KR100232701B1 - Process for preparing styrenic thermoplastic resin composition - Google Patents
Process for preparing styrenic thermoplastic resin composition Download PDFInfo
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- KR100232701B1 KR100232701B1 KR1019960006971A KR19960006971A KR100232701B1 KR 100232701 B1 KR100232701 B1 KR 100232701B1 KR 1019960006971 A KR1019960006971 A KR 1019960006971A KR 19960006971 A KR19960006971 A KR 19960006971A KR 100232701 B1 KR100232701 B1 KR 100232701B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
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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
- 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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Abstract
본 발명은 응력하에서의 균열과 관련하여 부식제와 접촉시 양호한 효과를 나타내는 스티렌계 열가소성 수지 조성물의 제조방법을 제공함을 그 목적으로 하는 것으로서, 모노 비닐 방향족 화합물 및 비닐 시아나이드 모노머와 폴리부타디엔계 고무를 첨가하고 여기에 상온에서 54 내지 76 센티스토크의 점도를 갖는 유동파라핀계의 미네랄 오일, 산화 방지제, 고급 지방산의 금속염 및 개시제를 투입하여 괴상 연속 중합 방법에 의해 중량평균 분자량이 17만에서 21만인 스티렌계 열가소성 수지 조성물을 제조함에 있어서, 전체 수지 조성물 100중량부에 대하여 모노 비닐 방향족 화합물은 79 내지 93중량부, 비닐 시아나이드 모노머는 0 내지 10중량부, 폴리부타디엔계 고무는 7 내지 11중량부를 첨가하며, 개시제로는 3급 부틸 퍼옥시벤조에이트를 0.05-0.1중량부 투입함을 특징으로 한다.It is an object of the present invention to provide a method for producing a styrene-based thermoplastic resin composition which exhibits a good effect upon contact with a caustic agent in relation to cracking under stress, and the addition of a monovinyl aromatic compound, a vinyl cyanide monomer and a polybutadiene-based rubber. Styrene system having a weight average molecular weight of 170,000 to 210,000 by bulk continuous polymerization method by adding a liquid paraffinic mineral oil, an antioxidant, a metal salt of a higher fatty acid and an initiator having a viscosity of 54 to 76 centistokes at room temperature. In preparing the thermoplastic resin composition, 79 to 93 parts by weight of the monovinyl aromatic compound, 0 to 10 parts by weight of the vinyl cyanide monomer, and 7 to 11 parts by weight of the polybutadiene rubber are added based on 100 parts by weight of the total resin composition. 0.05-0.1 parts by weight of tertiary butyl peroxybenzoate as an initiator Characterized in the input box.
Description
본 발명은 응력하에서 부식제와 접촉시 내균열성이 양호한 스티렌계 열가소성 수지 조성물의 제조방법에 관한 것이다.The present invention relates to a method for producing a styrenic thermoplastic resin composition having good crack resistance upon contact with a caustic under stress.
일반적으로 열가소성에 수지, 그 중에서 내충격성 폴리스티렌계 수지로 된 성형품은 부식을 유발하는 화학물질과 장시간 접촉될 때 응력에 의해 쉽게 균열이 생긴다. 이들 화학물질은 특히 사이클로펜탄과 같은 발포제로서, 상기 부식은 내충격성 폴리스티렌계 수지로 된 냉장고의 제조시에 나타나며 냉장고 체임버는 사이클로펜탄 같은 발포제에 의해 폴리우레탄이 팽창하는 동안 균열된다.In general, molded articles made of thermoplastic resins, particularly impact-resistant polystyrene-based resins, are easily cracked by stress when prolonged contact with chemicals causing corrosion. These chemicals are in particular blowing agents such as cyclopentane, the corrosion of which appears in the manufacture of refrigerators made of impact resistant polystyrene-based resins and the refrigerator chambers crack during expansion of the polyurethane by blowing agents such as cyclopentane.
