KR960005078B1 - Styrenic thermoplastic resin compositions with heat-resistance - Google Patents

Styrenic thermoplastic resin compositions with heat-resistance Download PDF

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KR960005078B1
KR960005078B1 KR1019920021493A KR920021493A KR960005078B1 KR 960005078 B1 KR960005078 B1 KR 960005078B1 KR 1019920021493 A KR1019920021493 A KR 1019920021493A KR 920021493 A KR920021493 A KR 920021493A KR 960005078 B1 KR960005078 B1 KR 960005078B1
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copolymer
parts
styrene
molecular weight
acrylonitrile
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KR940011572A (en
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장복남
정하식
박현길
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제일모직주식회사
채오병
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

To increase the heat resistance and impact resistance of N-phenylmaleimide copolymer, ultra-high molecular weight of N-phenylmaleimide copolymer is prepared and added to the N-phenylmaleimide copolymer and graft copolymer by compounding. The copolymer(A) is made by emulsion polymerization of N-phenylmaleimide, styrene, acrylonitrile. The copolymer(B) is made by same polymerization as above and same monomer is used but the copolymer has ultrahigh molecular weight. The copolymer(C) is graft copolymer that is made of rubber, styrene acrylonitrile by emulsion polymerization. The new styrene-acrylonitrile-N-phenylmaleimide copolymer is prepared by compounding the 35-60 wt.% of copolymer(A), 5-30 wt.% of copolymer(B) and 20-50 wt.% of graft copolymer(C). This polymer does not lose the mechanical property, shows a good heat resistance of styrene-acrylonitrile copolymer, and increases the heat deformation temperature of ABS resin as a resulting polymer.

Description

내열성 스티렌계 열가소성 수지 조성물Heat resistant styrene thermoplastic resin composition

본 발명은 열가소성 수지조성물에 관한 것으로, 상세하게로는 스티렌계 수지중 기존의 스티렌-아크릴로니트릴 2원 공중체의 내열 한계를 극복하고 기계적 특성을 손상시키지 아니하면서 최종 생산물인 ABS의 열변형온도를 상승시킨 스티렌-아크릴로니트릴-N-페닐말레이미드의 3원 공중합체 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition, and in particular, the heat deflection temperature of ABS, the final product, without overcoming the heat resistance limit of the existing styrene-acrylonitrile binary copolymer in styrene-based resins and without compromising mechanical properties. It relates to a ternary copolymer composition of styrene-acrylonitrile-N-phenylmaleimide obtained by raising the compound.

통상 사용되는 ABS제품은 스티렌-아크릴로니트릴의 2원 공중합물과 고무가 40-70부 포함된 그라프트 공중합체를 블렌딩하여 제조되는 것으로, 실제로 내열성을 갖게 하는 것은 스티렌-아크릴로니트릴의 2원 공중합물, 즉 SAN 자체의 물성에 크게 좌우된다. 기존의 ABS제품은 기계적 강도, 표면성질, 그리고 압사출시 가공성이 좋은 장점을 가지고 있지만 110℃이상의 고온에서는 변형이 발생하는 단점을 갖고 있으므 로 스티렌과 아크릴로니트릴의 일부를 알파-메틸스티렌 또는 N-페닐말레이미드로 대체하여 내열 한계를 극북하고자 하는 노력이 많이 이루어져 왔다.Commonly used ABS products are manufactured by blending a binary copolymer of styrene-acrylonitrile and a graft copolymer containing 40 to 70 parts of rubber. It is actually a binary member of styrene-acrylonitrile to have heat resistance. It depends greatly on the physical properties of the copolymer, SAN itself. Existing ABS products have the advantages of mechanical strength, surface properties, and workability when extruding, but they have disadvantages that deformation occurs at high temperatures above 110 ℃. Therefore, some of styrene and acrylonitrile may be converted to alpha-methylstyrene or N-. Many efforts have been made to replace the phenylmaleimide with the extreme heat resistance.

그러나 알파-메틸스티렌을 사용했을 경우는 내열 한계가 120℃이내이고, 반응성이 좋지 않으며 가공이 어렵고 고온 성형시 열분해하는 단점을 갖고 있지만 N-페닐말레이미드로 대체했을 경우는 그 함량에 따라 내열온도가 120-160℃에 이르는 우수한 내열성을 보이고 가공성도 좋은 제품을 만들 수 있는 장점이 있다.However, when alpha-methylstyrene is used, the heat resistance limit is within 120 ℃, the reactivity is difficult, the processing is difficult, and it has the disadvantage of pyrolysis during high temperature molding, but when it is replaced with N-phenylmaleimide, the heat resistance temperature depends on its content. The excellent heat resistance of 120-160 ℃ shows the advantage that can make a good product.

위와같은 성질을 이용한 일본특허 소57-167341, 58-206657, 61-073755와 미국 특허 3721724에서는 N-페닐말레이미드를 주로 사용하고 여기에 아크릴로니트릴, 알파-메틸스티렌 또는 메틸메타아크릴레이트를 공중합하여 내열성 및 내충격성을 향상시키고자 하였으나 내열성 향상의 측면에는 만족할 만한 수준이었지만 내충격성은 다소 저하되는 경향을 보였다.Japanese Patent Nos. 57-167341, 58-206657, 61-073755 and US Pat. No. 3721724 using the above properties mainly use N-phenylmaleimide and copolymerize acrylonitrile, alpha-methylstyrene or methylmethacrylate. In order to improve heat resistance and impact resistance, it was satisfactory in terms of heat resistance improvement, but the impact resistance tended to decrease somewhat.

한편 국내 특허공고 제89-3009호에서는 광유(MINERAL OIL)를 N-페닐말레이미드 공중합체에 첨가하여 내열성과 내충격성 등과 같은 기계적 특성을 개선시키기 위한 시도를 했는데 유동성 측면에서는 현저히 향상되었으나 내열성과 내충격성에 있어서는 만족할 만한 결과를 나타내지 않았다.Meanwhile, in Korean Patent Publication No. 89-3009, an attempt was made to improve mechanical properties such as heat resistance and impact resistance by adding mineral oil to N-phenylmaleimide copolymer, which was remarkably improved in terms of fluidity. The impact was not satisfactory.

상기와 같은 문제점을 해결하기 위해 본 발명자는 초고분자량의 N-페닐말레이미드 공중합체를 제조하여 기존의 N-페닐말레이미드 3원공중합체와 그라프트 공중합체에 균형있게 배합한 결과 상기와 같은 문제점을 해결할 수 있음을 밝혀내게 되었다.In order to solve the problems described above, the present inventors have prepared an ultra-high molecular weight N-phenylmaleimide copolymer to balance the conventional N-phenylmaleimide terpolymer and graft copolymer, resulting in the above problems. It turns out that can solve.

즉, 본 발명은 N-페닐말레이미드 30-50부, 스티렌 50-30부, 아크릴로니트릴 20-10부의 함량으로 유화중합하여 제조된 공중합체(A)와, 같은 단량체 함량비의 초고분자량 3원 공중합체를 유화중합하여 제조된 공중합체(B)와, 고무함량 40-70부, 스티렌 20-30중량부, 아크릴로 니트릴 10-20중량부를 유화 중합하여 제조된 그라프트 공중합체(C)를, (A)는 35-60중량부로, (B)는 5-30중량부로 (C)는 20-50중량부로 배합함을 특징으로 하는 내열성 및 내충격성이 우수한 물성을 보이는 열가소성 스티렌계 수지 조성물에 대한 것이다.That is, the present invention is ultra-high molecular weight 3 of the same monomer content ratio as the copolymer (A) prepared by emulsion polymerization in an amount of 30-50 parts of N-phenylmaleimide, 50-30 parts of styrene, and 20-10 parts of acrylonitrile. Graft copolymer (C) prepared by emulsion polymerization of the original copolymer (B), rubber content 40-70 parts, styrene 20-30 parts by weight, acrylonitrile 10-20 parts by weight emulsion polymerization (A) is 35-60 parts by weight, (B) is 5-30 parts by weight and (C) is 20-50 parts by weight of thermoplastic styrene resin composition showing excellent physical and shock resistance properties, characterized in that It is about.

상기 공중합체(A)와 (C)는 통상적인 유화중합 방법으로 제조된 것으로 그 중(A)는 분자량이 90,000-350,000이고 분자량 분포가 2.0-4.0의 물성을 보이는 3원 공중합체이고, 공중합체 (B)는 공중합체(A)와 같은 단량체 비율로 1.0-2.0부의 유화제와 이온교환수 존재하에서 0.1부 이하의 개시제를 넣고 적당한 교반력을 부여하면서 6-8시간 정도의 중합시간으로 중합하여 중량평균 분자량 1,500,000-2,500,000, 분자량 분포 2.0-2.5정도의 중합물성을 갖는 것을 특징으로 하는 3원 공중합체이다.The copolymers (A) and (C) are prepared by a conventional emulsion polymerization method, in which (A) is a tertiary copolymer having a molecular weight of 90,000-350,000 and a molecular weight distribution of 2.0-4.0. (B) is the same monomer ratio as the copolymer (A) in the presence of 1.0-2.0 parts of emulsifier and ion-exchanged water in the presence of 0.1 parts or less of initiator, giving a suitable agitation force and polymerization by polymerization time of about 6-8 hours It is a ternary copolymer characterized by having an average molecular weight of 1,500,000-2,500,000, and a polymerizable substance having a molecular weight distribution of about 2.0-2.5.

이와같은 초고분자량 3원 공중합체는 내열성 및 기타 기계적 물성이 매우 우수한 반면 유동성이 저하되는 특성이 있다. 즉 3원 공중합체인 (B) 단독으로 그라프트 공중합체(C)와 배합하면 가동성이 현저히 떨어지기 때문에 본 발명자는 중합체(A)와 (B)를 (C)와 함께 배합가공하여 유동성이 크게 저하되지 않을 정도로 다른 물성 즉 내열성과 내충격성을 향상시키고자 한 것이다. 초고분자량 공중합체(B)를 전체 N-페닐말레이미드 공중합체 (A+B)에 대해 10% 이하로 배합하면 물성 향상을 기대하기 어렵고 40％이상 사용하면 유동성 및 가공성이 현저히 떨어지기 때문에 좋지 않는 영향을 미치므로 초고분자량 공중합체(B)를 전체 N-페닐말레이미드 공중합체 (A+B)에 대한 중량비로 10-40%로 또는 최종 ABS제품에 대해서는 5-25%로 배합하는 것이 바람직하다.Such ultra high molecular weight terpolymer is very excellent in heat resistance and other mechanical properties, while the fluidity is lowered. In other words, when blending with the graft copolymer (C) alone (B), which is a tertiary copolymer, the mobility is remarkably decreased, so the present inventors blend and process the polymers (A) and (B) together with (C) to significantly reduce fluidity. It is intended to improve other physical properties, that is, heat resistance and impact resistance. When the ultra high molecular weight copolymer (B) is blended at 10% or less with respect to the total N-phenylmaleimide copolymer (A + B), it is difficult to expect the improvement of physical properties. It is desirable to mix the ultrahigh molecular weight copolymer (B) at 10-40% by weight relative to the total N-phenylmaleimide copolymer (A + B) or 5-25% for the final ABS product. .

본 발명에서 사용될 수 있는 유화제로는 로진산염, 라우릴 황산염, 도데실 벤젠술폰산염 등을 들 수 있으며, 특히 바람직 하기로는 도데실 벤젠술폰산염이 적당하고 개시제로는 과황산칼륨 또는 큐멘하이드로퍼옥사이드를 사용이 바람직하다.Emulsifiers that can be used in the present invention include rosin, lauryl sulfate, dodecyl benzenesulfonate, and the like, particularly preferably dodecyl benzenesulfonate and potassium initiator or cumene hydroperoxide as an initiator Preference is given to using.

본 발명의 실시예는 다음과 같다.Embodiments of the present invention are as follows.

[제조실시예 1)][Production Example 1)]

* 그라프트 공중합체의 제조* Preparation of Graft Copolymer

이온교환수 150부와 t-도데실머캅탄 0.2부, 로진산염 0.5부와 부타디엔 고무 55부, 스티렌 28부, 아크릴로니트릴 17부의 단량체 비율로 중합초기에 부타디엔고무 전량과 스티렌 15부, 아크릴로니트릴 8부를 투입하고 0.5부의 포도당과 0.4부의 큐멘하이드로퍼옥사이드를 첨가한 후 2시간 반응시키고 남은 단량체 혼합물을 1시간동안 연속투입하고 70℃에서 30분간 유지시킨 후 상온으로 냉각하여 그라프트 공중합체를 제조하였다.150 parts of ion-exchanged water, 0.2 parts of t-dodecylmercaptan, 0.5 parts of rosinate, 55 parts of butadiene rubber, 28 parts of styrene, and 17 parts of acrylonitrile in the initial stage of polymerization, the total amount of butadiene rubber, 15 parts of styrene, acrylonitrile 8 parts were added, 0.5 parts of glucose and 0.4 parts of cumene hydroperoxide were added, followed by reaction for 2 hours. The remaining monomer mixture was continuously added for 1 hour, and maintained at 70 ° C. for 30 minutes, followed by cooling to room temperature to prepare a graft copolymer. It was.

[제조실시예 2)][Production Example 2)]

* N-페닐말레이트 공중합체의 제조(1)* Preparation of N-phenylmaleate Copolymer (1)

이온교환수 200부에 도데실 벤젠술폰산염 1.25부와 조제를 반응기 내에 넣고 잘 교반하며 온도로 50℃로 승온시킨다. 여기에 N-페닐말레이미드 35부, 아크릴로니트릴 20부, 스티렌 45부를 t-도데실 마캅탄 0.2부, 포도당 0.5부와 0.4부의 큐멘하이드로 퍼옥사이드를 잘 혼합하여 4시간 동안 연속으로 투입시킨다. 투입 중 유화제 소모시점을 잘 고려하여 추가로 0.5부의 유화제를 첨가한다. 발열량에 의한 중합이기 때문에 정확한 온도조절이 필요하다. 1차 투입이 끝나고 30분간 70℃서 유지시킨 후 아크릴로니트릴 4부를 연속적으로 5분간 추가 투입하고 다시 30분 유지한 후 반응을 종료시켜 N-페닐말레이트 공중합체를 제조하였다.1.25 parts of dodecyl benzenesulfonate and the preparation were added to 200 parts of ion-exchanged water in a reactor, stirred well, and the temperature was raised to 50 ° C. 35 parts of N-phenylmaleimide, 20 parts of acrylonitrile and 45 parts of styrene were mixed well with 0.2 parts of t-dodecyl marcaptan, 0.5 parts of glucose and 0.4 parts of cumene hydroperoxide, and continuously added for 4 hours. 0.5 parts of emulsifier is added in consideration of the point of consumption of the emulsifier. Accurate temperature control is necessary because it is polymerization by calorific value. After completion of the first input and maintained at 70 ℃ for 30 minutes, 4 parts of acrylonitrile was added continuously for 5 minutes and maintained again for 30 minutes to terminate the reaction to prepare an N-phenyl maleate copolymer.

[제조실시예 3)][Production Example 3)]

* N-페닐말레이트 공중합체의 제조(2)* Preparation of N-phenylmaleate Copolymer (2)

N-페닐말레이미드 20부, 아크릴로 니트릴 19부, 스티렌 58부로 220부의 이온교환수에 2.0부의 도데실 벤젠술폰산염과 0.1부의 t-도데실 머캅탄을 첨가하고 제조예 2와 같은 방법으로 반응기내에 첨가시킨 후 70℃에서 아크릴로니트릴 3부를 연속적으로 투입하고 중합을 종료시켜 N-페닐말레이트 공중합체를 제조하였다.20 parts of N-phenylmaleimide, 19 parts of acrylonitrile and 58 parts of styrene were added 2.0 parts of dodecyl benzenesulfonate and 0.1 parts of t-dodecyl mercaptan to 220 parts of ion-exchanged water and the reactor was prepared in the same manner as in Preparation Example 2. After addition in the mixture, 3 parts of acrylonitrile was continuously added at 70 ° C, and polymerization was completed to prepare an N-phenylmaleate copolymer.

[제조실시예 4)][Production Example 4)]

* 초고분자량 중합체의 제조* Preparation of ultra high molecular weight polymer

이온교환수 200부, N-페닐말레이미드 35부 스티렌 45부, 아크릴로니트릴 20부를 과황산칼륨 0.05부와 도데실 벤젠술폰산염 1.5부를 중합 초기에 일관 투입하고 적당한 교반력을 부여하며, 중합온도를 실온에서 부터 70℃까지 승온시키며 6시간의 연속반응을 실시하여 70℃에서 1시간 유지후 반응을 종료시켜 초고분자량 중합체를 제조하였다. 이 3원 공중합체의 중량 평균분자량은 2,00,000이고 분자량 분포는 2.1이었다.200 parts of ion-exchanged water, 35 parts of N-phenylmaleimide, 45 parts of styrene, 20 parts of acrylonitrile, 0.05 parts of potassium persulfate and 1.5 parts of dodecyl benzenesulfonate are added at the initial stage of polymerization, giving proper stirring power, and polymerization temperature. The reaction was carried out for 6 hours while raising the temperature from room temperature to 70 ° C., and the reaction was terminated after 1 hour of holding at 70 ° C. to prepare an ultra high molecular weight polymer. The weight average molecular weight of this terpolymer was 2,00,000 and the molecular weight distribution was 2.1.

[실시예 1-5)]Example 1-5)

제조실시예 1에서 제조한 그라프트 공중합체의 함량과 제조예 4에서 만든 초고분자량 공중합체와 제조실시예 3에서 제조한 N-페닐말레이미드 공중합체의 함량을 아래의 표 1과 같이 변화시켜 각각 압출, 가공하였으며, 물성 측정 결과는 아래의 표 2와 같다.The graft copolymer prepared in Preparation Example 1, the ultra-high molecular weight copolymer prepared in Preparation Example 4, and the N-phenylmaleimide copolymer prepared in Preparation Example 3 were changed as shown in Table 1 below. Extruded and processed, the physical properties are shown in Table 2 below.

[표 1]TABLE 1

[비교예 1-2)]Comparative Example 1-2

비교예 1은 그라프트 공중합체의 함량이 35부, 제조실시예 2에서 제조한 공중합체 함량을 65부로 하였으며, 비교예 2는 그라프트 공중합체 함량을 35부, 제조실시예 3에서 만든 공중합체 함량을 65부로 배합하여 압출가공하였으며, 그 물성 측정 결과는 아래의 표 2와 같다.In Comparative Example 1, the graft copolymer content was 35 parts, and the copolymer content prepared in Preparation Example 2 was 65 parts. In Comparative Example 2, the graft copolymer content was 35 parts, and the copolymer prepared in Preparation Example 3 was used. The amount was blended into 65 parts and extruded, and the measurement results of the physical properties are shown in Table 2 below.

[표 2]TABLE 2

이상의 실시예를 통하여 알 수 있는 바와 같이, 본 발명의 조성물은 기계적 물성의 손상없이 우수한 내열특성을 나타내며, 사용되는 N-페닐말레이미드의 적절한 조성비는 전체 수지조성물의 5-25중량%이다.As can be seen from the above examples, the composition of the present invention exhibits excellent heat resistance without damage to mechanical properties, and the appropriate composition ratio of N-phenylmaleimide used is 5-25% by weight of the total resin composition.

Claims (5)

A) N-페닐말레이미드-스타이렌-아크릴로니트릴 3원 공중합체 35-60중량부, B) N-페닐말레이미드 30-50중량부, 스티렌 30-55중량부, 아크릴로니트릴 15-20중량부로 구성된 초고분자량 3원 공중합체 5-30중량부, C) 스티렌-아크릴로니트릴 2원 공중합물과 고무가 포함된 그라프트 공중합체 20-50중량부로 구성된 것을 특징으로 하는 내열성 스티렌계 열가소성 수지 조성물.A) 35-60 parts by weight of N-phenylmaleimide-styrene-acrylonitrile terpolymer, B) 30-50 parts by weight of N-phenylmaleimide, 30-55 parts by weight of styrene, 15-20 by acrylonitrile 5-30 parts by weight of ultra-high molecular weight terpolymer, consisting of 5 parts by weight, and C) a styrene-acrylonitrile binary copolymer and 20-50 parts by weight of a graft copolymer containing rubber. Composition. 제1항에 있어서, 초고분자량 3원 공중합체(B)의 중량 평균분자량이 1,500,000-2,500,000인 것을 특징으로 하는 내열성 스티렌계 열가소성 수지 조성물.The heat resistant styrene thermoplastic resin composition according to claim 1, wherein the weight average molecular weight of the ultrahigh molecular weight terpolymer (B) is 1,500,000-2,500,000. 제1항에 있어서, 초고분자량 3원 공중합체(B)가 6-8시간 동안 중합최고온도 70℃ 범위 내에서 완속중합하여 생성된 것을 특징으로 하는 내열성 스티렌계 열가소성 수지 조성물.The heat-resistant styrene-based thermoplastic resin composition according to claim 1, wherein the ultrahigh molecular weight terpolymer (B) is produced by slow polymerization within a polymerization maximum temperature of 70 ° C for 6-8 hours. 제1항에 있어서, 초고분자량 3원 공중합체(B)의 분자량 분포가 2-2.5인 것을 특징으로 하는 내열성스티렌계 열가소성 수지 조성물.The heat resistant styrene-based thermoplastic resin composition according to claim 1, wherein the molecular weight distribution of the ultrahigh molecular weight terpolymer (B) is 2-2.5. 제1항에 있어서, 초고분자량 3원 공중합체(B)의 조성비가 전체 수지조성물의 5-25%인 것을 특징으로 하는 내열성 스티렌계 열가소성 수지 조성물.The heat resistant styrene-based thermoplastic resin composition according to claim 1, wherein the composition ratio of the ultrahigh molecular weight terpolymer (B) is 5-25% of the total resin composition.
KR1019920021493A 1992-11-16 1992-11-16 Styrenic thermoplastic resin compositions with heat-resistance KR960005078B1 (en)

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Publication number Priority date Publication date Assignee Title
WO2018084417A1 (en) * 2016-11-01 2018-05-11 주식회사 엘지화학 Highly heat-resistant styrene-acrylonitrile resin and preparation method therefor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018084417A1 (en) * 2016-11-01 2018-05-11 주식회사 엘지화학 Highly heat-resistant styrene-acrylonitrile resin and preparation method therefor
US10696766B2 (en) 2016-11-01 2020-06-30 Lg Chem, Ltd. Styrene-acrylonitrile resin with high thermal resistance and method for producing the same

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