# US 10,479,856 B2 · Manufacturing method for propylene block copolymer

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,479,856 B2
- Document ID: US10479856B2
- Status: Granted
- Kind: B2
- Application number: 16/213,349
- Filed: 2018-12-07
- Published: 2019-04-18
- Granted: 2019-11-19
- Earliest claimed: 2014-08-26
- Assignees: Toho Titanium Co., Ltd.
- Applicants: Toho Titanium Co., Ltd.
- Inventors: Masafumi Imai; Toshihiko Sugano; Toshiya Uozumi; Yuta Haga
- Web page: https://patentgrep.com/patent/US10479856B2

## CPC

- C08F 297/083: {the monomers being ethylene or propylene}
- C08F 4/654: with magnesium or compounds thereof
- C08F 210/06: Propene
- C08F 297/06: using a catalyst of the coordination type
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A method for producing a propylene-based block copolymer produces a propylene-based copolymer that exhibits excellent stereoregularity, rigidity, and impact resistance in a convenient and efficient manner while achieving high polymerization activity. The method for producing a propylene-based block copolymer includes bringing a catalyst into contact with propylene, or propylene and an α-olefin, and bringing an electron donor compound into contact with the resulting product to produce a propylene-based block copolymer, the catalyst including a solid catalyst component that includes titanium, magnesium, a halogen, and an internal electron donor compound, a specific organoaluminum compound, and a specific external electron donor compound.

## Claims

### Claim 1

A method for producing a propylene-based block copolymer comprising:
a first step of homopolymerizing propylene during which an electron donor compound (IV) is added to form a propylene homopolymer by bringing an olefin polymerization catalyst into contact with propylene;
subsequent to the first step, a second step of copolymerizing propylene and an α-olefin other than propylene in the presence of the olefin polymerization catalyst and the propylene homopolymer;
the olefin polymerization catalyst comprising a solid catalyst component for olefin polymerization that comprises titanium, magnesium, a halogen, and an internal electron donor compound, an organoaluminum compound represented by a general formula (I), and an external electron donor compound represented by a general formula (II) or an external electron donor compound represented by a general formula (III),
R1pAlQ3-p (I)
wherein R1 is a hydrocarbyl group having 1 to 6 carbon atoms, p is a real number that satisfies 0<p≤3, provided that a plurality of R1 are either identical to or different from each other when a plurality of R1 are present, and Q is a hydrogen atom,
a hydrocarbyloxy group having 1 to 6 carbon atoms, or a halogen atom, provided that
a plurality of Q are either identical to or different from each other when a plurality of Q are present,
R2Si(OR3)3 (II)
wherein R2 is a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms,
a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group,
a linear or branched alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms,
an aromatic hydrocarbon group having 6 to 24 carbon atoms, a nitrogen atom-containing hydrocarbon group having 2 to 24 carbon atoms that is terminated by a carbon atom, or an amino group having 2 to 24 carbon atoms, and R3 is a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, a linear or branched alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 24 carbon atoms, provided that the three R3 are either identical to or different from each other,
(R4R5N)Si(OR6)3 (III)
wherein R4 and R5 are a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, a linear or branched alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, a nitrogen atom-containing hydrocarbon group having 2 to 24 carbon atoms that is terminated by a carbon atom, or an amino group having 2 to 24 carbon atoms, provided that R4 and R5 are either identical to or different from each other, and are optionally bonded to each other to form a ring, and R6 is a linear alkyl group having 1 to 20 carbon atoms,
a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group,
a linear or branched alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, or
an aromatic hydrocarbon group having 6 to 24 carbon atoms, provided that the three R6 are either identical to or different from each other, and
wherein the electron donor compound (IV) is an alcohol.

### Claim 2 (depends on 1)

The method for producing a propylene-based block copolymer according to claim 1, wherein the electron donor compound (IV) is methanol or ethanol.

