Method for preparing acrylonitrile-butadiene-styrene graft copolymer and acrylonitrile-butadiene-styrene thermoplastic resin comprising the same

• US 10,266,615 B2
• Filed: 05/26/2017
• Issued: 04/23/2019
• Est. Priority Date: 12/11/2014
• Status: Active Grant

• Current Assignee: LG Chem Limited (LG Corporation)
• Original Assignee: LG Chem Limited (LG Corporation)
• Inventors: Chung, Sun Haeng, Kim, Young Min, Lee, Jin Hyoung, Han, Su Jeong, Kim, Yoo Vin, Jeong, Young Hwan, Suk, Jae Min
• Primary Examiner(s): Loewe, Robert S
• Application Number:
  US15/607,268
• Publication Number:
  US 20170260303A1
• Time in Patent Office: 697 Days
• Field of Search: None
• CPC Class Codes: C08F 2/22 Emulsion polymerisation
• CPC Class Codes: C08F 2/26 anionic
• CPC Class Codes: C08F 2/30 non-ionic
• CPC Class Codes: C08F 2/44 Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• CPC Class Codes: C08F 212/08 Styrene
• CPC Class Codes: C08F 212/10 with nitriles
• CPC Class Codes: C08F 220/44 Acrylonitrile
• CPC Class Codes: C08F 222/1006 of polyhydric alcohols or polyhydric phenols
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08F 222/1063 of alcohol terminated polyethers
• CPC Class Codes: C08F 236/06 Butadiene
• CPC Class Codes: C08F 279/02 on to polymers of conjugated dienes
• CPC Class Codes: C08F 2800/20 as weight or mass percentages
• CPC Class Codes: C08L 25/12 with unsaturated nitriles
• CPC Class Codes: C08L 55/02 ABS [Acrylonitrile-Butadiene-Styrene] polymers

Abstract

The present invention relates to a method for preparing an acrylonitrile-butadiene-styrene graft copolymer having improved impact strength, which comprises: a step of preparing diene-based rubber latex by adding an acrylate-based cross-linking agent (Step 1); and a step of inserting the same cross-linking agent with the acrylate-based cross-linking agent, an aromatic vinyl-based compound and a vinyl cyan-based compound to the diene-based rubber latex and then subjecting thereof to graft copolymerization (Step 2), an acrylonitrile-butadiene-styrene graft copolymer prepared by the method, and an acrylonitrile-butadiene-styrene thermoplastic resin comprising the same.

Claims

1. A method for preparing an acrylonitrile-butadiene-styrene graft copolymer, which comprises:

a first step of preparing a diene-based rubber latex by adding an acrylate-based cross-linking agent; and

a second step of inserting the acrylate-based cross-linking agent, an aromatic vinyl-based compound and a vinyl cyan-based compound into the diene-based rubber latex and subsequently performing graft copolymerization,

wherein the acrylate-based cross-linking agent is (propylene glycol)_n diacrylate, in which n is an integer of 1 to 15.

2. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 1, wherein the first step of preparing diene-based rubber latex comprises:

inserting 50 parts by weight to 75 parts by weight of a conjugated diene-based monomer, 1 part by weight to 3 parts by weight of an emulsifier, 0.1 parts by weight to 0.4 parts by weight of a polymerization initiator, 0.1 parts by weight to 3 parts by weight of an electrolyte, 0.1 parts by weight to 0.5 part by weight of a molecular weight modifier and 65 parts by weight to 100 parts by weight of ion exchanged water into a reactor in a batch, while stirring;

inserting 0.05 parts by weight to 0.3 parts by weight of an acrylate-based cross-linking agent, based on 100 parts by weight of the conjugated diene monomer, into the reactor and then performing a first polymerization;

adding the balance of conjugated diene-based monomer and from 0 to 0.1 parts by weight of emulsifier, into the reactor and then performing a second polymerization; and

terminating the second polymerization by inserting a polymerization inhibitor into the reactor at a time when the polymerization conversion rate of the first polymerization is at least 90%.

3. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 2, wherein the conjugated diene-based monomer is a homogeneous material of the conjugated diene-based monomer, or

wherein the conjugated diene-based monomer is a mixture comprising the conjugated diene-based monomer and at least one co-monomer selected from the group consisting of the aromatic vinyl-based monomer and the vinyl cyan-based monomer.

4. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 3, wherein the mixture of the conjugated diene-based monomer comprises 80 weight % to 99 weight % of the conjugated diene-based monomer;

and 1 weight % to 20 weight % of at least one co-monomer selected from the group consisting of the aromatic vinyl-based monomer and the vinyl cyan-based monomer.

5. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 3, wherein the conjugated diene-based monomer comprises at least two compounds selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene.

6. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 3, wherein the aromatic vinyl-based monomer comprises at least two compounds selected from the group consisting of styrene, α

-methyl styrene, m-methyl styrene, α

-ethyl styrene, p-methyl styrene and p-tert-butyl styrene.

7. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 3, wherein the vinyl cyan-based monomer comprises at least two compounds selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and isopropyl acrylonitrile.

8. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 1, wherein the acrylate-based cross-linking agent to be used when preparing the diene-based rubber latex is (propylene glycol)_n diacrylate, in which n is an integer of 3 to 15.

9. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 8, wherein the cross-linking agent is (propylene glycol)₇ diacrylate or (propylene glycol)₁₃ diacrylate.

10. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 1, wherein the diene-based rubber latex prepared in the first step is large-diameter diene-based rubber latex whose average particle diameter(D50) is 2,500 Å

to 5,000 Å

.

11. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 1, wherein in the second step, the aromatic vinyl-based compound and the vinyl cyan-based compound are added to the diene-based rubber latex in separately or simultaneously, respectively or in the form of a mixture before initiating a polymerization reaction;

or wherein the aromatic vinyl-based compound and the vinyl cyan-based compound are added continuously in an emulsified form before initiating the polymerization reaction.

12. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 1, wherein in the second step comprises adding 45 parts by weight to 70 parts by weight of the diene-based rubber latex prepared in the first step, and 0.05 part by weight to 0.3 part by weight of the acrylate cross-linking agent, 25 parts by weight to 40 parts by weight of styrene, 5 parts by weight to 20 parts by weight of acrylonitrile, 0.1 parts by weight to 0.4 parts by weight of polymerization initiator and 0.1 parts by weight to 0.5 parts by weight of the molecular weight modifier are inserted.

13. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 1, wherein the graft copolymerization step of the second step is performed at a temperature range of 50°

C. to 90°

C. for 2 hours to 5 hours.

14. The method for preparing an acrylonitrile-butadiene-styrene graft copolymer of claim 1, wherein the graft copolymerization step of the second step is performed by additionally adding an emulsifier, a polymerization initiator, an electrolyte or a molecular weight modifier.

15. An acrylonitrile-butadiene-styrene graft copolymer prepared by the method of claim 1,

wherein the acrylonitrile-butadiene-styrene graft copolymer has monomer a conversion rate of 93% or higher, and

coagulum of the acrylonitrile-butadiene-styrene graft copolymer is 0.06 weight % or higher.

16. An acrylonitrile-butadiene-styrene thermoplastic resin comprising 20 weight % to 50 weight % of the acrylonitrile-butadiene-styrene graft copolymer of claims 15 and 50 weight % to 80 weight % of a styrene-acrylonitrile copolymer.

17. The acrylonitrile-butadiene-styrene thermoplastic resin of claim 16, wherein a gloss value of the acrylonitrile-butadiene-styrene thermoplastic resin measured at 45°

using a gloss meter according to ASTM D-528 is 90 or higher.

18. The acrylonitrile-butadiene-styrene thermoplastic resin of claim 16, wherein, when rubber content is less than 20 parts by weight, Izod impact strength according to ASTM D256 of the acrylonitrile-butadiene-styrene thermoplastic resin is 32 kgf·

m/m or higher at specimen thickness of ¼

″ and

35 kgf·

m/m or higher at specimen thickness of ⅛

″

, and

when rubber content is 20 parts by weight or more, it is 38 kgf·

m/m or higher at specimen thickness of ¼

″ and

43 kgf·

m/m or higher at specimen thickness of ⅛

″

.