecylamino) hydride). Alternatively, in other embodiments, R'¹、R'²、R'³And R'⁴Is hydrogen, R 'remaining'¹、R'²、R'³And R'⁴Each is methyl, (as in accordance with other embodiments)Dimethyl dimethylsilylene (trimethylcyclopentadienyl) (cyclododecylamino) titanium) as in the HMP catalyst compound of (1). In still other embodiments, R'¹And R'²、R'²And R'³、R'³And R'⁴Any pair of the pairs may be bonded together so as to form an indenyl, s-indacenyl (indacenyl) or as-indacenyl group (as is the case with HMP catalyst compounds according to other embodiments, e.g., dimethylsilylene (6-methyl-1, 2,3, 5-tetrahydro-s-indacen-5-yl) (tert-butylamino) titanium dimethyl.

In still other embodiments, Z is nitrogen, R'⁵Is selected from C₁-C₃₀Hydrocarbyl, substituted hydrocarbyl, halocarbyl or substituted halocarbyl.

In other embodiment embodiments, Z is nitrogen, R'⁵Is C₁-C₁₂Examples of the hydrocarbon group include methyl, ethyl, propyl (n-or i-propyl), butyl (n-or i-butyl, sec-or t-butyl), and the like. For example, R'⁵May be a tert-butyl group. Or, in certain embodiments, R'⁵There may be cyclic groups such as adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclododecyl or norbornyl (norbonyl). Or, in certain embodiments, R'⁵May be an aromatic group such as phenyl, tolyl, naphthyl, anthracenyl, and the like. In some embodiments, R'⁵Is tert-butyl and/or cyclododecyl, preferably Z is N.

Specific examples of some suitable mono-Cp amido group 4 HMP catalyst compounds therefore include: dimethylsilylene (tetramethylcyclopentadienyl) (cyclododecylamino) titanium dimethyl; dimethylsilylene (tetramethylcyclopentadienyl) (tert-butylamino) titanium dimethyl; dimethylsilylene (tetramethylcyclopentadienyl) (adamantylamino) titanium dimethyl; dimethylsilylene (tetramethylcyclopentadienyl) (cyclooctylamino) titanium dimethyl; dimethylsilylene (tetramethylcyclopentadienyl) (cyclohexylamino) titanium dimethyl; dimethylsilylene (tetramethylcyclopentadienyl) (norbornylamino) titanium dimethyl; dimethylsilylene (trimethylcyclopentadienyl) (cyclododecylamino) titanium dimethyl; dimethylsilylene (trimethylcyclopentadienyl) (adamantylamino) titanium dimethyl; dimethylsilylene (trimethylcyclopentadienyl) (tert-butylamino) titanium dimethyl; dimethylsilylene (6-methyl-1, 2,3, 5-tetrahydro-s-indacen-5-yl) (tert-butylamino) titanium dimethyl; dimethylsilylene (6-methyl-1, 2,3, 5-tetrahydro-s-indacen-5-yl) (adamantylamino) titanium dimethyl; dimethylsilylene (6-methyl-1, 2,3, 5-tetrahydro-s-indacen-5-yl) (cyclooctylamino) titanium dimethyl; dimethylsilylene (6-methyl-1, 2,3, 5-tetrahydro-s-indacen-5-yl) (cyclohexylamino) titanium dimethyl; dimethylsilylene (6-methyl-1, 2,3, 5-tetrahydro-s-indacen-5-yl) (cyclododecylamino) titanium dimethyl; dimethylsilylene (2,2, 6-trimethyl-1, 2,3, 5-tetrahydro-s-indacen-5-yl) (adamantylamino) titanium dimethyl; dimethylsilylene (2,2, 6-trimethyl-1, 2,3, 5-tetrahydro-s-indacen-5-yl) (cyclohexylamino) titanium dimethyl; dimethylsilylene (2,2, 6-trimethyl-1, 2,3, 5-tetrahydro-s-indacen-5-yl) (cyclododecylamino) titanium dimethyl; dimethylsilylene (2,2, 6-trimethyl-1, 2,3, 5-tetrahydro-s-indacen-5-yl) (tert-butylamino) titanium dimethyl and any combination thereof.

As noted, other suitable HMP catalyst compounds can be characterized as bridged fluorenyl-cyclopentadienyl group 4 complexes. Suitable compounds according to these embodiments include compounds of the following general formula (3):

wherein: (1) m is a group 4 metal, preferably hafnium; (2) l is²Is a divalent substituted or unsubstituted fluorenyl, heterocyclopentanylcyclopentadienyl or heterofluorenyl ligand which is pi-bonded to M; (3) l is³Is a divalent cyclopentadienyl ring, substituted cyclopentadienyl ring, heterocyclopentadienyl ring or substituted heterocyclopentadienyl ligand which is pi-bonded to M; (4) j is a divalent bridging group; and (5) X is independently halo, hydrido, hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, silylhydrocarbyl, substituted silylhydrocarbyl, germylhydrocarbyl, or substituted germylhydrocarbyl; or two X's are joined and bonded to a metal atom to form a metallocycle ring containing from about 3 to about 20 carbon atoms; or two X together may be an alkene, diolefin or aryne ligand. In some embodiments, two xs may independently be halogen, alkoxy, aryloxy, amino, phosphorus group, or other monovalent anionic ligands or two xs may also be joined to form anionic chelating ligands.

In some embodiments, the fluorenyl-cyclopentadienyl group 4 complex includes a compound of the general formula (3 a):

wherein:

(1) j is a divalent bridging group containing C, Si or both; (2) m is a group 4 metal (e.g., Hf, Zr, or Ti, with Hf being preferred in certain embodiments); (3) each X is independently a monovalent anionic ligand, or two Xs are joined and bonded to a metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and (4) each R "¹、R”²、R”³、R”⁴、R”⁵、R”⁶、R”⁷、R”⁸、R”⁹And R "¹⁰Independently of each other is hydrogen, C₁-C₅₀A hydrocarbyl, substituted hydrocarbyl, halocarbyl or substituted halocarbyl group, with the proviso that R "¹And R "²、R”³And R "⁴、R”⁵And R "⁶、R”⁶And R "⁷、R”⁸And R "⁹And R "⁹And R "¹⁰Any one or more of the pairs may not be necessaryAre bonded together to form a saturated or partially saturated cyclic or fused ring structure. In certain embodiments, bridging group J is represented by R₂C、R*₂Si、R*₂CCR*₂、R*C＝CR*、R*₂CSiR*₂Or R₂SiSiR*₂Wherein each R is independently hydrogen or C₁-C₂₀And optionally, two or more adjacent R may be joined to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. In some embodiments, J is a bridging group comprising carbon and/or silicon atoms, such as a dialkylsilyl group; preferably J is selected from CH₂、CH₂CH₂、C(CH₃)₂、SiMe₂、SiEt₂、SiPh₂、SiMePh、Ph₂C、(p-(Et)₃SiPh)₂C、Si(CH₂)₃、Si(CH₂)₄And Si (CH)₂)₅. Alternatively, J may be any of the compounds described for "J" in the VTP catalyst above.

In certain embodiments, each X is selected according to the HMP compounds described herein before. That is, each X can be independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, halogens, hydrogen groups, amino groups, alkoxy groups, thio groups, phosphorus groups, halogen groups, dienes, amines, phosphines, ethers, and combinations thereof. Two X may form part of a fused ring or ring system. In particular embodiments, each X is independently selected from halo and C₁-C₅An alkyl group. For example, each X may be chloro, bromo, methyl, ethyl, propyl, butyl or pentyl. In particular embodiments, each X is methyl.