### Claim 3 (depends on 2)

The method for producing a propylene-based block copolymer according to claim 2, wherein the external electron donor compound represented by the general formula (II) is an external electron donor compound represented by a general formula (IIa), or the external electron donor compound represented by the general formula (III) is an external electron donor compound represented by a general formula (IIIa),
R7Si(OR8)3 (IIa)
wherein R7 is a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms,
a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, an allyl group,
a linear or branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms,
an aromatic hydrocarbon group having 6 to 12 carbon atoms, a nitrogen atom-containing hydrocarbon group having 2 to 12 carbon atoms that is terminated by a carbon atom, or an amino group having 2 to 12 carbon atoms, and R8 is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, an allyl group, a linear or branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, provided that the three R8 are either identical to or different from each other,
(R9R10N)Si(OR11)3 (IIIa)
wherein R9 and R10 are a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, an allyl group, a linear or branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, a nitrogen atom-containing hydrocarbon group having 2 to 12 carbon atoms that is terminated by a carbon atom, or an amino group having 2 to 12 carbon atoms, provided that R9 and R10 are either identical to or different from each other, and are optionally bonded to each other to form a ring, and R11 is a linear alkyl group having 1 to 12 carbon atoms,
a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, an allyl group,
a linear or branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or
an aromatic hydrocarbon group having 6 to 12 carbon atoms, provided that the three R11 are either identical to or different from each other.

### Claim 4 (depends on 2)

The method for producing a propylene-based block copolymer according to claim 2, wherein the external electron donor compound (II) is one or more compounds selected from isopropyltriethoxysilane, isopropyltrimethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, n-butyltriethoxysilane, n-butyltrimethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, t-butyltriethoxysilane, t-butyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

### Claim 5 (depends on 2)

The method for producing a propylene-based block copolymer according to claim 2, wherein the external electron donor compound (III) is one or more compounds selected from diethylaminotriethoxysilane, diethylaminotrimethoxysilane, dimethylaminotriethoxysilane, and dimethylaminotrimethoxysilane.

### Claim 6 (depends on 1)

The method for producing a propylene-based block copolymer according to claim 1, wherein the external electron donor compound represented by the general formula (II) is an external electron donor compound represented by a general formula (IIa), or the external electron donor compound represented by the general formula (III) is an external electron donor compound represented by a general formula (IIIa),
R7Si(OR8)3 (IIa)
wherein R7 is a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms,
a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, an allyl group,
a linear or branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms,
an aromatic hydrocarbon group having 6 to 12 carbon atoms, a nitrogen atom-containing hydrocarbon group having 2 to 12 carbon atoms that is terminated by a carbon atom, or an amino group having 2 to 12 carbon atoms, and R8 is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, an allyl group, a linear or branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, provided that the three R8 are either identical to or different from each other,
(R9R10N)Si(OR11)3 (IIIa)
wherein R9 and R10 are a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, an allyl group, a linear or branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, a nitrogen atom-containing hydrocarbon group having 2 to 12 carbon atoms that is terminated by a carbon atom, or an amino group having 2 to 12 carbon atoms, provided that R9 and R10 are either identical to or different from each other, and are optionally bonded to each other to form a ring, and R11 is a linear alkyl group having 1 to 12 carbon atoms,
a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, an allyl group,
a linear or branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or
an aromatic hydrocarbon group having 6 to 12 carbon atoms, provided that the three R11 are either identical to or different from each other.

### Claim 7 (depends on 1)

The method for producing a propylene-based block copolymer according to claim 1, wherein the external electron donor compound (II) is one or more compounds selected from isopropyltriethoxysilane, isopropyltrimethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, n-butyltriethoxysilane, n-butyltrimethoxysilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, t-butyltriethoxysilane, t-butyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

### Claim 8 (depends on 1)

The method for producing a propylene-based block copolymer according to claim 1, wherein the external electron donor compound (III) is one or more compounds selected from diethylaminotriethoxysilane, diethylaminotrimethoxysilane, dimethylaminotriethoxysilane, and dimethylaminotrimethoxysilane.