이와같은 내충격성 폴리스티렌계 수지의 성질 때문에 냉장고를 이미 완성한 경우에도 사이클로펜탄의 침투에 의한 부식이 발생하여 냉장고를 폐기처분하거나 분해 및 조립을 다시 해야하는 문제가 생긴다.Due to the nature of the impact-resistant polystyrene resin, even if the refrigerator has already been completed, corrosion occurs due to the penetration of cyclopentane, causing the refrigerator to be disposed of or to be disassembled and reassembled.
이 문제를 해결하기 위해서 사이클로펜탄과 접촉되는 냉장고 벽을 아크릴로니트릴-부타디엔-스티렌 3원 공중합체(ABS)와 같은 내화학성 필름으로 피복하는 것이 제안되었다. 그러나 이러한 장치를 설치하려면 비용이 많이 든다. 또한 ABS일부를 폴리에틸렌 필름으로 대체하는 것이 제안되었으나, 이 경우에는 이들 열가소성 물질을 접착시키는 것이 매우 어려운 문제가 있다.In order to solve this problem, it has been proposed to coat a refrigerator wall in contact with cyclopentane with a chemical resistant film such as acrylonitrile-butadiene-styrene terpolymer (ABS). However, installing such a device is expensive. In addition, it has been proposed to replace a portion of ABS with a polyethylene film, but in this case, it is very difficult to bond these thermoplastics.
본 발명은 상기와 같은 문제를 해결하기 위한 것으로, 응력하에서의 균열과 관련하여 부식제와 접촉시 양호한 효과를 나타내는 스티렌계 열가소성 수지 조성물의 제조방법을 제공함을 그 목적으로 한다.SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object thereof is to provide a method for producing a styrene-based thermoplastic resin composition which exhibits a favorable effect upon contact with a caustic agent in connection with cracking under stress.
즉, 본 발명은 모노 비닐 방향족 화합물 79 내지 93중량부, 비닐 시아나이드 모노머 0 내지 10중량부와 폴리부타디엔계 고무 7 내지 11중량부로 구성된 수지 100중량부에 대하여, 상온에서 54 내지 76센티스토크의 점도를 갖는 유동파라핀계의 미네랄 오일을 0.5 내지 1.5중량부, 그리고 적정량의 산화방지제 및 고급 지방산의 금속염을 첨가하고 개시제로 3급 부틸퍼옥시벤조에이트(Tertiary Butyl PeroxyBenzoate : 이하 “TBPB”라 칭함)을 0.05 - 0.1중량부 투입하여 괴상연속 중합에 의하여 중량평균 분자량이 17만 내지 21만인 스티렌계 열가소성 수지 조성물을 제조함을 특징으로 한다.That is, according to the present invention, the resin composition comprises 79 to 93 parts by weight of the monovinyl aromatic compound, 0 to 10 parts by weight of the vinyl cyanide monomer and 7 to 11 parts by weight of the polybutadiene rubber, at 54 to 76 centistokes at room temperature. 0.5 to 1.5 parts by weight of a liquid paraffinic mineral oil having a viscosity, and an appropriate amount of an antioxidant and a metal salt of a higher fatty acid are added and tertiary butyl peroxybenzoate (hereinafter referred to as “TBPB”) as an initiator. 0.05 to 0.1 parts by weight of the styrene-based thermoplastic resin composition having a weight average molecular weight of 170,000 to 210,000 by mass continuous polymerization.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에서의 폴리부타디엔계 고무는 그 중의 95중량% 이상이 니켈 촉매하에 연속중합으로 얻어지고, 1,4-cis함량이 50중량% 이하이며 전체 수지 조성물 100중량부에 대해 95중량부의 스티렌 모노머 용액에서 용액점도가 20 내지 100 센티포이즈 수준인 폴리부타디엔계 고무이다.The polybutadiene-based rubber in the present invention is 95% by weight or more of which is obtained by continuous polymerization under a nickel catalyst, 1,4-cis content is 50% by weight or less and 95 parts by weight of styrene monomer with respect to 100 parts by weight of the total resin composition Polybutadiene-based rubbers having a solution viscosity of 20 to 100 centipoise in solution.
