# US 10,501,570 B2 · Rubbery polymer, method of preparing the same, graft copolymer, and thermoplastic resin composition

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- Number: US 10,501,570 B2
- Document ID: US10501570B2
- Status: Granted
- Kind: B2
- Application number: 15/547,768
- Filed: 2016-11-29
- Published: 2018-11-29
- Granted: 2019-12-10
- Earliest claimed: 2016-02-19
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Jin Hyoung Lee; Young Min Kim; Su Jeong Han; Yoo Vin Kim; Young Hwan Jeong; Sun Haeng Chung; Jae Min Suk
- Web page: https://patentgrep.com/patent/US10501570B2

## CPC

- C08F 279/02: on to polymers of conjugated dienes
- C08F 2/24: with the aid of emulsifying agents
- C08F 2/28: cationic
- C08F 2/38: Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation}
- C08F 136/06: Butadiene
- C08F 236/10: with vinyl-aromatic monomers
- C08F 236/12: with nitriles
- C08F 236/14: containing elements other than carbon and hydrogen
- C08F 279/04: Vinyl aromatic monomers and nitriles as the only monomers
- C08L 25/12: with unsaturated nitriles
- C08L 51/06: grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
- C08F 2810/20: leading to a crosslinking, either explicitly or inherently
- 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

The present disclosure relates a method of preparing a rubbery polymer, a rubbery polymer, and a graft copolymer and thermoplastic resin composition including the rubbery polymer. In accordance with the present disclosure, a rubbery polymer, in which a large-diameter rubbery polymer and a small-diameter rubbery polymer are formed in a desired ratio by controlling the contents, addition time points, and types of a crosslinking agent, an emulsifier, and a molecular weight regulator when a conjugated diene monomer, the crosslinking agent, the molecular weight regulator, and the emulsifier are polymerized, and a graft copolymer and thermoplastic resin composition having excellent surface gloss and mechanical properties are provided.

## Claims

### Claim 1

A method of preparing a rubbery polymer, wherein a conjugated diene monomer is polymerized in the presence of a crosslinking agent, a molecular weight regulator, and an emulsifier,
wherein the crosslinking agent is a compound represented by Formula 1 below and is added before polymerization initiation or when a polymerization conversion rate is 30% or less:
[CH2═CR1CO2(R2O)nR3]mC(R4)l [Formula 1]
(wherein R1 is hydrogen or an alkyl group selected from C1 to C3 alkyl groups, R2 is an alkylene group selected from C1 to C4 alkylene groups, R3 is an alkylene group selected independently from C1 to C3 alkylene groups, R4 is an alkyl group selected from C1 to C3 alkyl groups, 1 is an integer of 0 to 2, n is an integer of 4 to 15, m is an integer of 3 or 4, and the product of m and n is 12 to 60),
the molecular weight regulator is added at a polymerization conversion rate of 40% to 75%, and
the emulsifier is an emulsifier having a critical micelle concentration (CMC) of 150 mg/L or less and is added at a polymerization conversion rate of 50% to 85%.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the conjugated diene monomer is split-added before polymerization initiation, at a polymerization conversion rate of 30% to 40%, and at a polymerization conversion rate of 60% to 70%, respectively.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the polymerization further comprises an aromatic vinyl monomer, a vinyl cyanide monomer, or a combination thereof.

### Claim 4 (depends on 1)

The method according to claim 1, wherein a conjugated diene monomer, an emulsifier, an initiator, an electrolyte, a molecular weight regulator, and ion exchanged water are present in a composition that undergoes the polymerization and the polymerization is initiated at 65 to 70° C.

### Claim 5 (depends on 4)

The method according to claim 4, wherein the initiator is one or more selected from the group consisting of potassium persulfate, sodium persulfate, ammonium persulfate, cumene hydroperoxide, diisopropylbenzene hydroperoxide, azobisisobutyronitrile, tertiary butyl hydroperoxide, para-methane hydroperoxide, and benzoyl peroxide.

### Claim 6 (depends on 4)

The method according to claim 4, wherein the electrolyte is one or more selected from the group consisting of KCl, NaCl, KHCO3, NaHCO3, K2CO3, Na2CO3, KHSO3, NaHSO3, Na2S2O7, K4P2O7, K3PO4, Na3PO4, K2HPO4, and Na2HPO4.

### Claim 7 (depends on 4)

The method according to claim 4, wherein the molecular weight regulator is one or more selected from the group consisting of n-decyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and n-octadecyl mercaptan.

### Claim 8 (depends on 1)

The method according to claim 1, wherein, in Formula 1, R1 is H or CH3, R2 is C2H4 or C3H6, R3 is CH2, R4 is C2H5, 1 is an integer of 0 to 2, n is an integer of 4 to 10, m is an integer of 3 to 4, and the product of m and n is 12 to 30.

### Claim 9 (depends on 1)

The method according to claim 1, wherein, in the polymerization, a portion of the conjugated diene monomer is added batchwise or continuously at a polymerization conversion rate of 30% to 40%.

### Claim 10 (depends on 9)

The method according to claim 9, wherein the polymerization is performed at 72 to 75° C.

### Claim 11 (depends on 1)

The method according to claim 1, wherein the molecular weight regulator is one or more selected from the group consisting of n-octyl mercaptan, sec-octyl mercaptan, n-nonyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and n-octadecyl mercaptan.

### Claim 12 (depends on 1)

The method according to claim 1, wherein the emulsifier having a CMC of 150 mg/L or less comprises an emulsifier having a CMC of 10 mg/L or less or an emulsifier having a CMC of greater than 10 mg/L and 150 mg/L or less.

### Claim 13 (depends on 12)

The method according to claim 12, wherein the emulsifier having a CMC of 10 mg/L or less is added, at a polymerization conversion rate of 60% to 85%.

### Claim 14 (depends on 12)

The method according to claim 12, wherein the emulsifier having a CMC of 10 mg/L or less is one or more selected from the group consisting of C16 to C18 alkenyl succinic acid di-potassium salt, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkylphenyl ether ammonium sulfate.

### Claim 15 (depends on 12)

The method according to claim 12, wherein the emulsifier having a CMC of greater than 10 mg/L and 150 mg/L or less is added, at a polymerization conversion rate 50 to 85%.

### Claim 16 (depends on 12)

The method according to claim 12, wherein the emulsifier having a CMC of greater than 10 mg/L and 150 mg/L or less is one or more selected from the group consisting of fatty acid soap, potassium oleate, and sodium oleate.

### Claim 17 (depends on 1)

The method according to claim 1, wherein, in the polymerization, a portion of the conjugated diene monomer and the emulsifier are added batchwise or continuously at a polymerization conversion rate of 60% to 70%.

### Claim 18 (depends on 17)

The method according to claim 17, wherein the polymerization is performed at 80 to 85° C.