KR0181633B1 - Process of producing styrenic thermoplastic resin compositions - Google Patents
Process of producing styrenic thermoplastic resin compositions Download PDFInfo
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- KR0181633B1 KR0181633B1 KR1019960003169A KR19960003169A KR0181633B1 KR 0181633 B1 KR0181633 B1 KR 0181633B1 KR 1019960003169 A KR1019960003169 A KR 1019960003169A KR 19960003169 A KR19960003169 A KR 19960003169A KR 0181633 B1 KR0181633 B1 KR 0181633B1
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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
- 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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- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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Abstract
본 발명은 저온, 저압,저속에서의 사출이 가능하여 구조가 복잡하고 얇은 성형품 및 대형 TV 하우징, 미세공 TV 하우징의 성형에 적합한 내열성과 내충격성이 조화되고 유동성이 우수한 스티렌계 열가소성 수지 조성물을 제조하기 위한 것으로서, 중량평균 분자량이 14만 내지 19만인 스티렌계 열가소성 수지 조성물을 제조함에 있어서, 전체 수지 조성물 100중량부에 대해 모노비닐 방향족 화합물 91내지 94중량부와 폴리부타디엔계 고무 6내지 9중량부를 첨가하고, 여기에 상온에서 54내지 76센티스토크의 점도를 갖는 유동 파라핀계의 미네랄오일 2.0 내지 4.5중량부, 고급 지방산의 금속염으로 징크-스테아레이트 0.01 내지 0.08중량부, 그리고 적정량의 산화방지제를 첨가하고 개시제로 3급 부틸 퍼옥시아세테이트를 0.02-0.1중량부 투입하여 괴상연속 중합에 의하여 제조함을 특징으로 한다.The present invention is a low-temperature, low-pressure, low-speed injection is possible to produce a styrene-based thermoplastic resin composition is complex structure, excellent heat resistance, impact resistance and fluidity suitable for molding thin molded products and large TV housing, micro-porous TV housing In order to prepare a styrenic thermoplastic resin composition having a weight average molecular weight of 140,000 to 190,000, 91 to 94 parts by weight of a monovinyl aromatic compound and 6 to 9 parts by weight of a polybutadiene rubber with respect to 100 parts by weight of the total resin composition. To this is added 2.0 to 4.5 parts by weight of liquid paraffinic mineral oil having a viscosity of 54 to 76 centistokes at room temperature, 0.01 to 0.08 parts by weight of zinc-stearate as a metal salt of higher fatty acid, and an appropriate amount of antioxidant. Tertiary butyl peroxyacetate was added 0.02-0.1 parts by weight as an initiator. It characterized by a W prepared.
Description
본 발명은 스티렌계 열가소성 수지 조성물의 제조방법에 관한 것으로서, 더욱 상세하게로는 저온, 저압, 저속에서의 사출이 가능하여 구조가 복잡하고 얇은 성형품 및 대형 TV 하우징, 미세공 TV 하우징의 성형에 적합한 내열성과 내충격성이 조화되고 유동성이 우수한 스티렌계 열가소성 수지 조성물의 제조방법에 관한 것이다.The present invention relates to a method for producing a styrene-based thermoplastic resin composition, and more particularly, it is possible to injection at low temperature, low pressure, low speed, complex structure, suitable for molding thin molded products, large TV housing, microporous TV housing The present invention relates to a method for producing a styrene-based thermoplastic resin composition having excellent heat resistance and impact resistance and excellent fluidity.
일반적으로 고무 변성된 폴리스티렌 수지 (이하 HIPS라고 칭함)는 내충격성, 유동성, 내열성 등의 물성 발란스가 양호하여 전기·전자 제품의 하우징으로 널리 사용되고 있다. 특히 최근들어 소비자들의 대형제품 선호경향에 따라 가전 메이커들은 대형제품을 주력으로 생산판매하고 있으며 동시에 이들 제품의 성형에 유리한 유동성이 우수한 수지를 개발하는데 노력하고 있다.In general, rubber-modified polystyrene resins (hereinafter referred to as HIPS) have a good balance of physical properties such as impact resistance, fluidity, and heat resistance, and thus are widely used as housings for electrical and electronic products. In particular, according to consumers' preference for large products, home appliance makers are mainly producing and selling large products, and at the same time, they are trying to develop resins having excellent flowability for molding these products.