상기 폴리부타디엔계 고무는 전체 수지 조성물 100중량부에 대해 7 내지 11중량부 사용되는데, 만일 폴리부타디엔 고무가 7중량부 미만으로 사용되면 내균열성과 신율이 떨어지며 11중량부를 초과하여 과량 사용되면 인장강도와 유동성이 떨어진다. 또한 스티렌계 열가소성 수지 상에 분산된 고무상 물질의 평균입자 직경은 4 내지 6.5마이크론이어야 하는데, 만일 입자평균직경이 4마이크론 미만인 경우에는 내균열성이 떨어지게 되며, 6.5마이크론을 초과하는 경우에는 제조제품 과정에서 입자가 파괴되어 물성에 변화를 일으키기 쉬으므로 좋지 않다.The polybutadiene-based rubber is used 7 to 11 parts by weight based on 100 parts by weight of the total resin composition, if the polybutadiene rubber is used less than 7 parts by weight, the crack resistance and elongation is lowered and the tensile strength is used in excess of 11 parts by weight And liquidity is poor. In addition, the average particle diameter of the rubbery material dispersed on the styrene-based thermoplastic resin should be 4 to 6.5 microns, if the average particle diameter is less than 4 microns, the crack resistance is inferior, if the product exceeds 6.5 microns This is not good because the particles are easily destroyed in the process and change in physical properties.
한편 본 발명의 모노비닐 방향족 화합물에는 스티렌, α-메틸스티렌, α-에틸스티렌, ρ-메틸스티렌 등을 사용할 수 있다.In addition, styrene, (alpha) -methylstyrene, (alpha) -ethylstyrene, (rho) -methylstyrene, etc. can be used for the monovinyl aromatic compound of this invention.
또한 본 발명의 비닐 시아나이드 모노머로는 아크릴로니트릴, 메타크릴로니트릴 중에서 선택된 1종 이상의 화합물을 사용할 수 있는데, 사용량은 전체 수지 조성물 100중량부에 대해 0 내지 10중량부로서, 만일 10중량부를 초과하여 과량 사용하게 되면 가격상으로 인해 경제성이 떨어지게 된다.In addition, as the vinyl cyanide monomer of the present invention, at least one compound selected from acrylonitrile and methacrylonitrile may be used, and the amount of use is 0 to 10 parts by weight based on 100 parts by weight of the total resin composition, and 10 parts by weight if Excessive use in excess results in inferior economics due to price.
한편 본 발명에서는 개시제로 3급 부틸 퍼옥시벤조에이트를 0.05 내지 0.1중량부 사용하는데, 만일 0.05중량부 미만으로 사용하면 중합물의 그라프트율이 떨어지게 되며, 0.1중량부를 초과하여 과량 사용하게 되면 중합반응이 급격히 일어나 위험하게 된다.Meanwhile, in the present invention, tertiary butyl peroxybenzoate is used in an amount of 0.05 to 0.1 parts by weight. If it is used in an amount less than 0.05 parts, the graft ratio of the polymer is lowered. Wake up and become dangerous.
본 발명에서 조성물을 제조하기 위한 중합방법으로는 특히 괴상연속 중합 방법을 사용하는 것이 좋은데, 그것은 순도가 높고 균일한 물성 특성을 갖는 제품을생산하기가 쉽기 때문이다. 상기의 방법에 의해 제조되는 최종 중합물의 그라프트율은 200 내지 280퍼센트를 나타내야 하는데, 만일 최종 종합물의 그라프트율이 200퍼센트 미만이 되면 내균열성이 떨어지게 되며, 280퍼센트를 초과하게 되면 내균열성이 더 이상 향상되제 않게 된다.In the present invention, it is particularly preferable to use a bulk continuous polymerization method for preparing the composition, because it is easy to produce a product having high purity and uniform physical properties. The graft rate of the final polymer produced by the above method should be in the range of 200 to 280 percent. If the graft rate of the final composite is less than 200 percent, the crack resistance will be lowered. If it exceeds 280 percent, the crack resistance will no longer be achieved. It will not improve.
