# US 10,119,016 B2 · Heterophasic copolymers and sequential polymerization

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- Number: US 10,119,016 B2
- Document ID: US10119016B2
- Status: Granted
- Kind: B2
- Application number: 15/644,528
- Filed: 2017-07-07
- Published: 2017-10-26
- Granted: 2018-11-06
- Earliest claimed: 2015-06-05
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Lubin Luo; Gregory S. Day; Matthew W. Holtcamp
- Web page: https://patentgrep.com/patent/US10119016B2

## CPC

- C08L 23/12: Polypropene
- C08J 9/00: Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof (mechanical aspects of shaping of plastics or substances in a plastic state for the production of porous or cellular articles B29C)
- C08L 23/24: having ten or more carbon atoms
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- C08F 2410/06: Catalyst characterized by its size
- C08F 2500/05: Bimodal or multimodal molecular weight distribution
- C08J 2323/10: Homopolymers or copolymers of propene
- C08L 2207/02: Heterophasic composition
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

This invention relates to heterophasic copolymers of propylene and an alpha olefin comonomer having a high fill phase content (≥15%), and heterophasic polymerization processes using a single site catalyst system with a support having high average particle size (PS≥30 μm), high surface area (SA≥400 m2/g), low pore volume (PV≤2 mL/g), and a mean pore diameter range of 1≤PD≤20 nm.

## Claims

### Claim 1

A process for polymerization of propylene and a comonomer, comprising:
(a) contacting propylene monomer under polymerization conditions with a first catalyst system, comprising a single site catalyst precursor compound, an activator, and a support having an average particle size of more than 30 microns, a surface area of 400 m2/g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 20 nm (10 to 200 angstroms) as determined by BET nitrogen adsorption, to form a matrix phase of propylene polymer comprising at least 50 mol% propylene and having a porosity of 15% or more as determined by mercury intrusion porosimetry; and
(b) contacting an alpha olefin monomer selected from ethylene, C3 to C20 alpha olefins, or a combination thereof, including at least one alpha olefin other than propylene, with a second catalyst system under polymerization conditions to form a fill phase for the pores of the matrix, wherein the second catalyst system comprises a metallocene catalyst precursor compound, an activator, and a support, and wherein the second catalyst system comprises, compositionally, the same or different single site catalyst precursor compound as in the first catalyst system, the same or different activator as in the first catalyst system, the same or different support as in the first catalyst system, or any combination thereof,
(c) obtaining a heterophasic propylene copolymer composition comprising:
A) a matrix phase comprising at least 50 mol % propylene and having:
1) a 1% Secant flexural modulus of at least 1000 MPa, determined according to ASTM D 790 (A, 1.0 mm/min);
2)more than 5 and less than 200 regio defects (defined as the sum of 2,1-erythro and 2,1-threo insertions, and 3,1-isomerizations) per 10,000 propylene units, determined by 13C NMR; and
3) when comonomer is present, a composition distribution breadth index of 50% or more; and
B) a fill phase at least partially filling pores in the matrix phase, wherein the fill phase comprises at least 30 wt % of the heterophasic propylene copolymer composition, based on the total weight of the matrix and fill phases.

### Claim 2 (depends on 1)

The process of claim 1, wherein the fill phase comprises 35 wt % or more of the heterophasic propylene copolymer composition, based on the total weight of the matrix and fill phases.

### Claim 3 (depends on 1)

The process of claim 1, wherein the matrix phase has a melting point (Tm, DSC peak second melt) of at least 100° C.

### Claim 4 (depends on 1)

The process of claim 1, wherein the matrix phase has a median pore diameter less than 165 μm, as determined by mercury intrusion porosimetry.

### Claim 5 (depends on 1)

The process claim 1, wherein the fill phase comprises a polyolefin having a Tg of −20° C. or less determined by DSC.

### Claim 6 (depends on 1)

The process of claim 1, wherein the matrix phase has a multimodal molecular weight distribution and an overall molecular weight distribution of 5 or more.

### Claim 7 (depends on 1)

The process of claim 1, wherein the fill phase of component B) comprises ethylene and from about 3 wt % to 75 wt % of one or more C3 to C20 alpha olefins.

### Claim 8 (depends on 1)

The process of claim 1, wherein the fill phase of component B) has a CDBI of 50% or more.

### Claim 9 (depends on 1)

The process of claim 1, wherein the heterophasic propylene copolymer composition is particulated and at least 95% by volume of the particles has a particle size greater than about 120 μm.

### Claim 10 (depends on 1)

The process of claim 1, wherein the heterophasic propylene copolymer composition has:
1) a total propylene content of at least 75 wt %;
2) a total co-monomer content from about 3 wt % up to about 25 wt %;
3) a CDBI of at least 60%;
4) a fill phase content of 35 wt % or more, based on the total weight of the matrix and fill phases;
5) a matrix median pore diameter greater than 6 μm and less than 160 μm, as determined by mercury intrusion porosimetry;
6) at least 50% isotactic pentads;
7) more than 10 regio defects per 10,000 propylene units, determined by 13C NMR;
8) a 1% Secant flexural modulus of greater than about 300 MPa;
9) a matrix phase having a melting point (Tm, DSC peak second melt) of at least 120° C.;
10) a fill phase having a Tg of −30° C. or less determined by DSC;
11) a heat of fusion (Hf, DSC second heat) of 60 J/g or more;
12) at least 95% by volume having a particle size greater than 150 μm up to 10 mm;
13) a melt flow rate (MFR, ASTM 1238, 230° C., 2.16 kg) from about 0.1 dg/min up to about 300 dg/min; and
14) an Mw (as measured by GPC-DRI) from 50,000 to 1,000,000 g/mol.

