# US 12,006,423 B2 · Methods of making polymer compositions with enhanced elasticity by employing VTP and HMP catalyst systems in parallel processes

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- Number: US 12,006,423 B2
- Document ID: US12006423B2
- Status: Granted
- Kind: B2
- Application number: 17/269,433
- Filed: 2019-08-15
- Published: 2021-06-17
- Granted: 2024-06-11
- Earliest claimed: 2018-08-29
- Assignees: ExxonMobil Engineering & Technology Company
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Francis C. Rix; Jo Ann M. Canich; Rainer Kolb
- Web page: https://patentgrep.com/patent/US12006423B2

## CPC

- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08L 23/0815: {with aliphatic 1-olefins containing one carbon-to-carbon double bond}
- C08F 210/18: with non-conjugated dienes, e.g. EPT rubbers
- C08L 23/16: Ethylene-propylene or ethylene-propylene-diene copolymers
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08L 2203/10: used for bottles
- 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 2207/07: Long chain branching
- C08L 2314/06: Metallocene or single site catalysts
- Y02P 20/52: using catalysts, e.g. selective catalysts
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Provided herein are methods of making blended polymer compositions having enhanced elasticity. The present methods comprise the steps of producing a first polymer composition using a VTP catalyst system, producing a second polymer composition using a HMP catalyst system and combining the first polymer composition and the second polymer composition to make the blended polymer composition. The present methods include blending/combining the polymer compositions produced by different catalyst systems. One such catalyst system includes (i) a vinyl-terminated polymer (VTP) catalyst system comprising a VTP catalyst compound (referred to herein also as a “VTP catalyst”) and one or more activators. Another catalyst system includes a high molecular-weight polymer (HMP) catalyst system comprising a HMP catalyst compound (referred to herein also as a “HMP catalyst”) and one or more activators. The activators of these different catalyst systems can be the same or different in whole or in part.

## Claims

### Claim 1

A method of making a blended polymer composition having enhanced elasticity, wherein the blended polymer composition comprises a sheer thinning ratio (STR) greater than 100, the method comprising the steps of:
(a) providing a first polymer composition, wherein the first polymer composition is a vinyl terminated polymer (VTP) composition produced with a VTP catalyst compound;
(b) providing a second polymer composition, wherein the second polymer composition is a high molecular-weight polymer (HMP) composition produced with a HMP catalyst compound;
(c) combining the first polymer composition and the second polymer composition; and
(d) recovering a blended polymer composition;
wherein weight average molecular weight of the HMP composition is greater than that of the VTP composition; and
wherein the VTP catalyst compound is represented by the formula:
wherein (1) J is a divalent bridging group comprising C, Si or both;
(2) M is a group 4 transition metal;
(3) each X is independently a univalent anionic ligand, or two Xs joined to form a chelating ligand, a diene ligand, or an alkylidene ligand; and
(4) each of 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 can optionally be bonded together to form a saturated or partially saturated cyclic or fused ring structure.

### Claim 2 (depends on 1)

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

### Claim 3 (depends on 2)

The method of claim 2, wherein the diene is 5-ethylidene-2-norbornene.

### Claim 4 (depends on 2)

The method of claim 2, wherein the one or more alpha-olefins or cyclic olefins is selected from propylene, 1-butene, 1-hexene, 1-octene, or combinations thereof.

### Claim 5 (depends on 4)

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

### Claim 6 (depends on 1)

The method of claim 1, wherein a total ethylene content of the VTP composition is about 20-100 wt %, a total alpha-olefin or cyclic olefin content of the VTP composition is about 20-80 wt %, and the a total diene content of the VTP composition is about less than or equal to about 20 wt %, based on the VTP composition.

### Claim 7 (depends on 1)

The method of claim 1, wherein the VTP composition is a copolymer of (ethylene)x(propylene)y(diene)z where x=20-80 wt %, y=80-20 wt %, z=0-20 wt % and x+y+z=100 wt %.

### Claim 8 (depends on 1)

The method of claim 1, wherein the HMP composition comprises ethylene, one or more olefins, cyclic olefins, and dienes.