또한 최종 중합물의 중량 평균 분자량은 중합온도와 반응기 중량 등을 조절하여 17만에서 21만이 되도록 하여야 하는데, 만일 중량평균 분자량이 17만 미만으로 되면 강성이 떨어지게 되며, 21만을 초과하게 되면 유동성이 저하되게 된다.In addition, the weight average molecular weight of the final polymer should be adjusted to 170,000 to 210,000 by adjusting the polymerization temperature and the reactor weight. If the weight average molecular weight is less than 170,000, the stiffness is lowered. do.
이상과 같은 본 발명에 따른 수지는 응력하에서 사이크롤펜탄과 같은 부식제와 접촉시 내균열성이 우수하므로 별도의 보호 처리를 하지 않고도 세정제를 세척해 주어야 하는 주방 용구의 제조용 및 냉동기 라이너와 도어라이너의 제조용으로 사용할 수 있다.Since the resin according to the present invention has excellent crack resistance when contacted with a corrosive agent such as cyclopentane under stress, the preparation of kitchen utensils and the freezer liner and door liner that require cleaning the cleaning agent without additional protective treatment. It can be used for manufacture.
이하 본 발명을 실시예 및 비교예를 통해 설명하면 다음과 같다.Hereinafter, the present invention will be described through Examples and Comparative Examples.
[실시예 1]Example 1
스티렌 87중량부, 아크릴로니트릴 2중량부에 폴리부타디엔계 고무 11중량부, 상온에서 54 내지 76센티스토크의 점도를 유동파라핀계의 미네랄오일 0.7중량부, 산화방지제인 트리에틸렌글리콜-비스-3-(3-t-부틸-4-하이드록시-5-메틸페닐)프로피오네이트 [Triethylene glycol-bis-3-(3-t-butyl-4-hydroxy-5-methyl phenyl) propionate] 0.05중량부 및 고급 지방산의 금속염으로 징크스테아레이트(Zinc-Stearate)를 0.02중량부 첨가하고, 개시제인 3급 부틸 퍼옥시 벤조에이트 0.06중량부를 투입하여 괴상연속 중합방법에 의해 중량 평균 분자량이 20만인 중합물을 제조하였다. 이를 사출성형기로 사출하고 압축하여 물성태스트 시편을 제작한 뒤, 고무상의 평균입자직경, 그라프트율을 측정하였고, 또한 부식제인 사이클로펜탄에 대한 저향력을 시험하기 위해 인장강도와 신율을 다음과 같은 조건으로 측정하여, 그 결과를 다음 표 1에 나타내었다.87 parts by weight of styrene, 2 parts by weight of acrylonitrile, 11 parts by weight of polybutadiene rubber, 54 to 76 centistokes of viscosity at room temperature, 0.7 parts by weight of mineral oil of liquid paraffin, and triethylene glycol-bis-3 as an antioxidant 0.05 parts by weight of-(3-t-butyl-4-hydroxy-5-methylphenyl) propionate [Triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methyl phenyl) propionate] and 0.02 parts by weight of zinc stearate was added as a metal salt of a higher fatty acid, and 0.06 parts by weight of tertiary butyl peroxy benzoate as an initiator was added to prepare a polymer having a weight average molecular weight of 200,000 by a bulk continuous polymerization method. . After injection into the injection molding machine and compression to make the material test specimen, the average particle diameter and graft ratio of rubber phase were measured, and the tensile strength and elongation were measured under the following conditions to test the resistance to cyclopentane, a caustic. It measured and the result is shown in following Table 1.
