Method for preparing weather resistant reinforced acrylate based resin

Patent metadata

Field	Value
Publication number	US-9683069-B2
Application number	US-201414773245-A
Country	US
Kind code	B2
Filing date	Aug 29, 2014
Priority date	Sep 4, 2013
Publication date	Jun 20, 2017
Grant date	Jun 20, 2017

Abstract

The present invention relates to a method for preparing a weather resistant reinforced acrylate based resin. More specifically, an activator-free conversion rate improver is included in an acrylate-styrene based graft copolymer, thereby improving the haze value, light transmittance, and yellow index when mixed with an acrylate-styrene based non-graft copolymer, and securing the weather resistance. In particular, according to the present invention, a weather resistant reinforced thermoplastic resin having excellent colors which are close to natural colors can be provided even without using sodium formaldehyde sulfoxylate (SFS) and iron ions.

First claim

What is claimed is:

1. A method of preparing a weather-resistant acrylate resin using an acrylate resin composition as a starting material, wherein the acrylate resin composition comprises an acrylate-styrene graft copolymer and an acrylate-styrene non-graft copolymer, wherein the acrylate-styrene graft copolymer is polymerized comprising an acrylate rubber latex, a (meth)acrylic acid alkyl ester compound, an aromatic vinyl compound, and an activator-free conversion improver,
wherein the activator-free conversion improver is one or more selected from among 2-hydroxy-2-sulfinatoacetic acid, disodium 2-hydroxy-2-sulfinatoacetate, and 2-hydroxy-2-sulfinatoacetate,
wherein the acrylate resin composition comprises 10-90 wt % of the acrylate-styrene graft copolymer and 90-10 wt % of the acrylate-styrene non-graft copolymer, and
wherein the graft copolymer comprises 5-50 parts by weight of the acrylate rubber latex, 20-75 parts by weight of the (meth)acrylic acid alkyl ester compound, 10-50 parts by weight of the aromatic vinyl compound, and 0-5 parts by weight of a vinyl cyan compound.

2. The method of claim 1 , wherein the activator-free conversion improver is used in an amount of 0.01-0.5 parts by weight based on 100 parts by weight of the sum of the rubber latex and compounds of the copolymer.

3. The method of claim 1 , wherein the acrylate rubber latex has a gel content of 60-90% and a mean particle size of 100-800 nm.

4. The method of claim 1 , wherein the graft copolymer is polymerized comprising one or more emulsifiers selected from the group consisting of sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, sodium styrene sulfonate, sodium dodecyl allyl sulfosuccinate, a styrene-sodium dodecyl allyl sulfosuccinate copolymer, polyoxyethylene alkyl phenyl ether ammonium sulfate, alkenyl C 16-18 succinic acid di-potassium salt, and sodium methallyl sulfonate, and non-reactive emulsifiers, comprising alkyl aryl sulfonate, sulfonated alkyl ester, soap of fatty acid, and an alkali salt of rosin acid, in an amount of 0.1-5 parts by weight based on 100 parts by weight of the sum of the latex and compounds of the graft copolymer.

5. The method of claim 1 , wherein the graft copolymer is polymerized comprising one or more oil-soluble initiators selected from among diisopropylbenzene hydroperoxide, t-hexyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, dicumyl peroxide, t-butylcumyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane, t-butylperoxy benzoate, t-butylperoxy 2-ethyl hexanoate, and bis(4-t-butylcyclohexyl)peroxydicarbonate, in an amount of 0.1-5 parts by weight based on 100 parts by weight of the sum of the latex and compounds of the graft copolymer.

6. The method of claim 1 , wherein each of the graft copolymer and the non-graft copolymer is polymerized comprising a mercaptan molecular weight regulator in an amount of 0.1-5 parts by weight based on 100 parts by weight of the sum of the latex and compounds of the graft copolymer.

7. The method of claim 1 , wherein the acrylate-styrene non-graft copolymer is a bulk polymer, a solution polymer or a suspension polymer, which is polymerized comprising 20-75 parts by weight of the (meth)acrylic acid alkyl ester compound, 10-50 parts by weight of the aromatic vinyl compound, and 0-10 parts by weight of a vinyl cyan compound.

8. The method of claim 1 , wherein the (meth)acrylic acid alkyl ester compound is one or more selected from among (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester.

9. The method of claim 1 , wherein the aromatic vinyl compound is one or more selected from among styrene, α-methyl styrene, p-methyl styrene, and vinyl toluene.

10. The method of claim 1 , wherein the vinyl cyan compound is one or more selected from among acrylonitrile, methacrylonitrile and ethacrylonitrile.

11. The method of claim 1 , wherein the composition further comprises one or more selected from among a lubricant, an antioxidant, an antistatic agent, a release agent and a UV stabilizer.

12. The method of claim 1 , comprising the steps of:
emulsion-polymerizing the acrylate rubber latex, the (meth)acrylic acid alkyl ester compound and the aromatic vinyl compound in the presence of the activator-free conversion improver, an emulsifier, an oil-soluble initiator and a molecular weight regulator to prepare an acrylate-styrene graft copolymer having a degree of conversion of 97% or higher;
subjecting 20-75 parts by weight of the (meth)acrylic acid alkyl ester compound, 10-50 parts by weight of the aromatic vinyl compound and 0-10 parts by weight of a vinyl cyan compound bulk polymerization, solution polymerization or suspension polymerization to prepare an acrylate-styrene non-graft copolymer having a degree of conversion of 97% or higher; and
melt-mixing 10-90 wt % of the acrylate-styrene graft copolymer with 90-10 wt % of the acrylate-styrene non-graft copolymer, and extruding or injecting the melt-mixed copolymer, thereby preparing a thermoplastic resin.

13. A weather-resistant acrylate resin which is prepared by the method of claim 12 and has a light transmittance of 92% or higher as measured on a 3 mm thick sheet in accordance with ASTM D 1003 at room temperature, a haze value of 1.2 or less on a 3 mm thick sheet in accordance with ASTM D1003 at room temperature, a yellow index (YI) of 0.89 or less as measured using a Color Quest II, a thermal stability of 0.36 or less as calculated based on a change in color (ΔE), and a weather resistance of 2.1 or less as calculated based on a change in color (ΔE).

14. The method of claim 7 , wherein the (meth)acrylic acid alkyl ester compound is one or more selected from among (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid decyl ester, and (meth)acrylic acid lauryl ester.

15. The method of claim 7 , wherein the aromatic vinyl compound is one or more selected from among styrene, α-methyl styrene, p-methyl styrene, and vinyl toluene.

16. The method of claim 7 , wherein the vinyl cyan compound is one or more selected from among acrylonitrile, methacrylonitrile and ethacrylonitrile.

17. A method of preparing a weather-resistant acrylate resin using an acrylate resin composition as a starting material, wherein the acrylate resin composition comprises an acrylate-styrene graft copolymer and an acrylate-styrene non-graft copolymer, wherein the acrylate-styrene graft copolymer is polymerized comprising an acrylate rubber latex, a (meth)acrylic acid alkyl ester compound, an aromatic vinyl compound, and an activator-free conversion improver,
wherein the activator-free conversion improver is one or more selected from among 2-hydroxy-2-sulfinatoacetic acid, disodium 2-hydroxy-2-sulfinatoacetate, and 2-hydroxy-2-sulfinatoacetate,
wherein the acrylate resin composition comprises 10-90 wt % of the acrylate-styrene graft copolymer and 90-10 wt % of the acrylate-styrene non-graft copolymer, and
wherein the acrylate-styrene non-graft copolymer is a bulk polymer, a solution polymer or a suspension polymer, which is polymerized comprising 20-75 parts by weight of the (meth)acrylic acid alkyl ester compound, 10-50 parts by weight of the aromatic

Assignees

• Lg Chemical Ltd

Inventors

• Lee Roo Da
• Park Sang Hoo
• Lee Won Seok
• Jang Seok Goo
• Choi Jeong Su
• Yoo Jeun Hoon

Classifications

• C08L51/04 Primary

  grafted on to rubbers · CPC title

• C08F285/00 Primary

  Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers · CPC title

• C08L51/003 Primary

  grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C08L51/04, C08L51/06 take precedence) · CPC title

• C08L51/06

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

• C08L33/04

  Homopolymers or copolymers of esters {(C08L43/04 takes precedence)} · CPC title