# US 2018/0022907 A1 · Bimodal Polypropylene Compositions and Method of Making Same

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- Number: US 2018/0022907 A1
- Document ID: US20180022907A1
- Status: Published application
- Kind: A1
- Application number: 15/628,191
- Filed: 2017-06-20
- Published: 2018-01-25
- Earliest claimed: 2016-07-25
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Yi Ping Ni; Rohan A. Hule; Sudhin Datta
- Web page: https://patentgrep.com/patent/US20180022907A1

## CPC

- C08L 23/12: Polypropene
- B29B 7/007: {for continuous mixing}
- B29B 7/30: continuous, with mechanical mixing or kneading devices
- B29B 7/726: {Measuring properties of mixture, e.g. temperature or density (B29B7/724 takes precedence)}
- B29B 7/82: Heating or cooling
- C08F 4/65922: {containing at least two cyclopentadienyl rings, fused or not}
- C08L 23/14: Copolymers of propene (C08L23/16 takes precedence)
- B01J 20/291: Gel sorbents
- B29B 7/484: {with two shafts provided with screws, e.g. one screw being shorter than the other (B29B7/482 takes precedence)}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer}
- 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: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B29B: PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

The present invention relates to a bimodal polypropylene composition comprising a blend of a HMW polypropylene component and a LMW polypropylene component, where the high molecular weight (HMW) component of the bimodal composition has a z-average molecular weight Mz of more than 400,000 g/mole, and a process to make such composition. The composition is suitable for thermoformed articles and injection molded articles.

## Claims

### Claim 1

A polypropylene composition comprising at least one high molecular weight (HMW) polypropylene component and at least one low molecular weight (LMW) polypropylene component, wherein the polypropylene composition has any one or more of the following features:
a) an extensional viscosity of the polypropylene composition of more than 10,000 Pa·s, when measured on an extensional rheometer at a temperature of 172° C., and an extensional rate of 10 second−1 measured at 0.3 seconds;
b) a zero shear viscosity of the polypropylene composition no less than the zero shear viscosity of the HMW polypropylene component alone, as determined in accordance with Small Angle Oscillatory Shear (SAOS) Rheology Test; and/or
c) a relaxation time of the polypropylene composition of more than 0.9 seconds, as determined in accordance with Small Angle Oscillatory Shear (SAOS) Rheology Test;
wherein the HMW polypropylene component has a z-average molecular weight Mz of more than 400,000 g/mole, as determined by Gel Permeation Chromatography (GPC), and is in an amount in the range of from 80.0 wt % to 99.9 wt %, based on the total weight of the composition.

### Claim 2 (depends on 1)

The polypropylene composition of claim 1, wherein the extensional viscosity of the polypropylene composition is more than 20,000 Pa·s, when measured on an extensional rheometer at a temperature of 172° C., and an extensional rate of 10 second−1 measured at 0.3 seconds.

### Claim 3 (depends on 1)

The polypropylene composition of claim 1, wherein the zero shear viscosity of the polypropylene composition is at least 30% greater than the zero shear viscosity of the HMW polypropylene component alone, as determined in accordance with SAOS Rheology Test.

### Claim 4 (depends on 1)

The polypropylene composition of claim 1, wherein the zero shear viscosity of the polypropylene composition is more than 15,000 Pa·s, as determined in accordance with SAOS Rheology Test.

### Claim 5 (depends on 1)

The polypropylene composition of claim 1, wherein the relaxation time of the polypropylene composition is more than 1.2 seconds, as determined in accordance with Small Angle Oscillatory Shear (SAOS) Rheology Test.

### Claim 6 (depends on 1)

The polypropylene composition of claim 1, wherein the Mz of the HMW polypropylene component is in the range of from 600,000 g/mole to 10,000,000 g/mole.

### Claim 7 (depends on 1)

The polypropylene composition of claim 1, wherein the HMW polypropylene component has a Mw/Mn in the range of from 2.0 to 5.0.

### Claim 8 (depends on 1)

The polypropylene composition of claim 1, wherein the Melt Flow Rate of the HMW polypropylene component is in the range from 0.5 to 5.0 g/10 min, as determined in accordance with ASTM D1238 (230° C., 2.16 kg).

### Claim 9 (depends on 1)

The polypropylene composition of claim 1, wherein the HMW polypropylene component is formed from a catalyst system comprising a metallocene catalyst compound represented by the formula:
where:
M is a group 4 metal, preferably Hf or Zr;
T is a bridging group;
X is an anionic leaving group;
each R2, R3, R5, R6, R7, R8, R9, R11, R12, and R13 is independently, a halogen atom, hydrogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, substituted germylcarbyl substituents or a —NR′2, —SR, —OR′, —OSiR′3 or —PR′2 radical, wherein R′ is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group; and
R4 and R10 are phenyl groups substituted at the 3′ and 5′ positions.

