Copolymers and thermoplastic resin composition including the same

Patent metadata

Field	Value
Publication number	US-9850333-B2
Application number	US-201514749861-A
Country	US
Kind code	B2
Filing date	Jun 25, 2015
Priority date	Jun 27, 2014
Publication date	Dec 26, 2017
Grant date	Dec 26, 2017

Abstract

A copolymer capable of realizing a synergistic effect of matting characteristics and heat resistance properties includes two or more types of compounds including at least two unsaturated reactive groups. A thermoplastic resin composition including the copolymer is also provided.

First claim

What is claimed is:

1. A copolymer of a mixture of monomers, comprising:
(A) about 50 wt % to about 80 wt % of an aromatic vinyl-based monomer;
(B) about 15 wt % to about 40 wt % of an unsaturated nitrile-based monomer; and
(C) about 1 wt % to about 10 wt % of a cross-linkable monomer, each based on the total weight of the mixture of monomers to be copolymerized;
wherein (C) the cross-linkable monomer comprises (c1) a first cross-linkable monomer including at least two unsaturated reactive groups, and (c2) a second cross-linkable monomer including at least two unsaturated reactive groups which is not the same as (c1) the first cross-linkable monomer including at least two unsaturated reactive groups,
wherein (c1) the first cross-linkable monomer includes a siloxane bond, and (c2) the second cross-linkable monomer includes no siloxane bonds.

2. The copolymer of claim 1 , comprising the first cross-linkable monomer (c1) in an amount of about 0.99 wt % to about 8 wt %, based on the total weight of a mixture of monomers to be copolymerized, and comprising the second cross-linkable monomer (c2) in an amount of about 0.01 wt % to about 2 wt %, based on the total weight of a mixture of monomers to be copolymerized.

3. The copolymer of claim 1 , comprising (c1) the first cross-linkable monomer and (c2) the second cross-linkable monomer in a weight ratio of about 2:1 to about 70:1.

4. The copolymer of claim 1 , wherein the first cross-linkable monomer (c1) has a structure represented by the following Formula 1:

wherein l, m and n are the same or different and each is independently an integer ranging from 0 to 100, provided that they are not zero simultaneously, and
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are the same or different and are each independently hydrogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 30 alkynyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 1 to C 30 heteroaryl group, a hydroxyl group, an alkoxy group, an amino group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group, or a mercapto group, provided that at least two of R 1 to R 8 include a polymerizable unsaturated reactive group.

5. The copolymer of claim 1 , wherein the first cross-linkable monomer (c1) has a structure represented by the following Formula 2:

wherein R 9 to R 14 are the same or different and are each independently hydrogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 30 alkynyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 1 to C 30 heteroaryl group, a hydroxyl group, an alkoxy group, an amino group, an epoxy group, a carboxyl group, a halogen group, an ester group, an isocyanate group, or a mercapto group, and p is an integer ranging from 1 to 6, provided that at least two of R 9 to R 14 include a polymerizable unsaturated reactive group.

6. The copolymer of claim 1 , wherein the first cross-linkable monomer (c1) comprises 1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, 1,3,5-triethyl-1,3,5-trivinyl-cyclotrisiloxane, 1,3,5,7-tetraethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane, and/or 1,3,5,7,9-pentaethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane.

7. The copolymer of claim 1 , wherein the first cross-linkable monomer (c1) has a weight average molecular weight of about 150 g/mol to about 6,000 g/mol.

8. The copolymer of claim 1 , wherein the second cross-linkable monomer (c2) comprises: a cross-linkable aromatic monomer comprising divinylbenzene; a vinyl group-containing monomer comprising 1,4-divinyloxybutane and/or divinylsulfone; an allyl compound comprising diallylphthalate, diallylacrylamide, triallyl(iso)cyanurate, and/or triallyltrimellitate; and/or a (meth)acrylate compound comprising hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, 1,3-butanediol methacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane, tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol tri(meth)acrylate, and/or allyl(meth)acrylate.

9. The copolymer of claim 1 , wherein the aromatic vinyl-based monomer (A) comprises styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, and/or vinylnaphthalene.

10. The copolymer of claim 1 , wherein the unsaturated nitrile-based monomer (B) comprises acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, and/or fumaronitrile.

11. The copolymer of claim 1 , wherein the copolymer has an insoluble content of about 5 wt % to about 100 wt %, as measured by a Soxhlet extraction method using tetrahydrofuran (THF) for 48 hours.

12. The copolymer of claim 1 , wherein the copolymer has a silicon content of about 0.33 wt % to about 2.61 wt %, as measured by an X-ray fluorescence spectrometer.

13. The copolymer of claim 1 , wherein the copolymer has a glass transition temperature (T g ) of about 95° C. to about 115° C.

14. A thermoplastic resin composition comprising the copolymer according to claim 1 .

15. The thermoplastic resin composition of claim 14 , wherein the thermoplastic resin composition comprises a styrene-acrylonitrile copolymer (SAN) resin composition, a methyl methacrylate-styrene-acrylonitrile copolymer (MSAN) resin composition, an acrylonitrile-butadiene-styrene copolymer (ABS) resin composition, a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS) resin composition, an acrylonitrile-styrene-acrylate copolymer (ASA) resin composition, a polycarbonate (PC)/acrylonitrile-butadiene-styrene copolymer (ABS) alloy resin composition, a polycarbonate (PC)/acrylonitrile-styrene-acrylate copolymer (ASA) alloy resin composition, a polymethyl methacrylate (PMMA)/acrylonitrile-butadiene-styrene copolymer (ABS) alloy resin composition, a polymethyl methacrylate (PMMA)/methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS) alloy resin composition, and/or a polymethyl methacrylate (PMMA)/acrylonitrile-styrene-acrylate copolymer (ASA) alloy resin composition.

16. A molded article comprising the thermoplastic resin composition according to claim 14 .

17. The molded article of claim 16 , wherein the molded article has a gloss of about 50% or less, as measured at an angle of 60° by an evaluation method according to ASTM D523, and has a Vicat softening temperature (VST) of about 101° C. to about 110° C., as measured for a ¼ inch-thick specimen under conditions of a load of 5 kg and a rate of 50° C./hr by an evaluation method according to ISO 306B50.

Assignees

• Lotte Advanced Mat Co Ltd

Inventors

• Jang Joo Hyun
• Heo Jae Won
• Kim Il Jin
• Park Kwang Soo
• Senthilkumar Natarajan
• Kang Tae Gon
• Kim Bo Eun
• Oh Jun Sung

Classifications

• C08F230/08

  containing silicon · CPC title

• C08F212/10 Primary

  with nitriles · CPC title

• C08L2207/53

  Core-shell polymer · CPC title

• C08L25/12

  with unsaturated nitriles · CPC title

• C08L2205/03

  containing three or more polymers in a blend · CPC title