Rubbery polymer, method of preparing the same, graft copolymer, and thermoplastic resin composition

Patent metadata

Field	Value
Publication number	US-10501570-B2
Application number	US-201615547768-A
Country	US
Kind code	B2
Filing date	Nov 29, 2016
Priority date	Feb 19, 2016
Publication date	Dec 10, 2019
Grant date	Dec 10, 2019

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.

First claim

The invention claimed is:

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:
[CH 2 ═CR 1 CO 2 (R 2 O) n R 3 ] m C(R 4 ) l   [Formula 1]

(wherein R 1 is hydrogen or an alkyl group selected from C 1 to C 3 alkyl groups, R 2 is an alkylene group selected from C 1 to C 4 alkylene groups, R 3 is an alkylene group selected independently from C 1 to C 3 alkylene groups, R 4 is an alkyl group selected from C 1 to C 3 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%.

2. 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.

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

4. 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.

5. 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.

6. The method according to claim 4 , wherein the electrolyte is one or more selected from the group consisting of KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , Na 2 S 2 O 7 , K 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 , K 2 HPO 4 , and Na 2 HPO 4 .

7. 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.

8. The method according to claim 1 , wherein, in Formula 1, R 1 is H or CH 3 , R 2 is C 2 H 4 or C 3 H 6 , R 3 is CH 2 , R 4 is C 2 H 5 , 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.

9. 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%.

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

11. 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.

12. 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.

13. 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%.

14. 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 C 16 to C 18 alkenyl succinic acid di-potassium salt, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkylphenyl ether ammonium sulfate.

15. 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%.

16. 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.

17. 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%.

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

Assignees

• Lg Chemical Ltd

Inventors

• Lee Jin Hyoung
• Kim Young Min
• Han Su Jeong
• Kim Yoo Vin
• Jeong Young Hwan
• Chung Sun Haeng
• Suk Jae Min

Classifications

• C08F279/04 Primary

  Vinyl aromatic monomers and nitriles as the only monomers · CPC title

• C08F2/24

  with the aid of emulsifying agents · CPC title

• C08F236/12

  with nitriles · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08L51/06

  grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond · CPC title