In some embodiments, each R "¹、R”²、R”³、R”⁴、R”⁵、R”⁶、R”⁷、R”⁸、R”⁹And R "¹⁰Independently selected from the following: h; CH (CH)₃；CH₂CH₃；CH₂CH₂CH₃；CH₂(CH₂)₂CH₃；CH₂(CH₂)_3-30CH₃；CH₂C(CH₃)₃；CH＝CH₂；CH(CH₃)₂；CH₂CH(CH₃)₂；CH₂CH₂CH(CH₃)₂；C(CH₃)₂CH(CH₃)₂；CH(C(CH₃)₃)CH(CH₃)₂；C(CH₃)₃；CH₂Si(CH₃)₃；CH₂Ph；C₄H₇；C₅H₉；C₆H₁₁；C₇H₁₃；C₈H₁₅；C₉H₁₇；C₆H₅；CH₂Si(CH₃)₃；CH₂CH＝CH₂；CH₂CH₂CH＝CH₂；CH₂CH₂(CF₂)₇CF₃；CF₃；N(CH₃)₂；N(C₂H₅)₂And OC (CH)₃)₃。

In certain embodiments, R "¹、R”²、R”³、R”⁴、R”⁵、R”⁶、R”⁷、R”⁸、R”⁹And R "¹⁰Any one or more of which may be hydrogen, methyl, ethyl, n-propyl, isopropyl, sec-butyl, isobutyl, n-butyl, tert-butyl, for C₅-C₁₀The various isomers of alkyl groups and so on. In certain embodiments, R "⁶And R "⁹May be a tert-butyl group. In some such embodiments, R "¹、R”²、R”³、R”⁴、R”⁵、R”⁷、R”⁸And R "¹⁰May each be independently selected from H, methyl and ethyl. In certain embodiments, except R "⁶And R "⁹Each R' except "¹-R”¹⁰Is H.

In particular embodiments, the fluorenyl-cyclopentadienyl group 4 complex is represented by the following formula (3 b):

wherein M, X, R'¹-R”¹⁰J' is a silicon or carbon atom, Ar, as defined above¹And Ar²Independently is C₆-C₃₀Aryl or substituted aryl, wherein the substituents are independently selected at each occurrence from the group consisting of hydrocarbyl, substituted hydrocarbyl, halocarbyl, and substituted halocarbyl.

In certain embodiments, Ar¹And Ar²At least one of which contains at least one compound of formula R'_nSiR”₃Wherein each R' is independently C₁-C₂₀Hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, silylhydrocarbyl or substituted silylhydrocarbyl substituent, R' is C between Si and aryl₁-C₁₀A substituted or unsubstituted alkyl, alkenyl and/or alkynyl linker, n ═ 0 or 1. For example, when n is 0, Ar¹And Ar²One or both of which may be trimethylsilylphenyl (Me)₃SiPh), triethylsilylphenyl (Et)₃SiPh), tripropylsilylphenyl (Pr)₃SiPh), and the like. Similarly, when n is 1, R' is present as a linking group, e.g. C₂A linking group (e.g., ethyl linking group), then Ar¹And Ar²One or both of which may be (trimethylsilyl) ethylphenyl (Me)₃SiCH₂CH₂Ph), and so on.

Thus, for example, in which (1) R "⁶And R "⁹Each is a tert-butyl group as described above; (2) r'¹–R”⁴、R”⁵、R”⁷、R”⁸And R "¹⁰Each is H, also as discussed above; (3) ar (Ar)¹And Ar²Each is Et₃SiPh; (4) j is C; (5) in embodiments where M is Hf and (6) each X is methyl, the example HMP catalyst can correspondingly be given as dimethyl 1,1' -bis (4-triethylsilylphenyl) methyleneYl- (cyclopentadienyl) (2, 7-di-tert-butyl-fluoren-9-yl) hafnium.

Particularly useful fluorenyl-cyclopentadienyl group 4 complexes include: dimethylsilylene (cyclopentadienyl) (2, 7-di-tert-butyl-fluoren-9-yl) hafnium dimethyl; dimethylsilylene (cyclopentadienyl) (3, 6-di-tert-butyl-fluoren-9-yl) hafnium dimethyl; diphenylmethylene (cyclopentadienyl) dimethyl (2, 7-di-tert-butyl-fluoren-9-yl) hafnium; diphenylmethylene (cyclopentadienyl) (3, 6-di-tert-butyl-fluoren-9-yl) hafnium dimethyl; isopropylidene (cyclopentadienyl) dimethyl (2, 7-di-tert-butyl-fluoren-9-yl) hafnium; isopropylidene (cyclopentadienyl) dimethyl (3, 6-di-tert-butyl-fluoren-9-yl) hafnium; dimethylsilylene (cyclopentadienyl) (2, 7-dimethylfluoren-9-yl) hafnium dimethyl; dimethylsilylene (cyclopentadienyl) (3, 6-dimethylfluoren-9-yl) hafnium dimethyl; diphenylmethylene (cyclopentadienyl) (2, 7-dimethylfluoren-9-yl) hafnium dimethyl; diphenylmethylene (cyclopentadienyl) (3, 6-dimethylfluoren-9-yl) hafnium dimethyl; dimethylsilylene (cyclopentadienyl) (fluoren-9-yl) hafnium dimethyl, isopropylidene (cyclopentadienyl) (fluoren-9-yl) hafnium dimethyl, diphenylmethylene (cyclopentadienyl) (fluoren-9-yl) hafnium dimethyl, and 1,1' -bis (4-triethylsilylphenyl) methylene (cyclopentadienyl) (2, 7-di-tert-butyl-fluoren-9-yl) hafnium dimethyl.

The HMP catalyst used in the examples of the invention was Cat1 as shown below:

in still other embodiments, suitable HMP catalyst compounds can be characterized as chelated transition metal complexes (type 1), such as those having the following general structural formula (4):

wherein: (1) j is a radical containingC. A divalent bridging group of Si or both; (2) m is a group 4 metal, preferably hafnium and zirconium; (3) o is oxygen; (4) each X is independently a monovalent anionic ligand, or two Xs are joined and bonded to a metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and (5) L⁴And L⁵Independently a substituted monocyclic or polycyclic aromatic group.

In some embodiments, J is a divalent substituted or unsubstituted C_3-6Aliphatic or cycloaliphatic radicals.

In some embodiments, L is⁴And L⁵Independently a monocyclic or polycyclic aromatic group substituted with any combination of alkyl, aryl, alkoxy, or amino substituents, which may optionally be substituted with halo.

In still other embodiments, suitable HMP catalyst compounds that are chelated transition metal complexes (type 1) can be characterized as biphenyl phenol transition metal complexes, such as those having the following general structural formula (4 a):

wherein: (1) j is a divalent bridging group comprising C, Si or both; (2) m is a group 4 metal, preferably hafnium and zirconium; (3) o is oxygen; (4) each X is independently a monovalent anionic ligand, or two Xs are joined and bonded to a metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and (5) each R'²⁰、R'²¹、R'²²、R'²³、R'²⁴、R'²⁵、R'²⁶、R'²⁷、R'²⁸、R'²⁹、R'³⁰、R'³¹、R'³²、R'³³、R'³⁴、R'³⁵Independently of one another is hydrogen, halogen, C₁-C₅₀Hydrocarbyl, substituted hydrocarbyl, halocarbyl or substituted halocarbyl.

In particular embodiments, each R'²⁰And R'³⁵Can be used forAre or may contain bulky substituents such as substituted or unsubstituted aryl, carbazolyl, fluorenyl and/or anthracenyl groups.

In other particular embodiments, each R'²⁰And R'³⁵Independently, it can be 3, 5-di (isopropyl) phenyl, 3, 5-di (isobutyl) phenyl, 3, 5-di (tert-butyl) phenyl, carbazol-9-yl, 3, 6-di-tert-butylcarbazol-9-yl, 2,3,4,5,6,7,8, 9-octahydrocarbazol-1-yl, anthracen-9-yl, 1,2,3,4,5,6,7, 8-octahydroanthracen-9-yl, naphthyl, fluoren-9-yl, 9-methylfluoren-9-yl, 1,2,3,4,5,6,7, 8-octahydrofluoren-9-yl or 9-methyl-1, 2,3,4,5,6,7, 8-octahydrofluoren-9-yl.

In other particular embodiments, R'²²And R'³³Independently is C₁-C₁₀A hydrocarbon radical, or C₁-C₁₀Alkyl groups such as methyl, ethyl and all isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.

