# US 2020/0399454 A1 · Propylene-based block copolymer, production method therefor, and solid titanium catalyst ingredient for olefin polymerization

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- Number: US 2020/0399454 A1
- Document ID: US20200399454A1
- Status: Published application
- Kind: A1
- Application number: 16/978,513
- Filed: 2019-03-07
- Published: 2020-12-24
- Earliest claimed: 2018-03-07
- Assignees: Mitsui Chemicals, Inc.
- Applicants: Mitsui Chemicals, Inc.
- Inventors: Atsushi SAKUMA; Kazutaka TSURU; Kenichiro OKAMURA
- Web page: https://patentgrep.com/patent/US20200399454A1

## CPC

- C08L 23/14: Copolymers of propene (C08L23/16 takes precedence)
- C08F 4/654: with magnesium or compounds thereof
- C08F 210/06: Propene
- C08F 297/083: {the monomers being ethylene or propylene}
- C08L 23/142: {at least partially crystalline copolymers of propene with other olefins}
- C08F 2410/06: Catalyst characterized by its size
- C08L 2207/02: Heterophasic composition
- C08L 2308/00: Chemical blending or stepwise polymerisation process with the same catalyst
- C08L 2314/02: Ziegler natta catalyst
- Y02P 20/52: using catalysts, e.g. selective catalysts
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The purpose of the present invention is to provide a propylene-based block copolymer, the deposition thereof on the inner wall of the polymerization vessel having been sufficiently inhibited. The propylene-based block copolymer of the present invention has a flowability evaluation value of 40% or less, the value being calculated with the following equation wherein X (sec) is the number of seconds over which 100 g of the copolymer having ordinary temperature falls from a stainless-steel funnel having an inner diameter of 11.9 mm and Y (sec) is the number of seconds over which 100 g of the copolymer which has been held at 80° C. for 24 hours under a load of 10 kg falls from the funnel having an inner diameter of 11.9 mm. Flowability evaluation value (%)={(Y/X)−1}×100.

## Claims

### Claim 1

A propylene block copolymer having an evaluated flowability value of 40% or less,
the evaluated flowability value being calculated by the following formula:
Evaluated flowability value (%)={(Y/X)−1}×100
where X (sec) is the number of seconds required for 100 g of the copolymer at normal temperature to fall through a stainless steel funnel having an inner diameter of 11.9 mm, and
Y (sec) is the number of seconds required for 100 g of the copolymer after being held at 80° C. for 24 hours under a load of 10 kg to fall through the funnel having an inner diameter of 11.9 mm.

### Claim 2 (depends on 1)

The propylene block copolymer according to claim 1, wherein a Dsol content relative to 100 mass % of a total amount of a component soluble in n-decane at 23° C. (Dsol) and a component insoluble in n-decane at 23° C. (Dinsol) is 30 mass % or more and 40 mass % or less.

### Claim 3 (depends on 2)

The propylene block copolymer according to claim 2, wherein the Dsol has an ethylene unit content of 36.0 mol % or more.

### Claim 4

A method for producing a propylene block copolymer, the method comprising:
a first polymerization step of preparing a crystalline propylene (co)polymer by polymerizing propylene and an optional α-olefin in the presence of a solid titanium catalyst component (i) produced by bringing
a solid compound (S) containing a magnesium compound (II-0) and having a first pore distribution index of 2 or more and a second pore distribution index of more than 0.5,
the first pore distribution index being represented by formula I:
First pore distribution index=x/y (I)
where x is a cumulative pore volume of pores with a size of 0.001 to 0.1 μm, and y is a cumulative pore volume of pores with a size of 0.1 to 1.0 μm, the cumulative pore volumes being measured with a mercury porosimeter,
the second pore distribution index being represented by formula I′:
Second pore distribution index=xα/xβ (I′)
where xα is a cumulative pore volume of pores with a size of 0.01 to 0.1 μm, and xβ is a cumulative pore volume of pores with a size of 0.001 to 1.0 μm, the cumulative pore volumes being measured with a mercury porosimeter,
a titanium compound represented by formula IV:
Ti(OR)gX4-g (IV)
where R is a hydrocarbon group, X is a halogen atom, and g is an integer satisfying 0≤g≤4, and
an electron donor
into contact with each other; and
a second polymerization step of polymerizing the crystalline propylene (co)polymer prepared in the first polymerization step and a raw material of a polymer selected from the group consisting of rubber components, amorphous or low-crystallinity ethylene.propylene copolymers (EPR), and amorphous ethylene.α-olefin copolymers.

### Claim 5 (depends on 4)

The method for producing a propylene block copolymer according to claim 4, wherein the first polymerization step and the second polymerization step are both performed in the presence of hydrogen.

### Claim 6 (depends on 4)

The method for producing a propylene block copolymer according to claim 4, wherein the magnesium compound (II-0) is a solid complex compound represented by formula II:
MgXaRsb.(RtOH)m (II)
where X is a halogen atom, Rs is a heteroatom-containing hydrocarbon group, Rt is a hydrocarbon group optionally containing a heteroatom, m is a real number satisfying 2.0≤m≤3.3, a is an integer satisfying 0≤a≤2, b is an integer satisfying 0≤b≤2, and a plus b is 2,
provided that when a is 0 in formula II, g is not 4 in formula IV.

### Claim 7

A solid titanium catalyst component produced by bringing
a solid compound (S) containing a magnesium compound (II-0) and having a first pore distribution index of 2 or more and a second pore distribution index of more than 0.5,
the first pore distribution index being represented by formula I:
First pore distribution index=x/y (I)
where x is a cumulative pore volume of pores with a size of 0.001 to 0.1 μm, and y is a cumulative pore volume of pores with a size of 0.1 to 1.0 μm, the cumulative pore volumes being measured with a mercury porosimeter,
the second pore distribution index being represented by formula I′:
Second pore distribution index=xα/xβ (I′)
where xα is a cumulative pore volume of pores with a size of 0.01 to 0.1 μm, and xβ is a cumulative pore volume of pores with a size of 0.001 to 1.0 μm, the cumulative pore volumes being measured with a mercury porosimeter, a titanium compound represented by formula IV:
Ti(OR)gX4-g (IV)
where R is a hydrocarbon group, X is a halogen atom, and g is an integer satisfying 0≤g≤4, and
an electron donor
into contact with each other.

### Claim 8 (depends on 4)

The method for producing a propylene block copolymer according to claim 4, wherein the first pore distribution index is 2 or more and 12 or less.