그런데 종래의 일반 HIPS를 사용하여 대형제품을 성형할 때는 과다한 온도 및 압력에서 사출하게 되고 이에 따라 높은 전단력으로 인해 수지가 분해될 가능성이 있는데 이러한 수지의 분해는 플로우 마크(FLOW MARK), 혹줄과 같은 사출외관 불량문제의 직접적인 원인이 되므로 좋지 않다.However, when molding large products using conventional HIPS, the resin may be injected at excessive temperatures and pressures, and thus the resin may be decomposed due to high shear force. It is not good because it is a direct cause of the problem of poor injection appearance.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로서 저온, 저압, 저속에서의 사출이 가능한 내열성과 내충격성이 조화되고 유동성이 우수한 스티렌계 열가소성 수지 조성물의 제조방법을 제공하는데, 그 목적이 있다.The present invention is to solve the above problems, to provide a method for producing a styrene-based thermoplastic resin composition that is excellent in fluidity and impact resistance and heat resistance that can be injected at low temperature, low pressure, low speed.
즉, 본 발명은 전체 수지 조성물 100중량부에 대해 모노비닐 방향족 화합물 91 내지 94 중량부와 폴리부타디엔계 고무 6내지 9중량부를 첨가하고, 여기에 상온에서 54내지 76센티스토크의 점도를 갖는 유동 파라핀계의 미네랄오일 2.0 내지 4.5중량부, 고급 지방산의 금속염으로 징크-스테아레이트(Zinc-stearate) 0.01 내지 0.08중량부, 그리고 적정량의 산화방지제를 첨가하고 개시제로 3급 부틸 퍼옥시아세테이트(tertiary Butylperoxy Acetate)를 0.02-0.1 중량부 투입하여 괴상연속 중합에 의하여 중량평균 분자량이 14만 내지 19만인 스티렌계 열가소성 수지 조성물을 제조함을 특징으로 한다.That is, the present invention adds 91 to 94 parts by weight of the monovinyl aromatic compound and 6 to 9 parts by weight of polybutadiene-based rubber with respect to 100 parts by weight of the total resin composition, and the liquid paraffin having a viscosity of 54 to 76 centistokes at room temperature. 2.0 to 4.5 parts by weight of mineral oil of the system, 0.01 to 0.08 parts by weight of zinc-stearate as a metal salt of a higher fatty acid, and an appropriate amount of antioxidant and tertiary butylperoxy acetate as an initiator ) To 0.02-0.1 parts by weight to prepare a styrene-based thermoplastic resin composition having a weight average molecular weight of 140,000 to 190,000 by bulk 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 얻어진 것으로, 1,4-cis 함량이 95중량% 이하이며 전체 수지조성물 100중량부에 대해 스티렌 모노머 95중량부 용액에서 용액점도가 20내지 100센티포이즈 수준인 폴리부타디엔계 고무이다.Polybutadiene-based rubber in the present invention is 95% by weight or more of which is obtained by the continuous polymerization under a nickel catalyst, 1,4-cis content is 95% 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 rubber with a solution viscosity of 20 to 100 centipoise in solution.
상기 폴리부타디엔계 고무는 전체 수지조성물 100중량부에 대해 6내지 9중량부 사용되는데 만일 폴리부타디엔계 고무가 6중량부 미만으로 사용되면 내충격성과 신율이 떨어지게 되며 9중량부를 초과하여 과량 사용되면 내열성 및 유동성과 인장강도가 떨어지게 된다. 또한 스티렌계 열가소성 수지 조성물상에 분산된 고무상 물질의 평균입자 직경은 0.7내지 3.5마이크론 이어야 하는데 만일 평균 입자 직경이 0.7마이크론 미만인 경우에는 내충격성이 떨어지게 되며 3.5마이크론을 초과하는 경우에는 표면 광택성이 떨어지게 된다.The polybutadiene-based rubber is used 6 to 9 parts by weight based on 100 parts by weight of the total resin composition. If the polybutadiene-based rubber is used less than 6 parts by weight, the impact resistance and elongation will be lowered. Fluidity and tensile strength will be reduced. In addition, the average particle diameter of the rubbery material dispersed on the styrene-based thermoplastic resin composition should be 0.7 to 3.5 microns. If the average particle diameter is less than 0.7 microns, the impact resistance is inferior. Will fall.