In other particular embodiments, R'²⁵And R'³⁰Independently is C₁-C₁₀Substituted or unsubstituted hydrocarbyl, halo, C₁-C₁₀Alkoxy and C₂-C₂₀A dialkylamino group. Or, R'²⁵And R'³⁰Independently is C₁-C₁₀Alkyl groups such as methyl, ethyl and all isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl (including cyclic and linear or branched cyclic combinations); halogen, such as fluorine, chlorine, bromine; c₁-C₁₀Alkoxy groups such as methoxy, ethoxy, and all isomers of propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, and decyloxy (including cyclic and linear or branched cyclic combinations); c₂-C₂₀Dialkylamino groups such as dimethylamino, diethylamino, and dipropylamino, dibutylamino, dipentylamino, dihexylamino, diheptylamino, dioctylamino, dinonylamino, didecylamino (including cyclic and linear or branched cyclic combinations), and mixed alkyl groups such as methylethylamino, methylbutylamino, and the like.

In other particular embodiments, J may be propane-1, 3-diyl, butane-1, 4-diyl, cyclohexanediyl, cyclohexene-4, 5-diyl, or bis (methylene) cyclohexane-1, 2-diyl.

Non-limiting examples of particularly useful biphenol transition metal complexes are shown below, where M is hafnium or zirconium, and X is methyl, benzyl, or chlorine:

other particularly useful transition metal complexes of biphenol are described in WO2003/091262, WO2005/108406, US2006/0025548, US2006/0052554, WO2007/136494, WO2007/136496, WO2007/136495, WO2009/064482 and WO2013/096573, and are incorporated by reference.

In still other embodiments, suitable HMP catalyst compounds can be characterized as chelated transition metal complexes (type 2), such as those having the following general structural formula (5):

wherein (1) M is a group 4 metal, preferably hafnium; (2) l is⁶Is C containing Lewis base functional groups₅-C₂₀Heteroaryl, in particular pyridin-2-yl or substituted pyridin-2-yl or divalent derivatives thereof; (3) r⁴⁰Is selected from C₁-C₃₀Alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and substituted derivatives thereof or divalent derivatives thereof; (4) t is a divalent bridging group containing carbon and/or silicon, preferably C₁-C₂₀Hydrocarbyl-substituted methylene or silane groups; (5) each X is independently a monovalent anionic ligand, or two X's are joined and bonded to a metal atom to form a metallocycle ring, or two X's are joined to form a chelating ligand, a dieneA ligand or alkylidene ligand; (6) n is nitrogen; and (7) bonds, optional bonds and coordination bonds are represented by lines, dashed lines and arrows, respectively.

In still other embodiments, suitable HMP catalyst compounds that are chelated transition metal complexes (type 2) can be characterized as pyridylamino metal complexes, such as those having the following general structural formula (5 a):

wherein M, T, N and X are as previously defined in formula (5); each R⁴¹、R⁴²、R⁴³And R⁴⁴Independently hydrogen, halo or alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl or silyl, or one or more adjacent R⁴¹-R⁴⁴May be joined together to form fused ring derivatives; r⁴⁵-R⁴⁹Independently is hydrogen or C₁-C₁₀Alkyl, most preferably R⁴⁵And R⁴⁹Is alkyl such as isopropyl or tert-butyl; t is preferably CR'⁵⁰R'⁵¹Wherein R'⁵⁰And R'⁵¹Independently of one another is hydrogen, halogen, C₁-C₂₀Hydrocarbyl, most preferably, R'⁵⁰And R'⁵¹One being hydrogen and the others being C₆-C₂₀Aryl, especially 2-isopropyl, phenyl or fused polycyclic aryl, most preferably anthracenyl; and bonds, optional bonds and coordination bonds are represented by lines, dashed lines and arrows, respectively.

Non-limiting examples of pyridylamino catalysts which are chelated transition metal complexes (type 2) are shown below, wherein X is preferably methyl, benzyl or chloro:

other particularly useful chelated transition metal complexes (type 2) including pyridylamido transition metal complexes are described in WO2010/0227990, US2004/0220050, WO2004/026925, WO2004/024740, WO2004/024739, WO2003/040201, and WO2002/046249, WO2002/038628 and incorporated by reference.

In still other embodiments, suitable HMP catalyst compounds can be characterized as chelated transition metal complexes (type 3), such as those having the following general structural formula (6):

wherein (1) M is a group 4 metal, preferably hafnium; (2) n is nitrogen; (3) l is⁷By a three-atom bridge⁵⁰A group attached to Z' and being C containing a Lewis base function₅-C₂₀Heteroaryl, in particular divalent pyridyl or substituted pyridyl, wherein the center of said three atoms is a group 15 or 16 element which preferably forms a coordinate bond with M; (4) z' is a divalent linking group, (R)⁵⁶)_pC-C(R⁵⁷)_qWherein R is⁵⁶And R⁵⁷Independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, and wherein adjacent R is⁵⁶And R⁵⁷The groups may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl ring wherein the ring has 5,6,7 or 8 ring carbon atoms and wherein substituents on the ring may be joined to form additional rings, and p is 1 or 2, q is 1 or 2; (5) r⁵⁰And R⁵³Each independently is ER⁵⁴R⁵⁵Wherein E is carbon, silicon or germanium, each R⁵⁴And R⁵⁵Independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R⁵⁴And R⁵⁵May join to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring, wherein substituents on the rings may join to form additional rings; (6) r⁵¹And R⁵²Independently selected from hydrocarbyl, substituted hydrocarbyl, silylhydrocarbyl and substituted silylhydrocarbyl groups; and (7) each X is independently a monovalent anionic ligand, or two Xs are joined and bonded to a metal atom to form a metallocycle ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.

In still other embodiments, suitable HMP catalyst compounds that are chelated transition metal complexes (type 3) can be characterized as pyridyldiamido metal complexes, such as those having the following general structural formula (6 a):

m, X, N, R therein⁵¹、R⁵²、R⁵⁴And R⁵⁵As defined hereinbefore in formula (6); r⁶⁰、R⁶¹、R⁶²、R⁶³、R⁶⁴、R⁶⁵、R⁶⁶Independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, aryloxy, halogen, amino and silyl, and any one or more adjacent R therein⁶⁰-R⁶⁶May be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring wherein the ring has 5,6,7 or 8 ring atoms and wherein substituents on the ring may be joined to form additional rings.

In one embodiment of the invention, R⁶⁰-R⁶⁶Is hydrogen.

In one embodiment of the invention R⁶²And R⁶³Joined to form a phenyl ring (e.g. naphthyl) fused to an existing phenyl ring, R⁶⁰、R⁶¹、R⁶⁴、R⁶⁵And R⁶⁶Independently hydrogen or alkyl, preferably hydrogen.

In one embodiment of the invention each R⁵⁴And R⁵⁵Independently hydrogen, alkyl or aryl or substituted aryl; preferably R⁵⁴Or R⁵⁵One or both of which are hydrogen, or an R⁵⁴Or R⁵⁵Is hydrogen and the other is aryl or substituted aryl. For R⁵⁴Or R⁵⁵Preferred but non-limiting aryl groups include phenyl, 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl and naphthyl.

In one embodiment of the invention, R⁵²And R⁵¹Independently is aryl or substituted aryl; preferably, R⁵¹Is a substituted phenyl group such as, but not limited to, 2, 6-diisopropylphenyl, 2, 6-diethylphenyl, 2, 6-dimethylphenyl,and the like, preferably, R⁵²Is phenyl or substituted phenyl such as, but not limited to, 2-tolyl, 2-ethylphenyl, 2-propylphenyl, 2-trifluoromethylphenyl, 2-fluorophenyl,a phenyl group, a2, 6-diisopropylphenyl group, a2, 6-diethylphenyl group, a2, 6-dimethylphenyl group, a 3, 5-di-tert-butylphenyl group and the like.