### Claim 11

A process for polymerization of propylene and a comonomer, comprising:
(a) contacting propylene monomer under polymerization conditions with a first catalyst system, comprising a single site catalyst precursor compound, an activator, and a support having an average particle size of more than 30 microns, a surface area of 400 m2/g or more, a pore volume of from 0.5 to 2 mL/g, and a mean pore diameter of from 1 to 20 nm (10 to 200 angstroms) as determined by BET nitrogen adsorption, to form a matrix phase of propylene polymer comprising at least 50 mol % propylene and having a porosity of 15% or more as determined by mercury intrusion porosimetry; and
(b) contacting an alpha olefin monomer selected from ethylene, C3 to C20 alpha olefins, or a combination thereof, including at least one alpha olefin other than propylene, with a second catalyst system under polymerization conditions to form a fill phase for the pores of the matrix, wherein the second catalyst system comprises a metallocene catalyst precursor compound, an activator, and a support, and wherein the second catalyst system comprises, compositionally, the same or different single site catalyst precursor compound as in the first catalyst system, the same or different activator as in the first catalyst system, the same or different support as in the first catalyst system, or any combination thereof.

### Claim 12 (depends on 11)

The process of claim 11, wherein (1) the polymerization of the alpha olefin monomer in (b) is in the presence of the matrix phase from (a), (2) the polymerization of the propylene monomer with the first catalyst system in (a) is in the presence of the fill phase from (b), or (3) a combination thereof.

### Claim 13 (depends on 11)

The process of claim 11, wherein the contacting in (a) comprises polymerizing the propylene monomer for a time period, A1, optionally increasing a concentration of hydrogen or other chain termination agent in the polymerization after time period A1 and polymerizing the propylene in the presence of the hydrogen or other chain transfer agent for a time period, A2, wherein a time period A equals the sum of time periods A1 and A2, and the contacting in (b) comprises polymerizing the alpha olefin monomer for a time period, B, after time period A.

### Claim 14 (depends on 13)

The process of claim 13, wherein time period A2 is greater than zero, wherein time period A1 is at least as long as time period A2, and wherein the concentration of the hydrogen or other chain transfer agent during time period A2 is at least three times greater than the concentration of the hydrogen or other chain transfer agent in time period A1.

### Claim 15 (depends on 13)

The process of claim 13, wherein the support of the first catalyst system has an average particle size of more than 50 μm, a surface area of less than 1000 m2/g, or a combination thereof.

### Claim 16 (depends on 13)

The process of claim 13, wherein the specific surface area of the support of the first catalyst system is more than 650 m2/g and the mean pore diameter is less than 7 nm (70 Å).

### Claim 17 (depends on 16)

The process of claim 16, wherein the first catalyst system has a bimodal particle size distribution, wherein a larger one of the first catalyst system modes comprises at least about 80 vol % and a smaller one of the catalyst system modes comprises at least about 5 vol %, based on the total volume of the first catalyst system.

### Claim 18 (depends on 13)

The process of claim 13, wherein the specific surface area of the support of the first catalyst system is less than 650 m2/g, the mean pore diameter is greater than 7 nm (70 Å), or both.

### Claim 19 (depends on 13)

The process of claim 13, wherein the support of the first catalyst system comprises agglomerates of primary particles, and the second catalyst system comprises fragments from the first catalyst system.

### Claim 20 (depends on 13)

The process of claim 13, wherein the alpha olefin monomer comprises ethylene and from about 3 wt % to 75 wt % of one or more C3 to C20 alpha olefins.

### Claim 21 (depends on 13)

The process of claim 13, wherein the propylene monomer in (a) is essentially free of ethylene and C4 to C20 alpha olefins, and the propylene polymer formed after time period A is a propylene homopolymer.

### Claim 22 (depends on 13)

The process of claim 13, wherein the activator of the first catalyst system comprises alumoxane.

### Claim 23 (depends on 13)

The process of claim 13, wherein the first catalyst system further comprises a co-activator selected from the group consisting of: trialkylaluminum, dialkylmagnesium, alkylmagnesium halide, and dialkylzinc.

### Claim 24 (depends on 13)

The process of claim 13, wherein the contacting of the propylene monomer with the first catalyst system during time period A1, time period A2, or the contacting of the alpha olefin monomer with the second catalyst system during time period B, or a combination thereof, are carried out in the liquid slurry phase.

### Claim 25 (depends on 13)

The process of claim 13, wherein the polymerization conditions during time periods A1, A2, and B comprise a pressure of from about 0.96 MPa (140 psi) to about 5.2 MPa (750 psi) and a temperature of from about 50° C. to 100° C.