1) 인장강도 : ASTM D638, TEST SPEED:20mm/min1) Tensile Strength: ASTM D638, TEST SPEED: 20mm / min
2) 신 율 : ASTM D638, TEST SPEED:20mm/min2) Elongation: ASTM D638, TEST SPEED: 20mm / min
3) 사이클로펜탄에 대한 저향력 실험은 25℃ 상온을 유지시킨 내용적이 10리터인 진공오븐 안에 외경 125mm인 반원형 응력부여 장치에 성형시편을 고정시켜 넣고 사이클로펜탄 70mm를 투입, 기화시켜 5시간 동안 방치하여 실험하였다.3) Low-force experiment on cyclopentane was carried out by fixing molded specimens in a semi-circular stress applying device with an outer diameter of 125 mm in a 10-liter vacuum oven maintained at 25 ° C, and adding cyclopentane 70 mm and evaporating it for 5 hours. The experiment was carried out.
[실시예 2]Example 2
아크릴로니트릴을 사용하지 않고, 대신 스티렌을 89중량부 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 20만인 중합물이 제조되었으며, 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.It carried out similarly to Example 1 except not using acrylonitrile but using 89 weight part of styrene instead. As a result, a polymer having a weight average molecular weight of 200,000 was prepared, and measured results are shown in Table 1 below.
[실시예 3]Example 3
스티렌 85중량부, 아크릴로니트릴 5중량부, 폴리부타디엔계 고무 10중량부, 유동파라핀계의 미네랄오일 0.5중량부, 개시제인 3급 부틸 퍼옥시 벤조에이트를 0.1중량부 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 21만인 중합물이 제조되었으며, 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Except 85 parts by weight of styrene, 5 parts by weight of acrylonitrile, 10 parts by weight of polybutadiene rubber, 0.5 parts by weight of liquid paraffinic mineral oil, and 0.1 parts by weight of tertiary butyl peroxy benzoate as an initiator. It carried out similarly to Example 1. As a result, a polymer having a weight average molecular weight of 210,000 was prepared, and measured results are shown in Table 1 below.
[실시예 4]Example 4
아크릴로니트릴을 사용하지 않고, 대신 스티렌을 90중량부, 유동파라핀계의 미네랄오일을 0.5중량부, 개시제인 3급 부틸 퍼옥시 벤조에이트를 0.1중량부 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 21만인 중합물이 제조되었으며, 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Not using acrylonitrile, but instead of 90 parts by weight of styrene, 0.5 parts by weight of liquid paraffin-based mineral oil, 0.1 parts by weight of tertiary butyl peroxy benzoate as an initiator is the same as in Example 1 It was carried out. As a result, a polymer having a weight average molecular weight of 210,000 was prepared, and measured results are shown in Table 1 below.
[실시예 5]Example 5
스티렌 84중량부, 아크릴로니트릴 8중량부, 폴리부타디엔계 고무 8중량부, 유동파라핀계의 미네랄오일 1.0중량부, 개시제인 3급 부틸 퍼옥시 벤조에이트를 0.05중량부 사용하는 것을 제외하고는 실시에 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 18만인 중합물이 제조되었으며, 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Except for using 84 parts by weight of styrene, 8 parts by weight of acrylonitrile, 8 parts by weight of polybutadiene rubber, 1.0 part by weight of liquid paraffinic mineral oil, and 0.05 parts by weight of tertiary butyl peroxy benzoate as an initiator. In the same manner as in 1. As a result, a polymer having a weight average molecular weight of 180,000 was prepared, and the results are shown in Table 1 below.
[실시예 6]Example 6
아크릴로니트릴을 사용하지 않고, 대신 스티렌을 92중량부, 유동파라핀계의 미네랄오일을 1.0중량부, 개시제인 3급 부틸 퍼옥시 벤조에이트를 0.05중량부 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다.실험결과 중량평균분자량이 18만인 중합물이 제조되었으며, 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Not using acrylonitrile, except that 92 parts by weight of styrene, 1.0 parts by weight of liquid paraffin-based mineral oil, and 0.05 parts by weight of tertiary butyl peroxy benzoate as an initiator were used. As a result, a polymer having a weight average molecular weight of 180,000 was prepared, and the physical properties were measured and the results are shown in Table 1 below.