In still other embodiments, suitable HMP catalyst compounds that are chelated transition metal complexes (type 3) can be characterized as pyridyldiamido metal complexes, such as those having the following general structural formula (6 b):

m, X, N, R therein⁵¹、R⁵²、R⁵⁴、R⁵⁵、R⁶¹-R⁶⁶As defined hereinbefore in formulae (6) and (6 a); each R⁷⁰-R⁷¹Independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, alkoxy, aryloxy, halogen, amino and silyl, and any one or more adjacent R therein⁷⁰-R⁷¹May be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring wherein the ring has 5,6,7 or 8 ring atoms and wherein substituents on the ring may be joined to form additional rings, t is 2 or 3 (corresponding to cyclopentyl and cyclohexyl rings, respectively).

In one embodiment of the invention, R⁶¹-R⁶⁶Is hydrogen.

In one embodiment of the invention, each R is⁷⁰And R⁷¹Independently hydrogen, t is 2 or 3, preferably 2.

In one embodiment of the inventionEach R⁵⁴And R⁵⁵Independently hydrogen, alkyl or aryl or substituted aryl; preferably R⁵⁴Or R⁵⁵One or both of which are hydrogen, or an R⁵⁴Or R⁵⁵Is hydrogen and the other is aryl or substituted aryl. Preferred but non-limiting aryl groups include phenyl and 2-methylphenyl, 2-ethylphenyl, 2-isopropylphenyl and naphthyl.

In one embodiment of the invention, R⁵²And R⁵¹Independently is aryl or substituted aryl; preferably, R⁵¹Is a substituted phenyl group such as, but not limited to, 2, 6-diisopropylphenyl, 2, 6-diethylphenyl, 2, 6-dimethylphenyl,and the like, preferably, R⁵²Is phenyl or substituted phenyl such as, but not limited to, 2-tolyl, 2-ethylphenyl, 2-propylphenyl, 2-trifluoromethylphenyl, 2-fluorophenyl,a phenyl group, a2, 6-diisopropylphenyl group, a2, 6-diethylphenyl group, a2, 6-dimethylphenyl group, a 3, 5-di-tert-butylphenyl group and the like.

In one embodiment of the invention, R⁵⁴、R⁵⁵、R⁶¹-R⁶⁶Each R⁷⁰-R⁷¹Is hydrogen, R⁵²Is phenyl, R⁵¹Is 2, 6-diisopropylphenyl and t is 2.

Non-limiting examples of pyridyldiamido catalysts that are chelated transition metal complexes (type 3) are shown below, where X is methyl, benzyl, or chlorine:

other particularly useful chelated transition metal complexes (type 3) including pyridyldiamido transition metal complexes are described in US2014/0316089, WO2012/134614, WO2012/134615, WO2012/134613, US2012/0071616, US2011/0301310, and US2010/0022726 and are incorporated by reference.

As indicated previously, the HMP catalyst system further comprises an activator, and optionally a support and co-activator(s). Suitable activators, optional supports, and optional co-activator(s) are discussed in more detail below.

First and second polymer compositions

As described herein, there is provided a method of making a polymer blend composition having high elasticity. The method comprises the following steps: the method includes the steps of preparing a first polymer composition using a VTP catalyst system, preparing a second polymer composition using a HMP catalyst system, and combining the first polymer composition and the second polymer composition to produce a blended polymer composition. The process of the present invention comprises blending/combining polymer compositions prepared by different catalyst systems. One such catalyst system includes (i) a vinyl terminated polymer ("VTP") catalyst system comprising a VTP catalyst compound (also referred to herein as a "VTP catalyst") and one or more activators. Another catalyst system includes a high molecular weight polymer ("HMP") catalyst system comprising an HMP catalyst compound (also referred to herein as an "HMP catalyst") and one or more activators. The activators of these different catalyst systems may be completely or partially the same or different.

In one aspect, the polymer composition and/or polymerization process uses ethylene, propylene, and 5-ethylidene-2-norbornene monomers (e.g., the process produces, and/or the polymer composition comprises or consists of, an ethylene-propylene-5-ethylidene-2-norbornene terpolymer). In this case, the diene content is preferably less than any one of 15, 10, 5,1 and 0.1 wt% of the total weight of the ethylene terpolymer.

Each of the polymer composition, the first polymer composition, the second polymer composition, and the blended polymer composition can be prepared from a variety of monomers, including ethylene and propylene, and ethylene-propylene (EP) copolymers. Alternatively, the polymer composition may be prepared from ethylene monomer and homo-polypropylene or ethylene-propylene copolymer VTP; or from propylene monomers and homopolyethylene or ethylene-propylene VTP, etc. The copolymer may also optionally include units derived from diene monomers (e.g., as third, fourth or other monomers, and/or incorporated into the VTP), such that the resulting polymer may be designated an ep (d) M polymer, indicating optional inclusion of diene-derived units. When such diene-derived units do exist, the copolymer can be characterized as an EPDM copolymer. In addition, ep (d) M and/or EPDM may be formed from a variety of monomers in addition to propylene comonomer, including other alpha-olefin comonomers, such as 1-butene. In one aspect, at least 50% of the VTPs can have at least one chain end unsaturation (of any kind).

As provided herein, the blended polymer composition will have a Mw of 5,000-1,000,000g/mol, preferably 50,000-700,000g/mol, even more preferably 100,000-500,000 g/mol. The blend will preferably have an MWD (Mw/Mn) greater than 2.6, more preferably>2.8, even more preferably 3 or more. The blends exhibit improved rheological properties such as high viscosity at low shear rates and low viscosity at high shear rates. The low angle oscillatory shear rheology of the polymer blend preferably has Tan (. delta.), i.e., at 0.245s^-1The ratio of the lower loss modulus to the storage modulus (G '/G') is not more than 1.1, more preferably Tan (. delta.) not more than 1, and even more preferably Tan (. delta.) not more than 0.9 at 100 ℃ or 125 ℃. Another characteristic of polymer blends is that the shear-thinning ratio (complex viscosity at 0.1 Rad/s)/(complex viscosity at 128 Rad/s) is preferred>70, more preferably>100, and in some embodiments, 150 or greater at 100 or 125 ℃. Another characteristic of polymer blends is the low frequency at which the storage and loss moduli are equal. In a preferred embodiment, in<1.8Rad/s, G "/G ═ 1, in a more preferred embodiment, in<0.9Rad/s, G "/G' ═ 1, in an even more preferred embodiment, in<0.5Rad/s, G "/G' ═ 1 at 100 or 125 ℃. In some even more preferred embodiments, in<0.1Rad/s, G "/G' ═ 1 at 100 or 125 ℃. In the latter case, the plots of G' and G "versus frequency for the blends did not intersect between 0.1 and 128 Rad/s. Thus, the blend may have shear thinningThe ratio (complex viscosity at 0.1 Rad/s)/(complex viscosity at 128 Rad/s)>70, preferably>100, even more preferably>125. In some embodiments, the blend may have a 100 or 125 ℃ shear-thinning ratio of 150 or greater. Other characteristics of the polymer blend are that the phase angle is less than 50 °, preferably less than 45 °, even more preferably less than 40 ° when G ═ 100,000Pa at 100 or 125 ℃. The blended polymer composition may be characterized as a blend of the reaction products of each of the first polymerization process and the second polymerization process.

Polymerization process

Methods according to other aspects include at least two polymerizations (using a VTP catalyst system and a HMP catalyst system). In preparing the first polymer composition or the second polymer composition, these aspects employ parallel polymerization (e.g., VTP polymerization and HMP polymerization are conducted in parallel, and then the products of each polymerization are blended).

For example, a polymerization process according to some of these aspects includes: reacting (i) VTP, (ii) one or more C's in a reactor₂-C₂₀(ii) contacting alpha-olefin monomer and optionally (iii) one or more dienes to form a VTP polymer composition and reacting (iv) HMP, (v) one or more Cs in a second reactor₂-C₂₀(vi) contacting an alpha-olefin monomer and optionally, (vi) one or more dienes to form the HMP polymer composition. In a particular aspect, C₂-C₂₀The alpha-olefin monomer is ethylene and the VTP polymer composition is comprised of units derived from one or more of ethylene, propylene, and optionally, one or more dienes. In other aspects, the one or more monomers further comprise a second C₃-C₂₀Alpha-olefin comonomers, for example propylene or 1-butene.