또한 본 발명에 사용되는 모노비닐 방향족화합물로는 스티렌 α-메틸스티렌, α-에틸스티렌, p-메틸스티렌 등을 들 수 있다.Moreover, styrene (alpha) -methylstyrene, (alpha)-ethylstyrene, p-methylstyrene etc. are mentioned as a monovinyl aromatic compound used for this invention.
본 발명에서는 개시제로 3급 부틸 퍼옥시아세테이트를 전체 수지 조성물 100 중량부에 대하여 0.02 내지 0.1 중량부 투입하는데 만일 0.02 중량부 미만으로 투입하면 중합물의 그라프트율이 떨어져 내충격성이 저하되며 0.1 중량부를 초과하여 과량 투입 하게 되면 중합반응이 급격히 일어나 위험하게 된다.In the present invention, tertiary butyl peroxyacetate is added in an amount of 0.02 to 0.1 parts by weight based on 100 parts by weight of the total resin composition. If the content is less than 0.02 parts by weight, the graft ratio of the polymer is lowered, and the impact resistance is lowered. If an excessive amount is added, a polymerization reaction may occur rapidly and become dangerous.
한편 본 발명에서 조성물을 제조하기 위한 중합방법으로는 특히 괴상연속 중합방법을 사용하는 것이 좋은데 그것은 대량생산으로 제조원가가 저렴하고 균일한 물성특성을 갖는 제품을 생산하기 쉽기 때문이다.On the other hand, the polymerization method for preparing the composition in the present invention is particularly preferably to use a bulk continuous polymerization method because it is easy to produce a product having low production cost and uniform physical properties by mass production.
상기의 방법에 의해 제조되는 최종 중합물의 그라프트율은 120 내지 200퍼센트를 나타내야 하는데 만일 최종 중합물의 그라프트율이 120퍼센트 미만이 되면 내충격성과 신율이 떨어지게 되며 200퍼센트를 초과하게 되면 내충격성이 떨어지게 된다.The graft rate of the final polymer produced by the above method should be in the range of 120 to 200 percent. If the graft rate of the final polymer is less than 120 percent, the impact resistance and elongation will be lowered.
또한 최종 중합물의 중량평균 분자량은 개시제 투입량 및 중합온도, 반응기 중량 등을 조절하여 14만 내지 19만이 되도록 하여야 하는데, 만일 14만 미만으로 되면 내충격성과 강성이 떨어지게 되며 19만을 초과하게 되면 유통성이 저하되게 된다.In addition, the weight average molecular weight of the final polymer should be adjusted to 140,000 to 190,000 by adjusting the input amount of the initiator, polymerization temperature, reactor weight, etc., if it is less than 140,000, impact resistance and stiffness will be lowered. do.
본 발명에서는 고급 지방산의 금속염으로 징크-스테아레이트를 전체 수지 조성물 100중량부에 대하여 0.01 내지 0.08중량부 사용하는데 만일 0.01 중량부 미만으로 사용하면 성형물의 이형성이 떨어지게 되며 0.08중량부를 초과하여 사용하게 되면 성형물 표면에 가스 실버스트리크(Gas sillver streak)가 발생하기 쉬우므로 좋지 않다.In the present invention, the zinc salt is used as a metal salt of higher fatty acid in an amount of 0.01 to 0.08 parts by weight based on 100 parts by weight of the total resin composition. Gas silver streak is apt to occur on the molding surface, which is not good.
