# US 10,246,542 B2 · Atactic polypropylene comb block polyolefins useful as modifiers in polyolefins and hydrocarbons

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- Number: US 10,246,542 B2
- Document ID: US10246542B2
- Status: Granted
- Kind: B2
- Application number: 15/214,133
- Filed: 2016-07-19
- Published: 2017-03-16
- Granted: 2019-04-02
- Earliest claimed: 2015-09-14
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Andy H. Tsou; George Rodriguez; Carlos R. Lopez-Barron; Donna J. Crowther; Hillary L. Bradshaw; Antonios K. Doufas
- Web page: https://patentgrep.com/patent/US10246542B2

## CPC

- C08F 290/042: {Polymers of hydrocarbons as defined in group C08F10/00}
- C08F 10/06: Propene
- 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}
- C08L 23/12: Polypropene
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08L 2207/14: Amorphous or atactic polypropylene
- 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)

## Abstract

An atactic polypropylene comb-block polyolefin comprising two blocks including a polyolefin backbone and atactic polypropylene combs pendant to the backbone having a weight average molecular weight of at least 8000 g/mole and a crystallinity of less than 20%, where the atactic polypropylene comb-block polyolefin has comb number of at least 2. The atactic polypropylene comb-block polyolefin is made by contacting at a temperature within a range from 20 to 70° C. propylene with a first metallocene precursor to form vinyl-terminated atactic polypropylene to form vinyl-terminated atactic polypropylene, then contacting at a temperature within a range from 40 to 150° C. the vinyl-terminated atactic polypropylene with ethylene, propylene, or both and a second metallocene precursor to form the backbone.

## Claims

### Claim 1

A process for preparing comb-block polyolefins comprising:
contacting, at a temperature within a range from 20 to 70° C., propylene with a first metallocene precursor and an activator to form vinyl-terminated atactic polypropylene having a weight average molecular weight of at least 8000 g/mole and a crystallinity of less than 20%;
contacting in a subsequent step, at a temperature within a range from 40 to 150° C., the vinyl-terminated atactic polypropylene with ethylene, propylene, or both, a second metallocene precursor, and an activator to form a comb-block polyolefin; and
forming in said subsequent step a linear low molecular weight component (LLMW) comprising ethylene or ethylene/propylene copolymers and having a number average molecular weight within a range from 7,000 to 50,000 g/mole,
wherein the comb-length of the comb-block polyolefin is greater than the entanglement molecular weight of atactic polypropylene.

### Claim 2 (depends on 1)

The process of claim 1, wherein the first metallocene precursor is selected from the group consisting of bridged C2 symmetric hafnocenes and zirconocenes.

### Claim 3 (depends on 1)

The process of claim 1, wherein the comb-block polyolefin is a comb-block polypropylene having a weight average molecular weight within the range from 50,000 to 500,000 g/mole.

### Claim 4 (depends on 1)

The process of claim 1, wherein the comb-block polyolefin is a comb-block polyethylene having a weight average molecular weight within the range from 100,000 to 5,000,000 g/mole.

### Claim 5 (depends on 1)

The process of claim 1, wherein the contacting steps occur in the same reactor.

### Claim 6 (depends on 1)

The process of claim 1, wherein the contacting steps occur in different reactors.

### Claim 7 (depends on 1)

The process of claim 1, wherein the first metallocene and/or second metallocene is selected from those having the following structure:
wherein M is a Group 4 metal;
each X is independently a halogen or C1 to C10 alkyl, or C6 to C10 aryl;
“A” is a methylene or ethylene, wherein the ethylene has two R1 groups on each carbon, or “A” is a silane;
each R1 is independently selected from hydrogens, C1 to C10 alkyls, and C6 to C10 aryls;
each of R2 to R7 is independently selected from hydrogens, C1 to C10 alkyls, C6 to C10 aryls, C7 to C24 alkylaryls, and C7 to C24 arylalkyls; and
wherein R2 and R3 may form a C4 to C7 saturated or unsaturated ring.

### Claim 8 (depends on 1)

The process of claim 1, wherein the GPC of the comb-block polyolefins exhibits bimodal molecular weight distribution.

### Claim 9 (depends on 1)

The process of claim 1, wherein the comb-block polyolefins has a z-average molecular weight of greater than 500,000 g/mole.

### Claim 10 (depends on 1)

The process of claim 1, wherein the comb-block polyolefins has a molecular weight distribution (Mw/Mn) greater than 10.

### Claim 11 (depends on 1)

The process of claim 1, wherein the comb-block polyolefins have comb number of 2 or more.

### Claim 12 (depends on 1)

The process of claim 1, wherein the second metallocene precursor is selected from Cs symmetric bis-cyclopentadienyl Group 4 complexes, C2 symmetric bis-cyclopentadienyl Group 4 complexes, and mono-cyclopentadienyl Group 4 complexes.

### Claim 13 (depends on 1)

The process of claim 1, wherein the second metallocene precursor is selected from those having the following structure:
wherein M is a Group 4 metal;
each X is independently a halogen or C1 to C10 alkyl, or C6 to C10 aryl;
“A” is a methylene or ethylene, wherein the ethylene has two R1 groups on each carbon, or “A” is a silane;
each R1 is independently selected from hydrogens, C1 to C10 alkyls, and C6 to C10 aryls;
each of R2 to R13 is independently selected from hydrogens, C1 to C10 alkyls, C6 to C10 aryls, C7 to C24 alkylaryls, and C7 to C24 arylalkyls; and
wherein R2 and R3 may form a C4 to C7 saturated or unsaturated ring.

### Claim 14 (depends on 1)

The process of claim 1, wherein the second metallocene precursor is selected from those having the following structure:
wherein:
M is a Group 4 metal;
each X is independently a halogen or C1 to C10 alkyl, or C6 to C10 aryl;
“A” is a methylene or ethylene, wherein the ethylene has two R1 groups on each carbon, or “A” is a silane;
Q is a heteroatom or hydrocarbon group; wherein “n” is 1, 2 or 3;
each R1 is independently selected from hydrogen, C1 to C10 alkyls, and C6 to C10 aryls;
each of R2 to R5 is independently selected from hydrogens, C1 to C10 alkyls, C6 to C10 aryls, C7 to C24 alkylaryls, and C7 to C24 arylalkyls; and
wherein R6 is selected from C1 to C10 alkyls, and C4 to C20 saturated or unsaturated rings.

### Claim 15 (depends on 1)

The process of claim 1, wherein at least the first contacting takes place at a pressure of at least 1 MPa.