Parallel polymerization can include, for example, a first polymerization zone containing a VTP catalyst system to produce a first polymer composition (comprising, for example, one or more VTPs) and a second polymerization zone containing a HMP catalyst system to produce a second polymer composition (comprising, for example, one or more HMP catalysts). At least a portion of each of the first and second polymer compositions are then blended together or otherwise combined to form the blended polymer composition.

Each of the polymerization processes described herein can be carried out using a variety of polymerization techniques. For example, suspension, homogeneous, bulk, solution, slurry or gas phase polymerization processes may be used. These processes may be run in batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes are useful.

In addition, while known polymerization techniques may be employed, methods according to certain aspects employ specific conditions (e.g., temperature and pressure). The temperature and/or pressure may generally comprise a temperature of from about 0 ℃ to about 300 ℃. Example ranges include a range from a lower limit at any one of about 20, 30, 35, 40, 45, 50, 55, 60, 65, and 70 ℃ to an upper limit at any one of about 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 250, and 300 ℃. For example, the polymerization temperature can be in the range of from about 40 ℃ to about 200 ℃, or from about 45 ℃ to about 150 ℃, 70 ℃ to about 150 ℃, or, in particular aspects, from about 70 ℃ to about 125 ℃. The pressure may depend on the desired scale of the polymerization system. For example, in some polymerizations, the pressure may generally range from about ambient pressure to 200 MPa. In various such aspects, the pressure can range from a lower limit of any of about 0.1, 1,5, and 10 to an upper limit of any of about 3,5, 10, 50, 100, 150, and 200MPa, provided that the upper limit of the range is greater than the lower limit. According to these aspects, the pressure is preferably in the range of about 2 to about 70 MPa.

Polymerization process components

Each of the polymerization processes described herein employs the HMP catalyst system or VTP catalyst system described herein. As previously mentioned, each catalyst system generally comprises its respective catalyst compound and one or more activators (which may be the same or different). The polymerization process includes contacting a plurality of monomers with either a HMP catalyst system or a VTP catalyst system, or contacting a suitable VTP with a HMP catalyst system along with one or more additional monomers. VTPs can be prepared by VTP catalyst systems. Similarly, HMP catalyst systems produce HMPs, which in some aspects can further introduce VTPs into the HMP structure to form long chain branched architectures.

Generally, the VTP catalyst system includes a VTP catalyst compound and an activator. The VTP catalyst system may further optionally include, but is not limited or constrained by, a support and/or one or more co-activators. The various activators, co-activators and supports may be the same or different for the VTP and HMP catalysts, and thus these components of the catalyst system are described in more detail below with respect to both catalysts.

In the polymerization process, the metallocene catalyst system can produce polymer compositions having unsaturated chain ends that can be incorporated into a growing chain and form long chain branches. See, for example, EP495099 and EP 608369. As a result, various polymerization processes have been designed to produce long chain branched metallocene polymer compositions. See US 4,814,540; JP 2005-336092A 2; US2012 and 0245311 a 1; rulhoff et al in 16Macromolecular Chemistry and Physics 1450-1460 (2006); kaneyoshi et al, 38Macromolecules 5425-5435 (2005); teuben et al 62 j.mol.catal.277-287 (1990); X.Yang et al 31 Angew.chem.Intl Ed.Engl.1375-1377 (1992); resconi et al, 114J.am.chem.Soc.1025-1032 (1992); small and Brookhart 32Macromolecules 2120-2130 (1999); weng et al 21Macromol Rapid Comm.1103-1107 (2000); 33 Macromolecules 8541-8548 (2000); moscardi et al, 20 Organometallics 1918-; coates et al, 38Macromolecules 6259-6268 (2005); rose et al 41 Macromolecules559-567 (2008); zhu et al 35Macromolecules 10062-10070(2002) and 24 Macromolecules rap. Commun.311-315 (2003); janiak and Blank in 236 Macromol. Symp.14-22 (2006).

Alpha-olefin monomers and dienes

As described herein, each of the polymer compositions (first polymer composition, second polymer composition, and blend composition) can be made from at least a portion of the plurality of monomers. The plurality of monomers may comprise: (1) first C₂-C₂₀An alpha-olefin; (2) a second C different from the first₂-C₂₀An alpha-olefin; and, optionally, (3) one or moreA plurality of dienes. For example, in one aspect, the plurality of monomers comprises: (1) ethylene; (2) second C₃-C₂₀Alpha-olefins such as propylene and/or butene; and (3) one or more dienes. Further, each of the polymer compositions (first polymer composition, second polymer composition, and blended polymer composition) can comprise a polymer made from one or more monomers, including homopolymers, copolymers, or both.

The polymerization process used to prepare the first polymer composition and the second polymer composition may use one or more monomers as reactants (e.g., to be contacted with a HMP catalyst system or a VTP catalyst system). Each of the one or more monomers useful in the polymerization process of the present invention (and/or included in the polymer composition) is independently selected from C₂-C₄₀Alpha-olefins, preferably C₂-C₂₀Alpha-olefins, more preferably C₂-C₁₂Alpha-olefins (e.g., ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof).

By way of example, in certain aspects, one or more monomers include both the first C₂-C₁₂The alpha-olefin further comprises a second C different from the first₂-C₁₂An alpha-olefin. In particular aspects of these aspects, the first monomer is ethylene and the second monomer is an alpha-olefin other than ethylene. For example, the second monomer may be C₃-C₁₂Or C₃-C₈An alpha-olefin, such as one of those given hereinbefore. In one aspect, the second monomer is propylene, butene (e.g., 1-butene), or hexene (e.g., 1-hexene). Additionally, the one or more monomers may include propylene and butylene in addition to ethylene.

Exemplary C₂-C₄₀Alpha-olefin and cyclic olefin monomers and comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, cyclopentene, cycloheptene, cyclooctene, cyclododecene, 7-oxanorbornene, substituted derivatives thereofAnd their isomers, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1-hydroxy-4-methyl-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene and any combination thereof.

The plurality of monomers may also include one or more dienes. Suitable diene monomers include any hydrocarbon structure having at least two unsaturated bonds, preferably C₄-C₃₀. Preferably, the diene is a non-conjugated diene containing at least two unsaturated bonds, one of which is readily incorporated into the polymer. The second bond may be partially involved in the polymerization to form a crosslinked polymer, but typically provides at least some unsaturated bonds in the polymer product that are suitable for subsequent functionalization (e.g., functionalization with maleic acid or maleic anhydride), curing, or vulcanization in a post-polymerization process. Examples of dienes include, but are not limited to, butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, eicosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, and polybutadiene having a molecular weight (Mw) of less than 1000 g/mol. Examples of linear acyclic dienes include, but are not limited to, 1, 4-hexadiene and 1, 6-octadiene. Examples of branched acyclic dienes include, but are not limited to, 5-methyl-1, 4-hexadiene, 3, 7-dimethyl-1, 6-octadiene, and 3, 7-dimethyl-1, 7-octadiene; examples of monocyclic cycloaliphatic dienes include, but are not limited to, 1, 4-cyclohexadiene, 1, 5-cyclooctadiene, and 1, 7-cyclododecadiene. Examples of polycyclic alicyclic fused and bridged cyclic dienes include, but are not limited to, tetrahydroindene; methyl-tetrahydroindene; dicyclopentadiene; bicyclo (2.2.1) -hepta-2, 5-diene; 2, 5-norbornadiene; and alkenyl-, alkylidene-, cycloalkenyl-and cycloalkylidene norbornenes [ including, for example, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene (ENB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbomeneLamenes, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene and 5-vinyl-2-norbornene]. Examples of cycloalkenyl-substituted alkenes include, but are not limited to, vinylcyclohexene, allylcyclohexene, vinylcyclooctene, 4-vinylcyclohexene, allylcyclodecene, vinylcyclododecene, and tetracyclic (A-11,12) -5, 8-dodecene. 5-ethylidene-2-norbornene (ENB) is a preferred diene in certain aspects.