또한 본 발명에서는 상온에서 54 내지 76센티스토크의 점도를 갖는 유동 파라핀계의 미네랄오일을 전체 수지 조성물 100 중량부에 대하여 2.0 내지 4.5중량부 사용하는데, 만일 미네랄오일을 2.0 중량부 미만으로 사용하면 유동성이 떨어지게 되며, 4.5 중량부를 초과하여 사용하면 내열성이 떨어지게 되므로 좋지 않다.In addition, the present invention uses 2.0 to 4.5 parts by weight of a liquid paraffinic mineral oil having a viscosity of 54 to 76 centistokes at room temperature with respect to 100 parts by weight of the total resin composition. This will fall, and if used in excess of 4.5 parts by weight is not good heat resistance is poor.
이상과 같은 본 발명에 따른 수지는 내열성과 내충격성이 조화되고 유동성이 우수하여 저온, 저압, 저속에서의 사출이 가능하여 구조가 복잡하고 얇은 성형품 및 대형 TV 하우징의 제조용으로 사용할 수 있다.The resin according to the present invention as described above can be used for the production of a thin molded article and a large TV housing because the structure is complicated and the injection is possible at low temperature, low pressure and low speed due to excellent heat resistance and impact resistance and fluidity.
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 94중량부에 폴리부타디엔 고무 6중량부, 상온에서 54내지 76센티스토크의 점도를 갖는 유동 파라핀계의 미네랄오일 4.5중량부, 산화방지제인 트리에틸렌글리콜-비스-3-(3-t-부틸-4-하이드록시-5-메틸페닐)프로피오네이트[Triethyleneglycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate] 0.05중량부 및 고급 지방산의 금속염으로 징크-스테아레이트(Zine-STearate)를 0.01중량부 첨가하고 개시제인 3급 부틸 퍼옥시아세테이트 0.1중량부를 투입하여 괴상연속 중합방법에 의해 고무상의 평균입자 직경이 3.5마이크론, 최종 중합물의 그라프트율이 200퍼센트, 그리고 중량평균 분자량이 19만인 중합물을 제조하였다. 이를 사출성형기로 사출하고 압출하여 물성테스트 시편을 제작한 뒤 다음과 같은 조건으로 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.6 parts by weight of polybutadiene rubber, 94 parts by weight of styrene, 4.5 parts by weight of liquid paraffinic mineral oil having a viscosity of 54 to 76 centistokes at room temperature, and triethylene glycol-bis-3- (3-t-butyl) as an antioxidant 4-hydroxy-5-methylphenyl) propionate [triethyleneglycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] Zinc-stearate with 0.05 parts by weight and a metal salt of a higher fatty acid (Zine-STearate) was added 0.01 part by weight, and 0.1 part by weight of tertiary butyl peroxyacetate as an initiator was added, and the average particle diameter of rubber phase was 3.5 micron, the graft ratio of the final polymer was 200%, and the weight average was obtained by the bulk continuous polymerization method. A polymer having a molecular weight of 190,000 was prepared. This was injected into an injection molding machine and extruded to produce a test specimen for physical properties. The physical properties were measured under the following conditions, and the results are shown in Table 1 below.
1) 아이조드 충격강도 : ASTM D258, 시편두께 : 1/8 inch1) Izod Impact Strength: ASTM D258, Specimen Thickness: 1/8 inch
2) 비캐트 연화점 : ISO R306B, 승온속도 : 50°C/hr2) Vicat softening point: ISO R306B, Heating rate: 50 ° C / hr
3) 인장강도 : ASTM D638, TEST SPEED : 20mm/min3) Tensile Strength: ASTM D638, TEST SPEED: 20mm / min
4) 유동성 : ASTM D1238, 200°C/5kg4) Fluidity: ASTM D1238, 200 ° C / 5kg
[실시예 2]Example 2
스티렌 92.5중량부, 폴리부타디엔 고무 7.5중량부, 유동 파라핀계의 미네랄오일 3.5중량부, 징크-스테아레이트 0.02중량부, 개시제인 3급 부틸 퍼옥시아세테이트 0.07중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 고무상의 평균입자 직경이 2.0마이크론, 최종 중합물의 그라프트율이 170퍼센트, 그리고 중량평균 분자량이 16만인 중합물이 제조되었으며 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Example 1 except that 92.5 parts by weight of styrene, 7.5 parts by weight of polybutadiene rubber, 3.5 parts by weight of liquid paraffin mineral oil, 0.02 part by weight of zinc-stearate, and 0.07 part by weight of tertiary butyl peroxyacetate as an initiator The same procedure was followed. As a result, a polymer having an average particle diameter of 2.0 microns in rubber, a graft rate of 170% and a weight average molecular weight of 160,000 was prepared, and the physical properties thereof were shown in Table 1 below.