### Claim 10 (depends on 9)

The polypropylene composition of claim 9, wherein the metallocene catalyst compound comprises one or more of:
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-t-butylphenyl)indenyl)ZrCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-t-butylphenyl)indenyl)HfCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-t-phenylphenyl)indenyl)ZrCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-t-phenylphenyl)indenyl)HfCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-isopropylphenyeindenyl)HfCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-isopropylphenyl)indenyl)ZrCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-methylphenyl)indenyl)HfCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-methylphenyl)indenyl)ZrCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-hexylphenyl)indenyl)HfCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-hexylphenyl)indenyl)ZrCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-n-butylphenyl)indenyl)HfCl2, and/or
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-t-butylphenyl)indenyl)ZrCl2.

### Claim 11 (depends on 9)

The polypropylene composition of claim 9, wherein the metallocene catalyst compound has a rac/meso ratio in the range of from 5:1 to 90:1.

### Claim 12 (depends on 1)

The polypropylene composition of claim 1, wherein the difference in Mw between the HMW polypropylene component and the LMW polypropylene component ΔMw is at least 100,000 g/mole.

### Claim 13 (depends on 1)

The polypropylene composition of claim 1, wherein the Melt Flow Rate of the LMW polypropylene component is in the range from 10 to 1000 g/10 min, as determined in accordance with ASTM D1238 (230° C., 2.16 kg).

### Claim 14 (depends on 1)

The polypropylene composition of claim 1, wherein the LMW polypropylene component has a Mw/Mn in the range of from 2.0 to 5.0.

### Claim 15 (depends on 1)

The polypropylene composition of claim 1, wherein the LMW polypropylene component has a Mw in the range of from 50,000 g/mole to 300,000 g/mole.

### Claim 16 (depends on 1)

The polypropylene composition of claim 1, wherein the LMW polypropylene component is formed from a single site catalyst.

### Claim 17

A process to form a polypropylene composition comprising at least one HMW polypropylene component in the range of from 80.0 wt % to 99.9 wt %, based on the total weight of the composition, and at least one LMW polypropylene component, in at least one single pass extrusion, which process comprises:
a) combining the HMW polypropylene component having a z-average molecular weight Mz of more than 400,000 g/mole with the LMW polypropylene component;
b) melt blending in an extruder the components in step a) at a melt temperature within a range from 350° C. to 450° C.;
c) isolating the blend produced in step b) to produce the polypropylene composition.

### Claim 18 (depends on 17)

The process of claim 17, further comprising a step of injection molding or blow molding articles from the polypropylene composition.

### Claim 19 (depends on 17)

The process of claim 17, wherein the melt blending takes place in an extruder having a feeder zone and a die zone, wherein a temperature gradient is provided from a feeder zone to a die zone of at least +20° C.

### Claim 20 (depends on 17)

The process of claim 17, wherein the Mz of the HMW polypropylene component is in the range of from 600,000 g/mole to 10,000,000 g/mole.

### Claim 21

A polymerization process to form HMW polypropylene component having a z-average molecular weight Mz of more than 400,000 g/mole, comprising contacting propylene monomers with a catalyst system comprising a metallocene catalyst compound represented by the formula:
where:
M is a group 4 metal, preferably Hf or Zr;
T is a bridging group;
X is an anionic leaving group;
each R2, R3, R5, R6, R7, R8, R9, R11, R12, and R13 is independently, a halogen atom, hydrogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, substituted germylcarbyl substituents or a —NR′2, —SR, —OR′, —OSiR′3 or —PR′2 radical, wherein R′ is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group; and
R4 and R10 are phenyl groups substituted at the 3′ and 5′ positions.

### Claim 22 (depends on 21)

The polymerization process of claim 21, wherein the metallocene catalyst compound comprises one or more of:
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-t-butylphenyl)indenyl)ZrCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-t-butylphenyl)indenyl)HfCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-t-phenylphenyl)indenyl)ZrCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-t-phenylphenyl)indenyl)HfCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-isopropylphenyeindenyl)HfCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-isopropylphenyl)indenyl)ZrCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-methylphenyl)indenyl)HfCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-methylphenyl)indenyl)ZrCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-hexylphenyl)indenyl)HfCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-hexylphenyl)indenyl)ZrCl2,
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-n-butylphenyl)indenyl)HfCl2, and
dimethylsilyl bis(2-cyclopropyl,4-(3′,5′-di-t-butylphenyl)indenyl)ZrCl2.

### Claim 23 (depends on 21)

The polymerization process of claim 21, wherein no hydrogen is added.

### Claim 24 (depends on 1)

Thermoformed articles, injection molded articles, or blow molded articles, foamed or non-foamed, comprising the polypropylene compositions of claim 1.