The diene monomer may have at least two polymerizable unsaturated bonds that can be incorporated into the polymer to form a crosslinked polymer. The polymerizable bond of the diene refers to a bond that can be introduced or inserted into the polymer chain during polymerization of the growing chain. For polymerizations using metallocene catalysts, examples of such dienes include alpha, omega-dienes (e.g., butadiene, 1, 4-pentadiene, 1, 5-hexadiene, 1, 6-heptadiene, 1, 7-octadiene, 1, 8-nonadiene, 1, 9-decadiene, 1, 10-undecadiene, 1, 11-dodecadiene, 1, 12-tridecadiene, and 1, 13-tetradecadiene) and certain polycyclic cycloaliphatic fused and bridged cyclic dienes (e.g., tetrahydroindene, 7-oxanorbornadiene, dicyclopentadiene; bicyclo (2.2.1) -hepta-2, 5-diene; 5-vinyl-2-norbornene; 3, 7-dimethyl-1, 7-octadiene; 1, 4-cyclohexadiene; 1, 5-cyclooctadiene; 1, 7-cyclododecadiene and vinylcyclohexene). In one aspect, in certain polymer compositions (and/or processes for making them), the content of diene having at least two polymerizable bonds in the polymer composition of the invention is less than 0.5 wt%, preferably less than 0.1 wt%, of the copolymer.

Notably, 5-ethylidene-2-norbornene ("ENB") has two unsaturated bonds, but only one of which is polymerizable in a metallocene system. During polymerization, 5-ethylidene-2-norbornene is incorporated into the growing polymer chain only via the endocyclic double bond; leaving the exocyclic double bond unreacted. Because it is non-reactive during polymerization, reactor crosslinking cannot occur. The unreacted double bonds can be used after the reactor (e.g., crosslinking and functionalization). In some embodiments, the polymer composition is then free of dienes having at least two polymerizable bonds (and/or the copolymerization process results in such a polymer composition). Such polymers (and/or polymer compositions comprising such copolymers) are free of cross-linking architectures having tetrafunctionality and gel-free products.

Catalyst system activators

The cocatalyst or activator converts the neutral catalyst compound into a catalytically active catalyst compound cation. Non-limiting activators include alumoxanes, aluminum alkyls, ionizing activators (which may be neutral or ionic), and cocatalysts of conventional type. Specific activators include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract reactive, sigma-bonded metal ligands to prepare metal coordinating cations and provide charge balancing non-coordinating or weakly coordinating anions.

Activator for catalyst systems

The terms "cocatalyst" and "activator" are used interchangeably herein.

The catalyst systems described herein typically comprise the above-described catalyst complex and an activator such as an alumoxane or a non-coordinating anion and may be formed by combining the catalyst components described herein with an activator in any manner known from the literature, including combining them with a support such as silica. The catalyst system may also be added to or generated from solution polymerization or bulk polymerization (in monomer). The catalyst system of the present disclosure may have one or more activators and one, two or more catalyst components. An activator is defined as any compound that can activate any of the above catalyst compounds by converting a neutral metal compound to a catalytically active metal compound cation. Non-limiting activators include, for example, alumoxanes, aluminum alkyls, ionizing activators (which may be neutral or ionic), and cocatalysts of conventional type. Preferred activators generally include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract reactive, sigma-bonded metal ligands, thereby cationizing the metal compound and providing a charge-balancing non-coordinating or weakly coordinating anion, such as a non-coordinating anion.

Alumoxane activators

Alumoxane activators are used as activators in the catalyst systems described herein. Aluminoxanes are generally those containing-Al (R)¹) -oligomer compounds of O-subunits, wherein R is¹Is an alkyl group. Examples of the aluminoxane include Methylaluminoxane (MAO), Modified Methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, especially when the abstractable ligand is an alkyl, halo, alkoxy or amino group. Mixtures of different aluminoxanes and modified aluminoxanes may also be used. It may be preferable to use methylaluminoxane which is visually transparent. The cloudy or gel aluminoxane can be filtered to prepare a clear solution or the clear aluminoxane can be decanted from the cloudy solution. Useful aluminoxanes are Modified Methylaluminoxane (MMAO) co-catalyst type 3A (commercially available from Akzo Chemicals, inc. under the trade name modified methylaluminoxane type 3A) covered by U.S. patent No. US 5,041,584. Another useful aluminoxane is U.S. patent nos. 9,340,630; 8,404,880 and 8,975,209.

When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of activator typically in up to 5000 times molar excess (Al/M) relative to the catalyst compound (each metal catalytic site). The minimum activator to catalyst compound ratio is 1:1 molar ratio. Alternative preferred ranges include 1:1 to 500:1, alternatively 1:1 to 200:1, alternatively 1:1 to 100:1, alternatively 1:1 to 50: 1.

In an alternative embodiment, little or no aluminoxane is used in the polymerization process described herein. Preferably, the aluminoxane is present in 0 mol% or the aluminoxane is present in a molar ratio of aluminum to transition metal of the catalyst compound of less than 500:1, preferably less than 300:1, preferably less than 100:1, preferably less than 1: 1.

Ionic/non-coordinating anion activators

The term "non-coordinating anion" (NCA) refers to an anion that does not coordinate to the cation or that coordinates only weakly to the cation, thereby remaining sufficiently labile to be displaced by a neutral lewis base. "compatible" noncoordinating anions are those which do not degrade to neutrality when the initially formed complex decomposes. In addition, the anion does not transfer an anionic substituent or moiety to the cation, causing it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions that can be used in accordance with the present invention are those that are compatible, stabilizing the transition metal cation at +1 in the sense of balancing its ionic charge, yet remain sufficiently labile to allow displacement during polymerization. Ionizing activators useful herein typically comprise NCA, especially compatible NCA.

It is within the scope of the invention to use ionizing activators (neutral or ionic). It is also within the scope of the present invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators. For a description of useful activators, see U.S. Pat. Nos. 8,658,556 and 6,211,105.

Preferred activators include N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N-dimethylanilinium tetrakis (perfluorophenyl) borate, N-dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borateTriphenylcarbon tetrakis (perfluorobiphenyl) borateTriphenylcarbon tetrakis (3, 5-bis (trifluoromethyl) phenyl) borateTriphenylcarbenium tetrakis (perfluorophenyl) borate，[Me3NH+][B(C6F5)4-](ii) a 1- (4- (tris (pentafluorophenyl) boronic acid) -2,3,5, 6-tetrafluorophenyl) pyrrolidine(ii) a And tetrakis (pentafluorophenyl) borate, 4- (tris (pentafluorophenyl) borate) -2,3,5, 6-tetrafluoropyridine.

In a preferred embodiment, the activator comprises a triaryl carbon(e.g. triphenylcarbeniumtetraphenylborate)Triphenylcarbenium tetrakis (pentafluorophenyl) borateTriphenylcarbenium tetrakis (2,3,4, 6-tetrafluorophenyl) borateTriphenylcarbon tetrakis (perfluoronaphthyl) borateTriphenylcarbon tetrakis (perfluorobiphenyl) borateTriphenylcarbon tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate)。

In another embodiment, the activator comprises one or more of the following: trialkylammonium tetrakis (pentafluorophenyl) borate, N-dialkylanilinium tetrakis (pentafluorophenyl) borate, N-dimethyl- (2,4, 6-trimethylphenylammonium tetrakis (pentafluorophenyl) borate, trialkylammonium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, N-dialkylanilinium tetrakis (2,3,4, 6-tetrafluorophenyl) borate, trialkylammonium tetrakis (perfluoronaphthyl) borate, N-dialkylanilinium tetrakis (perfluoronaphthyl) borate, trialkylammonium tetrakis (perfluorobiphenyl) borate, N-dialkylanilinium tetrakis (perfluorobiphenyl) borate, trialkylammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N-dialkylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, n, N-dialkyl- (2,4, 6-trimethylanilinium) 5-bis (trifluoromethyl) phenyl) borate, di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate, (where alkyl is methyl, ethyl, propyl, N-butyl, sec-butyl, or tert-butyl).

In one embodiment of the invention, the activator is represented by the formula:

(Z)_d ⁺(A^d-),

wherein Z is (L-H) or a reducible Lewis acid, L is a neutral Lewis base; h is hydrogen; (L-H) + is a Bronsted acid; ad-is a non-coordinating anion having a charge d-; and d is an integer from 1 to 3, preferably Z is (Ar3C +), wherein Ar is aryl or substituted with a heteroatom, C₁-C₄₀Hydrocarbyl or substituted C₁-C₄₀An aryl group of a hydrocarbyl group.

Typical activator to catalyst ratios, for example all NCA activator to catalyst ratios are about 1:1 molar ratios. Alternative preferred ranges include from 0.1:1 to 100:1, alternatively from 0.5:1 to 200:1, alternatively from 1:1 to 500:1, alternatively from 1:1 to 1000: 1. A particularly useful range is from 0.5:1 to 10:1, preferably from 1:1 to 5: 1.

It is also within the scope of the present disclosure that the catalyst compound may be combined with an aluminoxane and NCA combination (see, e.g., U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,453,410; EP 0573120B 1; WO 94/07928; and WO 95/14044, the disclosures of which are incorporated herein by reference in their entirety), which discuss the use of aluminoxanes in combination with ionizing activators.

Useful chain transfer agents are typically alkylaluminoxanes, i.e. compounds of the formula AlR₃，ZnR₂A compound of (wherein each R is independently C)₁-C₈Aliphatic groups, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof) or combinations thereof, such as diethyl zinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum or combinations thereof.

The activators may be mixed together before or after mixing with the catalyst compound, preferably before mixing with one or both of the HMP and VTP catalyst compounds. In some aspects, the same activator or mixture of activators may be used for both the HMP and VTP catalyst compounds. However, in other aspects, a different activator or mixture of activators may be used for each of the HMP and VTP catalyst compounds.

In one aspect, the activator(s) are contacted with the catalyst compound to form a catalyst system comprising an activated catalyst and an activator or other charge-balancing moiety, and then the catalyst system is contacted with one or more monomers. Alternatively, the activator(s) may be co-fed with the monomer(s) to the catalyst compound(s). If both the HMP catalyst system and the VTP catalyst system are used in one polymerization zone (e.g., in a process using a multiple catalyst system such as a dual catalyst system), each catalyst may be contacted with one or more activator(s) (which may likewise be the same or different) and then mixed together. In each case where the same activator is used, the HMP catalyst and VTP catalyst can be contacted with the activator (either before or while the monomers are supplied to the catalyst mixture).

Optionally scavengers or co-activators

In addition to the activator compound, a scavenger or co-activator may also be used in either or both of the HMP and VTP catalyst systems. Aluminum alkyls or organoaluminum compounds that can be used as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and the like. Other oxophilic materials such as diethyl zinc may be used.

Optionally a support material

One or both of the HMP catalyst system and the VTP catalyst system may comprise an inert support material. The support material may be a porous support material, for example, talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays or any other organic or inorganic support material and the like, or mixtures thereof.

The support material may be an inorganic oxide in finely divided form. Suitable inorganic oxide materials for use in the HMP and/or VTP catalyst systems herein include group 2,4, 13, and 14 metal oxides such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be used alone or in combination with the silica or alumina are magnesia, titania, zirconia, and the like. However, other suitable support materials may be employed, for example, finely divided functionalised polyolefins such as finely divided polyethylene. Some aspects may employ any carrier, and/or method for making such a carrier, as described in U.S. published application No. 2015/0025210 (issued as US 9,458,260, incorporated herein by reference) paragraphs [00108] to [00114 ].

VTP composition

The VTP compositions provided herein can include ethylene-derived units in an amount from a lower limit of any one of about 25, 30, 35, 40, 45, 50, 55, 60, 65, and 70 wt% to an upper limit of any one of about 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 100 wt%, provided that the upper limit of the range is greater than the lower limit. Additionally, when the VTP can include one or more diene-derived units, the VTP composition can include diene-derived units in an amount from a lower limit of any one of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1,2,3,4,5,6,7,8, 9, and 10 wt% to an upper limit of any one of about 1,2,3,4,5,6,7,8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, and 30 wt%, provided that the upper limit of the range is greater than the lower limit. The remainder of the VTP composition may be derived from one or more C₃-C₁₂Units of alpha-olefins. In one aspect, the remainder of the VTP composition may consist of propylene-derived units, 1-butene-derived units, 1-hexene-derived units, 1-octene-derived units, or combinations thereof.

The VTP composition may have an Mw of about 5,000 to about 500,000 g/mol. A particular VTP may have a VTP of 5,000; 10,000; 15,000; 20,000; 25,000; 30,000; a lower limit of any of 35,000 and 40,000g/mol to 45,000; 50,000; 55,000; 60,000; 65,000; 70,000; 75,000; 80,000; 85,000; 90,000; 100,000; 110,000; 120,000; 130,000; 150,000; 200,000; 250,000; 300,000; 400,000; mw within the range of from an upper limit of any one of 500,000g/mol, with the proviso that the upper limit of the range is greater than the lower limit of the range. Thus, for example, the VTP composition may have an Mw in the range of about 5,000 to about 500,000g/mol, about 20,000 to about 400,000g/mol, or about 40,000 to about 300,000g/mol, and the like.

In one aspect, the VTP composition can have a moderate to low Mw, such as a Mw of less than or equal to any of about 50,000, 45,000, and 40,000g/mol, such as from about 5,000 to about 50,000g/mol, or from about 5,000 to about 45,000 g/mol. In one aspect, VTP compositions can advantageously impart broad MWD (e.g., Mw/Mn of about 3 or higher) in blended polymer compositions comprising the VTP.

The VTP may be highly branched, including long chain branching. Thus, in particular aspects, the VTP can have a branching index (g' vis) of 0.95 or less, preferably 0.9 or less, preferably 0.85 or less, as determined by GPC as described in the experimental methods section below.

The monomer make-up of the VTP-containing VTP composition may vary as provided by the method of the invention. In one aspect, the VTP composition may comprise units derived from one or more monomers, each monomer independently selected from C₂-C₂₀An alpha-olefin. In one aspect, the monomers are each selected from C₂-C₁₂An alpha-olefin. Suitable monomers may include any monomer(s) suitable for polymerization using a VTP catalyst or HMP catalyst. For example, in one aspect, the VTP present in the VTP composition can be homopolyethylene or homopolypolypropylene. Furthermore, the VTP may be a copolymer, such as ep (d) M. In particular aspects, the VTP composition may comprise one or more cs derived from ethylene₃-C₁₂Units of an alpha-olefin and one or more dienes. One or more C₃-C₁₂The alpha-olefin may, for example, comprise one or more of propylene and 1-butene. The VTP composition may comprise about 20 to about 80 wt% ethylene-derived units, about 0 to about 20 wt% diene-derived units and the balance of one or more C₃-C₈An alpha-olefin. More particularly, toAnd one or more C₃-C₈The olefin may include one or more of propylene and 1-butene.

High molecular weight polymer composition

For the purposes of this disclosure, labeling high molecular weight polymer compositions ("HMP compositions") is done to facilitate differentiation from the VTPs described above, and/or to differentiate polymers prepared by HMP catalyst systems from those prepared by VTP catalyst systems. The use of "HMP" labels alone is not intended to limit the molecular weight (e.g., Mw) of these or other polymers. Rather, suitable ranges for the Mw of these polymers are described herein and guidance should be gained from the description.

In general, the HMP composition may have the same monomer and/or comonomer content as described above for the VTP composition as appropriate. The HMP composition may be a copolymer. For example, the HMP composition may be a blend of ethylene, optional dienes and other C's with the values noted previously for the various VTPs₃-C₁₂A vinyl copolymer having a content of α -olefin derived units. The HMP composition may be an ep (d) M copolymer.

Generally, HMPs will show some differences from VTPs. For example, while HMPs may have vinyl end groups, there is no particular amount required for HMPs used herein.

