# US 2019/0169413 A1 · Polymer Compositions and Processes for Their Production

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- Number: US 2019/0169413 A1
- Document ID: US20190169413A1
- Status: Published application
- Kind: A1
- Application number: 16/266,186
- Filed: 2019-02-04
- Published: 2019-06-06
- Earliest claimed: 2015-01-14
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Jo Ann M. Canich; Rainer Kolb; Periagaram S. Ravishankar; Phillip T. Matsunaga; Peijun Jiang; Rhutesh K. Shah; Narayanaswami Dharmarajan
- Web page: https://patentgrep.com/patent/US20190169413A1

## CPC

- C08L 23/16: Ethylene-propylene or ethylene-propylene-diene copolymers
- C08F 2/001: {Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer (C08F295/00, C08F297/00 take precedence)}
- C08F 4/76: selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
- C08F 210/06: Propene
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F 210/18: with non-conjugated dienes, e.g. EPT rubbers
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 2500/09: Long chain branches
- C08F 2500/17: Viscosity
- C08L 2205/02: containing two or more polymers of the same C08L -group
- C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
- C08L 2205/06: having improved processability or containing aids for moulding methods
- C08L 2207/07: Long chain branching
- C08L 2312/04: with phenolic resin
- C08L 2314/06: Metallocene or single site catalysts
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Provided herein are polymerization processes and polymer compositions including reactor blends formed by such polymerization processes. The polymerization processes include copolymerization using two metallocene catalyst systems: the first catalyst system capable of producing polymers having 60% or more vinyl terminations, the second catalyst system capable of producing high molecular weight polymers, preferably incorporating at least some of the polymers produced by the first catalyst system into the high molecular weight polymers. The reactor blends formed thereby therefore include first and second copolymer components, which may differ in monomer content and weight-average molecular weight (Mw). Furthermore, the reactor blends may exhibit advantageous rheological properties, at least some of which are consistent with long-chain branching. Preferred reactor blends comprise ethylene-propylene-diene (EPDM) terpolymers.

## Claims

### Claim at position 1

-15. (canceled)

### Claim 16

A polymer composition comprising a reactor blend of:
(a) a first EPDM copolymer having ethylene-derived content in a range of 20 to 80 wt %, diene-derived content in a range of 0.3 to 15 wt %, Mw of 5,000 to 80,000 g/mol, and at least 60% vinyl terminations relative to the total number of end-group unsaturations in the first EPDM copolymer; and
(b) a second EPDM copolymer having at least 5 wt % less ethylene content than the first EPDM copolymer, diene-derived content in a range of 0.3 to 15 wt %, and Mw at least 1.5 times greater than the Mw of the first EPDM copolymer;
wherein the reactor blend has both (i) a phase angle δ at complex shear modulus G*=100,000 Pa of less than 54.5° and (ii) LCB index measured at 125° C. of less than 5.

### Claim 17 (depends on 16)

The polymer composition of claim 16, wherein the reactor blend is formed by a polymerization process comprising:
(I) copolymerizing ethylene, propylene, and diene monomers in the presence of a VTP catalyst system, thereby forming a first polymerization intermediate comprising the first EPDM copolymer; and
(II) copolymerizing the first polymerization intermediate, and optionally additional ethylene, propylene, and diene monomers in the presence of a HMP catalyst system, thereby forming the reactor blend;
wherein:
(i) the HMP catalyst system comprises a HMP catalyst compound and a first activator;
(ii) the VTP catalyst system comprises a VTP catalyst compound and a second activator; and
(iii) the VTP catalyst compound has the structural formula:
where: (1) J is a divalent bridging group comprising C, Si, or both; (2) M is Hf; (3) each X is independently a univalent anionic ligand, or two Xs are joined and bound to the 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 R2-R7 is independently hydrogen, C1-C50 substituted or unsubstituted hydrocarbyl, or C1-C50 substituted or unsubstituted halocarbyl, provided that any one or more of the pairs R4 and R5, R5 and R6, and R6 and R7 may be bonded together to form a saturated or partially saturated cyclic or fused ring structure.

### Claim 18 (depends on 16)

The polymer composition of claim 16, wherein the HMP catalyst compound is selected from mono-cyclopentadienyl amido group 4 transition metal complexes; mono-Cp amido variants; bridged fluorenyl-cyclopentadienyl group 4 transition metal complexes; Cp-fluorenyl variants; biphenyl phenol (BPP) transition metal complexes; pyridyl amide transition metal complexes; pyridyl diamide transition metal complexes; and any combination thereof.

### Claim 19 (depends on 17)

The polymer composition of claim 17, wherein at least a portion of the second EPDM copolymer incorporates at least a portion of the first EPDM copolymer in the first polymerization intermediate.

### Claim 20 (depends on 16)

The polymer composition of claim 16, wherein the second EPDM copolymer comprises either: (i) comb-type polymers with amorphous backbones and semi-crystalline branches and (ii) comb-type polymers with semi-crystalline backbones and amorphous branches.

### Claim 21 (depends on 16)

The polymer composition of claim 16, wherein the first EPDM copolymer has a Mooney viscosity (1+4 at 125° C.) of 10 mu or less and the second EPDM copolymer has a Mooney viscosity (1+4 at 125° C.) of 20 mu or more.

### Claim 22 (depends on 16)

The polymer composition of claim 16, having MWD (Mw/Mn) of 3.5 or greater.

### Claim 23 (depends on 16)

The polymer composition of claim 16, having:
(i) corrected Mooney Large Relaxation Area (cMLRA) at Mooney Large Viscosity (ML)=80 Mooney Units (mu), such that cMLRA is from 240 to 2000 mu*sec, where ML is determined at (1+4@ 125° C.);
(ii) MLRA/ML ratio greater than R, where R=9.57(ML)−40.83, where ML is the Mooney Large Viscosity of the copolymer composition determined at (1+4@ 125° C.);
(iii) shear thinning index (STI) measured at 125° C. greater than 0.950;
(iv) LCB index measured at 125° C. of less than 5; and
(v) relaxation time τ (determined at 125° C. using the Cross equation) greater than 1.4 sec.

### Claim 24 (depends on 16)

The polymer composition of claim 16, further comprising one or more curing agents, such that the first EPDM copolymer and second EPDM copolymer are at least partially cross-linked.

### Claim 25 (depends on 24)

The polymer composition of claim 24, further comprising one or more of: extender oil, processing oil; carbon black, plasticizer, and antioxidant.