[실시예 7]Example 7
스티렌 83중량부, 아크릴로니트릴 10중량부, 폴리부타디엔계 고무 7중량부, 유동파라핀계의 미네랄오일 1.5중량부, 개시제인 3급 부틸 퍼옥시 벤조에이트를 0.08중량부 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 17만인 중합물이 제조되었으며, 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Except 83 parts by weight of styrene, 10 parts by weight of acrylonitrile, 7 parts by weight of polybutadiene rubber, 1.5 parts by weight of liquid paraffinic mineral oil, and 0.08 parts by weight of tertiary butyl peroxy benzoate as an initiator. It carried out similarly to Example 1. As a result, a polymer having a weight average molecular weight of 170,000 was prepared, and the results are shown in Table 1 below.
[실시예 8]Example 8
아크릴로니트릴을 사용하지 않고, 대신 스티렌을 93중량부, 유동파라핀계의 미네랄오일을 1.5중량부, 개시제인 3급 부틸 퍼옥시 벤조에이트를 0.08중량부 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 17만인 중합물이 제조되었으며, 물성을 측정하여 그 결과를 표 1에 나타내었다.Not using acrylonitrile, except that 93 parts by weight of styrene, 1.5 parts by weight of liquid paraffinic mineral oil, and 0.08 parts by weight of tertiary butyl peroxy benzoate as an initiator are used. It was carried out. Experimental results A polymer having a weight average molecular weight of 170,000 was prepared, and the results are shown in Table 1 by measuring the physical properties.
[비교예 1]Comparative Example 1
스티렌 90중량부, 폴리부타디엔계 고무 10중량부, 유동파라핀계의 미네랄오일 0.8중량부, 개시제인 3급 부틸 퍼옥시 벤조에이트를 0.03중량부 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 19만인 중합물이 제조되었으며, 물성을 측정하여 그 결과를 표 1에 나타내었다.The same procedure as in Example 1 was carried out except that 90 parts by weight of styrene, 10 parts by weight of polybutadiene rubber, 0.8 parts by weight of liquid paraffinic mineral oil, and 0.03 parts by weight of tertiary butyl peroxy benzoate as an initiator were used. . Experimental results A polymer having a weight average molecular weight of 190,000 was prepared, and the results are shown in Table 1 by measuring the physical properties.
[비교예 2]Comparative Example 2
스티렌 94중량부, 폴리부타디엔계 고무 6중량부, 유동파라핀계의 미네랄오일 1.2중량부, 개시제인 3급 부틸 퍼옥시 벤조에이트를 0.09중량부 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 21만인 중합물이 제조되었으며, 물성을 측정하여 다음 표 1에 나타내었다.The same procedure as in Example 1 was repeated except that 94 parts by weight of styrene, 6 parts by weight of polybutadiene rubber, 1.2 parts by weight of liquid paraffinic mineral oil, and 0.09 part by weight of tertiary butyl peroxy benzoate as an initiator were used. . As a result, a polymer having a weight average molecular weight of 210,000 was prepared, and the physical properties thereof are shown in Table 1 below.
[비교예 3]Comparative Example 3
스티렌 95중량부, 폴리부타디엔계 고무 5중량부, 유동파라핀계의 미네랄오일 1.5중량부, 개시제인 3급 부틸 퍼옥시 벤조에이트 0.1중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 21만인 중합물이 제조되었으며, 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.The same procedure as in Example 1 was carried out except that 95 parts by weight of styrene, 5 parts by weight of polybutadiene rubber, 1.5 parts by weight of liquid paraffinic mineral oil, and 0.1 parts by weight of tertiary butyl peroxy benzoate as an initiator were used. As a result, a polymer having a weight average molecular weight of 210,000 was prepared, and measured results are shown in Table 1 below.
[표 1]TABLE 1
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