### Claim 9 (depends on 1)

The method of claim 1, wherein the first polymer composition and the second polymer composition are blended in solution to form the blended polymer composition.

### Claim 10 (depends on 1)

The method of claim 1, wherein the first polymer composition and/or the second polymer composition are produced at a temperature between about 75° C. and about 250° C.

### Claim 11 (depends on 1)

The method of claim 1, wherein the blended polymer composition has an elasticity, as measured by the tangent of the phase angle, of between about 0.650 rad/s and about 0.975 rad/s.

### Claim 12 (depends on 1)

The method of claim 1, wherein each R3 of the VTP catalyst compound is hydrogen; each R4 is independently a C1-C10 alkyl; each R2 and R7 is independently hydrogen, or C1-C10 alkyl, each R5 and R6 is independently hydrogen, C1-C50 substituted or unsubstituted hydrocarbyl, or C1-C50 substituted or unsubstituted halocarbyl; R4 and R5, R5 and R6, and/or R6 and R7 may optionally be bonded together to form a ring structure; and J is represented by a formula Ra2J′, where J′ is C or Si, and each Ra is, independently, C1 to C20 substituted or unsubstituted hydrocarbyl, provided that the two Ra may be bonded together to form a saturated or partially saturated cyclic or fused ring structure that incorporates J′.

### Claim 13 (depends on 1)

The method of claim 1, wherein the two Ra in a formula Ra2J′ are bonded together to form a saturated or partially saturated cyclic or fused ring structure that incorporates J′.

### Claim 14 (depends on 1)

The method of claim 1, wherein, within the VTP catalyst compound, J is selected from the group consisting of: cyclopentamethylenesilylene, cyclotetramethylenesilylene, and cyclotrimethylenesilylene.

### Claim 15 (depends on 1)

The method of claim 1, wherein, within the VTP catalyst compound, R2 is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl and isomers thereof; and further wherein R4 is independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, octyl, nonyl, decyl and isomers thereof.

### Claim 16 (depends on 1)

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

### Claim 17 (depends on 1)

The method of claim 1, wherein the VTP composition has one or more of the following properties:
(a) weight average molecular weight in the range of about 5,000 g/mol to about 500,000 g/mol;
(b) weight average molecular weight (Mw)/number average molecular (Mn) of greater than about 2.5;
(c) g′ (vis average) of less than about 0.95;
(d) Storage modulus is equivalent to the loss modulus at less than about 4 rad/s at 100° C.;
(e) Storage modulus is not equivalent to the loss modulus between about 0.1 rad/s and 128 rad/s at 100° C.;
(f) cMLRA greater than about 300 if ML (1+4, 125° C.) is greater than or equal to about 10; and
(g) tan (δ) at 0.245 rad/s of less than about 1 at 100° C.

### Claim 18 (depends on 1)

The method of claim 1, wherein the blended polymer composition has one or more of the following properties:
(a) δ at G* of 100,000 Pa is less than about 48°;
(b) Storage modulus is equivalent to the loss modulus at less than about 0.9 rad/s at 100° C.;
(c) tan (δ) at 0.245 rad/s of less than about 1.2 at 100° C.; and
(d) tan (δ) at 0.245 rad/s of less than about 1.6 at 125° C.

### Claim 19 (depends on 1)

The method of claim 1, wherein the HMP catalyst compound is represented by the formula:
wherein (1) J is a divalent bridging group comprising C, Si, or both;
(2) M is a group 4 metal;
(3) each X is independently a univalent anionic ligand, or two Xs joined and bound to the metal atom to form a metallocycle ring, or two Xs 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″9, and R″10 is independently hydrogen, C1-C50 hydrocarbyl, substituted hydrocarbyl, halocarbyl, or substituted halocarbyl provided that any one or more of the pairs R″1 and R″2, R″3 and R″4, R″5 and R″6, R″6 and R″7, R″8 and R″9, and R″9 and R″10, can 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 R*2C, R*2Si, R*2CCR*2, R*C═CR*, R*2CSiR*2, or R*2SiSiR*2, where each R* is, independently, hydrogen or a C1 to C20 containing hydrocarbyl or substituted hydrocarbyl and optionally two or more adjacent R* join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent.