KR100455102B1 - High Impact Polystyrene Resin with Good Heat Resistance and Falling Dart Impact Prepared by Continuous Mass Polymerization Process - Google Patents
High Impact Polystyrene Resin with Good Heat Resistance and Falling Dart Impact Prepared by Continuous Mass Polymerization Process Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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Abstract
본 발명의 괴상중합 연속공정으로 제조된 내열성과 낙하충격강도가 우수한 고충격 폴리스티렌 수지는 고무입자직경이 0.5∼1.0 마이크론인 스티렌계 모노머와 1,4-cis 함량이 95 중량% 이상인 폴리부타디엔계 고무(Ⅰ)로 이루어진 중합체(Ⅰ) 70∼90 중량부, 및 고무입자직경이 1.0∼1.5 마이크론인 스티렌계 모노머와 1,4-cis 함량이 40 중량% 이하인 폴리부타디엔계 고무(Ⅱ)로 이루어진 중합체(Ⅱ) 10∼30 중량부로 이루어진다.The high impact polystyrene resin having excellent heat resistance and drop impact strength prepared by the bulk polymerization continuous process of the present invention is a styrene monomer having a rubber particle diameter of 0.5 to 1.0 micron and a polybutadiene rubber having a 1,4-cis content of 95% by weight or more. 70-90 parts by weight of polymer (I) consisting of (I) and a polymer consisting of a styrene-based monomer having a rubber particle diameter of 1.0-1.5 micron and a polybutadiene-based rubber (II) having a 1,4-cis content of 40% by weight or less (II) It consists of 10-30 weight part.
Description
발명의 분야Field of invention
본 발명은 고충격 폴리스티렌 수지에 관한 것이다. 보다 구체적으로, 본 발명은 1,4-cis 함량이 상이한 2종의 폴리부타디엔계 고무를 사용한 괴상중합 연속공정으로 제조된 상이한 고무입자직경을 갖는 2종의 중합체로 이루어진 내열성과 낙하충격강도가 우수한 고충격 폴리스티렌 수지 및 그 제조방법에 관한 것이다.The present invention relates to a high impact polystyrene resin. More specifically, the present invention is excellent in heat resistance and drop impact strength composed of two polymers having different rubber particle diameters produced by a bulk polymerization continuous process using two kinds of polybutadiene rubbers having different 1,4-cis contents. It relates to a high impact polystyrene resin and a method for producing the same.
발명의 배경Background of the Invention
스티렌계 수지는 투명성, 열안정성, 가공성 등이 우수하여 상업적으로 많이 제조되고 있다. 특히, 스티렌계 수지에 고무입자를 도입함으로써 내충격성이 강화된 고무변성 폴리스티렌 수지가 개발되었는데 이를 고충격 폴리스티렌(HIPS : High Impact Polystyrsne)이라고 한다.Styrene-based resins are excellent in transparency, thermal stability, processability, etc., have been commercially produced a lot. In particular, rubber-modified polystyrene resins with enhanced impact resistance have been developed by introducing rubber particles into styrene resins, which are referred to as high impact polystyrenes (HIPS).
이러한 고충격 폴리스티렌 수지(HIPS)는 스티렌, α-메틸스티렌 및 링-치환된 스티렌과 같은 모노비닐리덴 방향족 화합물에 낮은 Tg(유리전이온도)를 갖는 고무, 특히 가교 결합된 폴리부타디엔 입자를 스티렌 고분자의 매트릭스에 분산시킨 것으로 내충격성, 내열성 및 유동성 등의 물성이 양호하여 전기, 전자 제품의 부품으로 널리 사용되고 있다.These high impact polystyrene resins (HIPS) are made of styrene polymers containing rubbers having low Tg (glass transition temperature) in monovinylidene aromatic compounds such as styrene, α-methylstyrene and ring-substituted styrene, especially crosslinked polybutadiene particles. It is dispersed in a matrix, and has good physical properties such as impact resistance, heat resistance, and fluidity, and is widely used as an electric and electronic component.
특히, 최근 들어 소비자들의 대형제품 선호경향이 증대됨에 따라 가전 회사들은 대형제품의 생산량을 증가시키고 있으며, 이와 동시에 대형제품의 무게 및 제조원가를 낮추기 위하여 제품의 두께를 줄이는 방안이 시도되고 있다. 그러나, 제품의 두께를 줄이면 낙하충격강도가 떨어지기 때문에 작은 충격에도 성형품의 외관에 크랙이 발생되는 문제점이 있다. 또한, 통상적인 고충격 폴리스티렌의 경우는 내열성 부족으로 인해 고온에 장시간 방치되면 성형품이 변형되는 문제점이 있다.In particular, as consumers' preference for large products has increased in recent years, home appliance companies are increasing the output of large products, and at the same time, a method of reducing the thickness of products to reduce the weight and manufacturing cost of large products has been attempted. However, if the thickness of the product is reduced, the drop impact strength is lowered, so there is a problem in that a crack occurs in the appearance of the molded article even with a small impact. In addition, the conventional high-impact polystyrene has a problem that the molded article is deformed when left at high temperature for a long time due to the lack of heat resistance.
따라서, 본 발명자는 상기의 문제점을 해결하고자 우수한 낙하충격강도를 요구하며 동시에 고온에 장시간 방치되어도 성형품이 변형되지 않는 사출 성형품에 적합한 괴상중합 연속공정으로 제조된 내열성과 낙하충격강도가 우수한 고충격 폴리스티렌 수지를 개발하기에 이른 것이다.Therefore, the present inventors demanded excellent impact resistance of the impact strength and high impact polystyrene excellent in heat resistance and drop impact strength produced by a batch polymerization continuous process suitable for injection molded articles that do not deform the molded article even if left for a long time at high temperature to solve the above problems It is early to develop the resin.
본 발명의 목적은 내열성과 낙하충격강도가 우수한 고충격 폴리스티렌 수지를 제공하기 위한 것이다.An object of the present invention is to provide a high impact polystyrene resin excellent in heat resistance and drop impact strength.
본 발명의 다른 목적은 내열성과 낙하충격강도가 우수한 고충격 폴리스티렌 수지의 제조방법을 제공하기 위한 것이다.Another object of the present invention is to provide a method for producing a high impact polystyrene resin excellent in heat resistance and drop impact strength.
발명의 상기 목적 및 기타의 목적들은 하기 설명되는 본 발명에 의해 모두 달성될 수 있다.The above and other objects of the invention can be achieved by the present invention described below.
도 1은 본 발명에 따른 고충격 폴리스티렌 수지의 제조법을 나타낸 개략적인 공정도이다.1 is a schematic process chart showing a manufacturing method of a high impact polystyrene resin according to the present invention.
본 발명의 내열성과 낙하충격강도가 우수한 고충격 폴리스티렌 수지는 고무입자직경이 0.5∼1.0 마이크론인 스티렌계 모노머와 폴리부타디엔계 고무(Ⅰ)로 이루어진 중합체(Ⅰ) 70∼90 중량부; 및 고무입자직경이 1.0∼1.5 마이크론인 스티렌계 모노머와 폴리부타디엔계 고무(Ⅱ)로 이루어진 중합체(Ⅱ) 10∼30 중량부로 이루어진다.The high impact polystyrene resin having excellent heat resistance and drop impact strength of the present invention comprises 70 to 90 parts by weight of a polymer (I) consisting of a styrene monomer having a rubber particle diameter of 0.5 to 1.0 micron and a polybutadiene rubber (I); And 10 to 30 parts by weight of polymer (II) consisting of a styrene monomer having a rubber particle diameter of 1.0 to 1.5 microns and a polybutadiene rubber (II).
본 발명에 사용되는 스티렌계 모노머로는 스티렌, α-메틸 스티렌, α-에틸 스티렌, ρ-메틸 스티렌 등이 있다. 상기 폴리부타디엔계 고무(Ⅰ)로는 1,4-cis 함량이 95 중량% 이상인 것이 사용 가능하고, 폴리부타디엔계 고무(Ⅱ)로는 1,4-cis 함량이 40 중량% 이하인 것이 사용 가능하다.Styrene-based monomers used in the present invention include styrene, α-methyl styrene, α-ethyl styrene, ρ-methyl styrene and the like. As the polybutadiene-based rubber (I), a 1,4-cis content of 95 wt% or more may be used, and as the polybutadiene-based rubber (II), a 1,4-cis content of 40 wt% or less may be used.
상기 고충격 폴리스티렌 수지는 그라프트율이 150∼200 퍼센트이고 분자량 분포도가 1.8∼2.3 범위를 갖는다.The high impact polystyrene resin has a graft ratio of 150 to 200 percent and a molecular weight distribution of 1.8 to 2.3.
본 발명의 내열성과 낙하충격강도가 우수한 고충격 폴리스티렌 수지는 1,4-cis 함량이 상이한 2종의 폴리부타디엔계 고무를 사용한 괴상중합 연속공정으로 제조된다. 상기 고충격 폴리스티렌 수지를 제조하는 방법은 도 1에 개시된 공정도에 나타난 바와 같다.The high impact polystyrene resin having excellent heat resistance and drop impact strength of the present invention is prepared by a bulk polymerization continuous process using two kinds of polybutadiene-based rubbers having different 1,4-cis contents. The method for producing the high impact polystyrene resin is as shown in the process chart disclosed in FIG.
본 발명에 따른 고충격 폴리스티렌 수지의 제조방법은 두 개의 반응기(R11,R12)에 스티렌계 모노머와 1,4-cis 함량이 95 중량% 이상인 폴리부타디엔계 고무(Ⅰ) 및 스티렌계 모노머와 1,4-cis 함량이 40 중량% 이하인 폴리부타디엔계 고무(Ⅱ)를 각각 투입하고, 110∼140 ℃에서 1.5∼2.5시간 동안 20∼35 %의 전환율로 중합하여 중합체(Ⅰ) 및 중합체(Ⅱ)를 생성하고; 생성된 2종의 중합체(Ⅰ,Ⅱ)를 혼합하여 다음 반응기(R2)로 이송하고, 150∼180 ℃에서 1∼2시간 동안 45∼50 %의 전환율로 중합하고; 그리고 생성된 중합체를 다음 반응기(R3)로 이송하여 170∼200 ℃에서 0.5∼1.5시간 동안 70∼75 %의 전환율로 중합하는 단계로 이루어진다.Method for producing a high impact polystyrene resin according to the present invention is a polybutadiene rubber (I) and styrene monomer having a styrene monomer and 1,4-cis content of at least 95% by weight in two reactors (R 11, R 12 ) and Polybutadiene-based rubber (II) having a 1,4-cis content of 40% by weight or less was added thereto, and the polymer (I) and the polymer (II) were polymerized at 110-140 ° C. for 1.5-2.5 hours at a conversion rate of 20-35%. ); The resulting two polymers (I, II) were mixed and transferred to the next reactor (R 2 ) and polymerized at a conversion rate of 45-50% at 150-180 ° C. for 1-2 hours; The resulting polymer is then transferred to the next reactor (R 3 ) and polymerized at a conversion rate of 70 to 75% at 0.5 to 1.5 hours at 170 to 200 ° C.
이하 본 발명의 고충격 폴리스티렌 수지를 제조하는 방법을 보다 구체적으로 설명하면 다음과 같다.Hereinafter, a method of manufacturing the high impact polystyrene resin of the present invention will be described in detail.
제1단계 반응에서, 스티렌계 모노머 및 1,4-cis 함량이 상이한 폴리부타디엔계 고무를 혼합하여 서로 상이한 고무입자직경을 갖는 2종의 중합체를 제조한다.In the first step reaction, two polymers having different rubber particle diameters are prepared by mixing styrene monomer and polybutadiene rubber having different 1,4-cis contents.
반응기(R11)에 스티렌계 모노머, 1,4-cis 함량이 95 중량% 이상인 폴리부타디엔계 고무(Ⅰ) 및 중합개시제를 투입하여 110∼140 ℃에서 1.5∼2.5시간 동안20∼35 %의 전환율로 중합시킨다. 본 발명에서 사용 가능한 스티렌계 모노머는 스티렌, α-메틸 스티렌, α-에틸 스티렌, ρ-메틸 스티렌 등이다. 상기 반응기(R11) 내의 고무용액은 95 중량부의 스티렌 모노머 및 5 중량부의 폴리부타디엔계 고무(Ⅰ)로 이루어지며, 점도는 상온에서 45∼65 센티포이즈 수준이다. 상기 반응에 의해 생성된 중합체(Ⅰ)는 고무입자직경이 0.5∼1.0 마이크론 이다.A styrene-based monomer, polybutadiene-based rubber (I) having a 1,4-cis content of 95% by weight or more, and a polymerization initiator were added to the reactor (R 11 ), and the conversion rate was 20-35% at 110-140 ° C. for 1.5-2.5 hours. To polymerize. Styrene-based monomers usable in the present invention are styrene, α-methyl styrene, α-ethyl styrene, p-methyl styrene and the like. The rubber solution in the reactor (R 11 ) is composed of 95 parts by weight of styrene monomer and 5 parts by weight of polybutadiene-based rubber (I), the viscosity is 45 to 65 centipoise level at room temperature. Polymer (I) produced by the above reaction has a rubber particle diameter of 0.5 to 1.0 micron.
또 하나의 반응기(R12)에 스티렌계 모노머, 1,4-cis 함량이 40 중량% 이하 폴리부타디엔계 고무(Ⅱ) 및 중합개시제를 투입하여 110∼140 ℃에서 1.5∼2.5시간 동안 20∼35 %의 전환율로 중합시킨다. 상기 반응에 사용되는 스티렌계 모노머는 상기 중합체(Ⅰ)의 제조시 사용된 모노머와 동일하다. 상기 반응기(R12) 내의 고무용액은 95 중량부의 스티렌 모노머 및 5 중량부의 상기 폴리부타디엔계 고무(Ⅱ)로 이루어지며, 점도는 상온에서 155∼185 센티포이즈 수준이다. 상기 반응에 의해 생성된 중합체(Ⅱ)는 고무입자직경이 1.0∼1.5 마이크론 이다.In another reactor (R 12 ), a styrene-based monomer, 1,4-cis content of 40 wt% or less of polybutadiene-based rubber (II) and a polymerization initiator were added, and 20-35 at 110-140 ° C. for 1.5-2.5 hours. Polymerize at% conversion. The styrene monomer used in the reaction is the same as the monomer used in the preparation of the polymer (I). The rubber solution in the reactor (R 12 ) is composed of 95 parts by weight of styrene monomer and 5 parts by weight of the polybutadiene-based rubber (II), the viscosity is 155 ~ 185 centipoise level at room temperature. Polymer (II) produced by the above reaction has a rubber particle diameter of 1.0 to 1.5 microns.
제2단계 반응에서, 상기 제1단계 반응에 의해 생성된 2종의 중합체를 혼합하여 다음 반응기(R2)로 이송하고, 150∼180 ℃에서 1∼2시간 동안 45∼50%의 전환율로 중합한다.In the second stage reaction, the two polymers produced by the first stage reaction are mixed and transferred to the next reactor (R 2 ) and polymerized at a conversion rate of 45-50% for 1 to 2 hours at 150 to 180 ° C. do.
즉, 반응기(R2)에 서로 상이한 고무입자직경을 갖도록 제조된 상기 중합체(Ⅰ,Ⅱ)를 투입하여 재차 중합하는데, 전환율이 37 %인 시점에 징크-스테아레이트, 산화방지제 및 분자량 조절제를 투입하여 전환율이 45∼50 %가 되도록 한다. 상기반응에 의해 생성된 중합체는 고무입자직경 0.5∼1.0 마이크론인 중합체 70∼90 중량% 및 고무입자직경 1.0∼1.5 마이크론인 중합체 10∼30 중량%로 구성된다.That is, the polymers (I, II) prepared to have different rubber particle diameters were added to the reactor (R 2 ) to polymerize again, and zinc-stearate, an antioxidant, and a molecular weight regulator were added at a conversion rate of 37%. The conversion rate is 45-50%. The polymer produced by the above reaction is composed of 70 to 90% by weight of a polymer having a rubber particle diameter of 0.5 to 1.0 micron and 10 to 30% by weight of a polymer having a rubber particle diameter of 1.0 to 1.5 micron.
제3단계 반응에서, 상기 제2단계 반응에 의해 생성된 중합체를 다음 반응기(R3)로 이송하고, 170∼200 ℃에서 0.5∼1.5시간 동안 70∼75 %의 전환율로 중합한다. 마지막으로 휘발조(Devolatilizer)를 거쳐 미반응된 모노머를 회수하여 응축 콘덴서로 보내면 전환율이 99.9 %인 고충격 폴리스티렌(HIPS) 수지가 제조된다.In the third stage reaction, the polymer produced by the second stage reaction is transferred to the next reactor (R 3 ) and polymerized at 170-200 ° C. for a conversion of 70-75% for 0.5-1.5 hours. Finally, the unreacted monomer is recovered through a devolatilizer and sent to a condenser to produce a high impact polystyrene (HIPS) resin having a conversion rate of 99.9%.
상기와 같이 제조된 본 발명의 고충격 폴리스티렌(HIPS) 수지는 고무입자가 수지 내에 바이모달 형태로 분산되고, 그라프트율이 150∼200 퍼센트로 유지되고 분자량 분포도가 1.8∼2.3 범위를 갖는다. 그라프트율이 150 퍼센트 미만이 되면 낙하충격강도가 떨어지게 되며 200 퍼센트를 초과하게 되어도 낙하충격강도가 떨어지게 된다. 그리고, 분자량 분포도가 1.8∼2.3 범위를 벗어나면 낙하충격강도가 떨어지게 된다.The high impact polystyrene (HIPS) resin of the present invention prepared as described above has rubber particles dispersed in the resin in a bimodal form, the graft ratio is maintained at 150 to 200 percent and the molecular weight distribution ranges from 1.8 to 2.3. If the graft rate is less than 150 percent, the drop impact strength drops, and if it exceeds 200 percent, the drop impact strength drops. If the molecular weight distribution is out of the range of 1.8 to 2.3, the drop impact strength drops.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예Example
중합체(Ⅰ)의 제조Preparation of Polymer (I)
93 중량부의 스티렌 모노머 및 7 중량부의 폴리부타디엔계 고무(Ⅰ)를 첨가하고, 개시제로는 3급 부틸 퍼옥시벤조에이트를 0.05 중량부로 투입하여 116 ℃에서 2.2시간 동안 중합시켜 전환율이 30 %인 중합체를 합성하였다. 이때, 고무입자직경은 0.5∼1.0 마이크론 이었다.93 parts by weight of a styrene monomer and 7 parts by weight of polybutadiene-based rubber (I) were added, and tertiary butyl peroxybenzoate was added as 0.05 part by weight of a polymer, and polymerized at 116 ° C. for 2.2 hours to give a conversion of 30%. Was synthesized. At this time, the rubber particle diameter was 0.5-1.0 micron.
중합체(Ⅱ)의 제조Preparation of Polymer (II)
93 중량부의 스티렌 모노머 및 7 중량부의 폴리부타디엔계 고무(Ⅱ)를 첨가하고, 개시제로는 3급 부틸 퍼옥시아세테이트를 0.07 중량부로 투입하여 115 ℃에서 2시간 동안 중합시켜 전환율이 27 %인 중합체를 합성하였다. 이때, 고무입자직경은 1.0∼1.5 마이크론 이었다.93 parts by weight of styrene monomer and 7 parts by weight of polybutadiene-based rubber (II) were added, and tertiary butyl peroxyacetate was added as 0.07 part by weight of an initiator and polymerized at 115 ° C. for 2 hours to obtain a polymer having a conversion of 27%. Synthesized. At this time, the rubber particle diameter was 1.0 to 1.5 micron.
실시예1∼3 및 비교실시예 1∼3 : 고충격 폴리스티렌 수지의 중합Examples 1-3 and Comparative Examples 1-3: Polymerization of High Impact Polystyrene Resin
상기 중합체(Ⅰ) 및 중합체(Ⅱ)를 표 1에 나타낸 조성으로 혼합하고,전환율이 37 %인 시점에 징크-스테아레이트, 산화방지제 및 분자량 조절제를 투입하여 150∼180 ℃에서 1∼2시간 동안 전환율이 45∼50 %가 되도록 중합하였다. 생성된 중합체를 다른 반응기로 이송하여 170∼200 ℃에서 0.5∼1.5시간 동안 전환율이 70∼75 %가 되도록 중합하고, 휘발조를 거쳐 전환율이 99.9 %인 고충격 폴리스티렌(HIPS) 수지를 제조하였다.The polymer (I) and the polymer (II) were mixed in the composition shown in Table 1, and zinc-stearate, an antioxidant, and a molecular weight regulator were added at a conversion rate of 37% for 1 to 2 hours at 150 to 180 ° C. The polymerization was carried out so that the conversion was 45 to 50%. The resulting polymer was transferred to another reactor to polymerize at 170-200 ° C. for 0.5-1.5 hours with a conversion of 70-75%, and a high impact polystyrene (HIPS) resin having a conversion of 99.9% was prepared through a volatilization bath.
비교실시예 1은 중합체(Ⅰ) 50 중량부 및 중합체(Ⅱ) 50 중량부를 사용한 것이고, 비교실시예 2, 3은 각각 중합체(Ⅰ), 중합체(Ⅱ)만을 사용하여 제조하였다.Comparative Example 1 used 50 parts by weight of polymer (I) and 50 parts by weight of polymer (II), and Comparative Examples 2 and 3 were prepared using only polymer (I) and polymer (II), respectively.
상기 수지를 사출성형기로 사출하여 시험시편을 제조한 뒤 물성을 측정하여 표 1에 나타내었다. 낙하충격강도는 JIS K7211, 비캐트 연화점은 ISO R306B(승온속도: 50 ℃/hr), 유동성은 ASTM D1238(200 ℃, 5 kg)에 의거하여 각각 측정되었다.The resin was injected into an injection molding machine to prepare a test specimen, and the physical properties thereof were shown in Table 1 below. Drop impact strength was measured according to JIS K7211, non-cat softening point, ISO R306B (heating rate: 50 ° C / hr), and fluidity based on ASTM D1238 (200 ° C, 5 kg).
상기 표 1의 결과로부터, 상이한 고무입자직경을 갖는 2종의 중합체로부터 제조된 본 발명의 수지가 한 종류의 중합체로부터 제조된 비교실시예 2, 3의 수지에 비해 내열성과 낙하충격강도가 우수함을 알 수 있다. 또한, 2종의 중합체(Ⅰ,Ⅱ)를 각각 70∼90 중량부 및 10∼30 중량부의 양으로 사용한 경우 내열성과 낙하충격강도가 우수함을 알 수 있다.From the results of Table 1, the resin of the present invention prepared from two polymers having different rubber particle diameters is superior in heat resistance and drop impact strength than the resins of Comparative Examples 2 and 3 prepared from one type of polymer. Able to know. In addition, it can be seen that when the two polymers (I, II) are used in amounts of 70 to 90 parts by weight and 10 to 30 parts by weight, respectively, the heat resistance and the drop impact strength are excellent.
본 발명은 상이한 고무입자직경을 갖는 2종의 중합체로 이루어진 내열성과 낙하충격강도가 우수한 고충격 폴리스티렌 수지 및 괴상중합 연속공정으로 이를 제조하는 방법을 제공하는 효과를 지닌다.The present invention has the effect of providing a high-impact polystyrene resin excellent in heat resistance and drop impact strength composed of two polymers having different rubber particle diameters and a method for producing the same by a bulk polymerization continuous process.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01275649A (en) * | 1988-04-27 | 1989-11-06 | Asahi Chem Ind Co Ltd | Rubber-modified polystyrene resin composition excellent in gloss and impact resistance |
| JPH01279945A (en) * | 1988-01-29 | 1989-11-10 | Sumitomo Chem Co Ltd | Rubber-modified styrene resin composition |
| US5240993A (en) * | 1989-08-02 | 1993-08-31 | The Dow Chemical Company | Process for the preparation of rubber-reinforced monovinylidene aromatic polymers |
| US5942575A (en) * | 1996-09-27 | 1999-08-24 | Enichem S.P.A. | Process for manufacturing rubber-reinforced vinyl-aromatic polymers |
| KR20010056844A (en) * | 1999-12-17 | 2001-07-04 | 안복현 | High Impact Polystyrene Resin with Good Falling Dart Impact Prepared by Continuous Mass Polymerization process |
| KR20010109785A (en) * | 2000-06-02 | 2001-12-12 | 안복현 | High Impact Polystyrene Resin with Good Falling Dart Impact and Anti-Abrasion Prepared by Continuous Mass Polymerization Process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01279945A (en) * | 1988-01-29 | 1989-11-10 | Sumitomo Chem Co Ltd | Rubber-modified styrene resin composition |
| JPH01275649A (en) * | 1988-04-27 | 1989-11-06 | Asahi Chem Ind Co Ltd | Rubber-modified polystyrene resin composition excellent in gloss and impact resistance |
| US5240993A (en) * | 1989-08-02 | 1993-08-31 | The Dow Chemical Company | Process for the preparation of rubber-reinforced monovinylidene aromatic polymers |
| US5942575A (en) * | 1996-09-27 | 1999-08-24 | Enichem S.P.A. | Process for manufacturing rubber-reinforced vinyl-aromatic polymers |
| KR20010056844A (en) * | 1999-12-17 | 2001-07-04 | 안복현 | High Impact Polystyrene Resin with Good Falling Dart Impact Prepared by Continuous Mass Polymerization process |
| KR20010109785A (en) * | 2000-06-02 | 2001-12-12 | 안복현 | High Impact Polystyrene Resin with Good Falling Dart Impact and Anti-Abrasion Prepared by Continuous Mass Polymerization Process |
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