Additionally, the HMP composition may have a high Mw. For example, the HMP composition may have a Mw of 100,000. In various embodiments, the HMP composition may have a molecular weight of 50,000, 75,000, 100,000; 105,000; 110,000; 115,000; 120,000; 125,000; 130,000; 135,000; 140,000; 145,000; 150,000; 155,000; 160,000; 165,000; 170,000; an Mw of at least any one of 175,000 and 180,000 g/mol. Although an upper limit for Mw is not necessary for the HMP composition, the HMP composition can have a Mw from any of the above lower limits to about 190,000; 200,000; 210,000; 220,000; 230,000; 240,000; 250,000; 260,000; 270,000; 280,000; 290,000; 300,000; 310,000; 320,000; 330,000; 340,000; 350,000; 400,000; 450,000; 500,000; mw of any one of 550,000 and 600,000g/mol at an upper limit value.

Examples

The catalysts used in the examples of the present invention are catalyst 1 and catalyst 2 and the activators used in the examples are activator 1 and activator 2, both shown below. Catalyst 1 and activators 1 and 2 were obtained from Albemarle corp. Catalyst 2 was prepared according to the method described in U.S. patent No. 9,458,254, incorporated herein by reference.

Polymer synthesis: examples 1 to 7

The polymerization was carried out in a 1L Continuous Stirred Tank Reactor (CSTR) using the solution process. Solvent (isohexane, iC6), monomer and scavenger (tri-n-octylaluminum as 1.843X 10^-6A feed of tri-n-octylaluminum (TNOAL)) in mol/mL with a solution of iC6 was supplied to the reactor. A solution of metallocene and activator (1.02 eq) in toluene was metered into the reactor and heating was maintained with a steam/water mixture. Samples were taken directly from the reactor, quenched with water, treated with antioxidant (Irganox 1076), and then dried. The process conditions are specified in tables 1a and 1b.

Polymer synthesis: examples 8 to 10

The polymerization was carried out in a 28L CSTR using a solution process. Feeds of solvent (isohexane, iC6), monomer, hydrogen, and scavenger (TNOAL 3 wt%, in iC6) were provided to the reactor. A solution of metallocene 1 and activator (1.0 eq) in toluene was metered into the reactor and the heat of polymerization was used to drive the solution temperature to the target value. Samples were taken directly from the reactor, quenched with water, treated with an antioxidant, and then dried. The process conditions are specified in tables 1c and 1d.

Polymer blend synthesis: blend samples 1-3 and comparative sample 1

Using the polymers and amounts specified in table 5, melt blends were prepared on a PHI press set at 285 ° f, and each press was 10 tons pressure for 10-15 s. The samples were pressed into circular films between Mylar sheets, then combined and pressed again. The sample was then folded twice and pressed again. This was repeated for a total of 4 presses. The samples were then analyzed by SAOS.

Polymer blend synthesis: blend samples 4-6 and comparative sample 2

The polymer cut into small pieces (in the amounts given in table 8), toluene (300mL) and Irganox 1076 (about 20mg) were combined and stirred in a flask for about 24 h. Poured into a Teflon-lined dish. The flask was rinsed into the dish with toluene (100 mL). The plates were heated with steam to evaporate the solvent. After about one hour, most of the solvent was removed. MeOH (100mL) was added and heating was continued for an additional hour to evaporate the MeOH and residual toluene. The polymer, which was a film, was removed from the tray and then dried in a vacuum oven (110-. The starting materials and blends were pressed into films before running the SAOS. The SAOS data are classified as follows.

TABLE 1a reactor conditions for the preparation of polymers in examples 1-7

TABLE 1b reactor conditions for the preparation of polymers in examples 1-7

TABLE 1c reactor conditions for the preparation of polymers in examples 8-10

TABLE 1d reactor conditions for the preparation of polymers in examples 8-10

TABLE 2 Mooney and compositional data for examples 1-10 (C2 and ENB from IR)

TABLE 3a summary of SAOS data (125 ℃) for examples 1-4

TABLE 3b summary of SAOS data (100 ℃) for examples 5-10

TABLE 4a comparison of SAOS data (125 ℃) for examples 2(Cat 2) and 3(Cat 1)

TABLE 4b comparison of SAOS data (100 ℃) for examples 6(Cat 2) and 8(Cat 1)

Table 5 blend design: blend samples 1-3 and comparative blend sample 1

TABLE 6 summary of SAOS data (125 ℃) for blends 1-3 and comparative blend 1

TABLE 7 comparison of SAOS data (125 ℃) for blend 1 and comparative blend 1

Table 8 blend design: blend samples 4-6 and comparative blend 2

TABLE 9 molecular weight data for examples 5-10 and blends 4-6 and comparative blend 2

TABLE 10 SAOS data (100 ℃ C.) for blend samples 4-6 and comparative blend sample 2

TABLE 11 comparison of SAOS (100 ℃) data for blend 5 and comparative blend 2

TABLE 12 passage of examples 1 to 10¹H NMR Spectroscopy of olefins/1000C

Fig. 1,4, 7 and 10 show the complex viscosity versus frequency for the inventive and comparative blends. Figures 2,5, 8 and 11 show the tan (d) relative frequencies of the inventive and comparative blends. Fig. 3,6, 9 and 12 show Van Gurp Palmen plots of phase angle (d) versus complex viscosity for the inventive and comparative blends.

As shown in the examples and figures of the present invention, the inventors have found that the EPDM of the present invention has advantageous rheological properties. As shown in examples 6(Cat 2, 5.1E 7 Kg Pol/mol Cat) and 4(Cat 1, 2.0E7 Kg Pol/mol Cat) of tables 1a and 1b, this system, Cat2, was superior to Cat1 in that: has higher catalyst activity under the condition of manufacturing EPDM.

The advantages of this system, Cat2, compared with those EPDM polymers derived from Cat1, are: more vinyl olefin end groups are produced in the EPDM polymer. This is shown in the data of table 12. All EPDM from Cat2 had a vinyl >0.1/1000C, while those from Cat1 had a vinyl ≦ 0.02/1000C. This high vinyl content is believed to allow EPDM having vinyl end groups to incorporate into EPDM chains growing on the catalyst, resulting in Long Chain Branching (LCB).

Molecular weight analysis indicated: the polymers made with Cat2 under steady state conditions had broader MWDs than Cat1, and in addition had lower viscosity average g' than those made with Cat1 (Table 9). This is consistent with the presence of LCB in these materials. These two factors give the advantage of improved processability of EPDM derived from Cat 2.

Improved processability is seen in the higher cMLAs of Ex 1,2 vs Ex 3 and Ex 5-7 vs Ex 8. The cMLRA normalizes MLRA to a constant ML of 80. The longer the material takes to relax is consistent with the greater entanglement due to LCB in the polymer.

The improved processability is also seen in the shear rheology of EPDM derived only from Cat2 (tables 3,4 and figures 1, 2) and blends containing other EPDM of different molecular weights (tables 6,7, 10, 11 and figures 3, 4). Cat 2EPDM had a higher shear-thinning ratio (STR) at 0.245s than EPDM made with Cat1^-1Lower tan (δ) and lower δ at G ═ 100KPa, as shown in example 2(Cat 2) vs example 3(Cat 1), table 4a and example 6(Cat 2) vs example 8(Cat 1), table 4b. Higher shear-thinning ratios indicate: at high shear rates and increased viscosity, whether used alone or as a compound with carbon black, oil and other additives, the polymer will have a reduced viscosity and thus higher throughput in the extruder, which is important for bubble stability in foams at low shear rates. Lower tan (δ) and at G ═ 100KPaLower δ indicates: the material behaves more like an elastic solid than the comparative material. This is also consistent with the crossover point (where storage and loss moduli are equal) for the inventive sample shifted to lower frequencies. These important attributes contribute to the increased part stability, post extrusion (post extrusion) of the material itself or compounded with carbon black, oil and other additives.

Blends of polymers made with Cat2 and Cat1 also had significantly improved processability compared to comparative blends made with materials from Cat1 alone, resulting from higher shear-to-thinning ratio (STR) at 0.245s^-1Lower tan (δ) and lower δ at G ═ 100KPa indicate. This is shown in tables 5-7 and is best shown by careful comparison of blend 1 and comparative blend 1 in table 7. It is also shown in a set of individual blends in tables 8-11, especially in table 11 as a careful comparison of blend 5 and comparative blend 2.