[실시예 3]Example 3
스티렌 91중량부, 폴리부타디엔 고무 9중량부, 유동 파라핀계의 미네랄오일 2.0중량부, 징크-스테아레이트0.08중량부, 개시제인 3급 부틸 퍼옥시아세테이트 0.02중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 고무상의 평균입자직경이 0.7마이크론, 최종 중합물의 그라프트율이 120퍼센트, 그리고 중량평균 분자량이 14만인 중합물이 제조되었으며 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Example 1 except that 91 parts by weight of styrene, 9 parts by weight of polybutadiene rubber, 2.0 parts by weight of liquid paraffinic mineral oil, 0.08 part by weight of zinc-stearate, and 0.02 part by weight of tertiary butyl peroxyacetate as an initiator The same procedure was followed. As a result, a polymer having an average particle diameter of 0.7 micron in rubber phase, a graft ratio of 120% in final polymer, and a molecular weight of 140,000 in weight average molecular weight was prepared, and the results are shown in Table 1 below.
[비교예 1]Comparative Example 1
스티렌 92.5중량부, 폴리부타디엔 고무 7.5 중량부, 유동 파라핀계의 미네랄오일 1.8중량부, 징크-스테아레이트 0.02중량부, 개시제인 3급 부틸 퍼옥시아세테이트 0.07중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 고무상의 평균입자 직경이 2.0 마이크론, 최종 중합물의 그라프트율이 180퍼센트, 그리고 중량평균 분자량이 20만인 중합물이 제조되었으며 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Example 1 except that 92.5 parts by weight of styrene, 7.5 parts by weight of polybutadiene rubber, 1.8 parts by weight of liquid paraffinic mineral oil, 0.02 part by weight of zinc-stearate, and 0.07 part by weight of tertiary butyl peroxyacetate as an initiator The same procedure was followed. As a result, a polymer having an average particle diameter of rubber of 2.0 microns, a graft ratio of the final polymer of 180%, and a weight average molecular weight of 200,000 was prepared. The results of the measurement are shown in Table 1 below.
[비교예 2]Comparative Example 2
스티렌 92.0중량부, 폴리부타디엔 고무 8.0 중량부, 유동 파라핀계의 미네랄오일 0.5중량부, 징크-스테아레이트 0.04중량부, 개시제인 3급 부틸 퍼옥시아세테이트 0.05중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 고무상의 평균입자 직경이 4.0마이크론, 최종 중합물의 그라프트율이 140퍼센트, 그리고 중량평균 분자량이 13만인 중합물이 제조되었으며 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Example 1, except that 92.0 parts by weight of styrene, 8.0 parts by weight of polybutadiene rubber, 0.5 parts by weight of liquid paraffinic mineral oil, 0.04 parts by weight of zinc-stearate, and 0.05 parts by weight of tertiary butyl peroxyacetate as an initiator The same procedure was followed. As a result, a polymer having an average particle diameter of 4.0 microns in rubber, a graft ratio of 140% in a final polymer, and a weight average molecular weight of 130,000 was prepared, and the results are shown in Table 1 below.
[비교예 3]Comparative Example 3
스티렌 93.5중량부, 폴리부타디엔 고무 6.5 중량부,유동 파라핀계의 미네랄오일 2.5중량부, 징크-스테아레이트 0.05중량부, 개시제인 3급 부틸 퍼옥시아세테이트 0.11중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 고무상의 평균입자 직경이 0.5마이크론, 최종 중합물의 그라프트율이 210퍼센트, 그리고 중량평균 분자량이 16만인 중합물이 제조되었으며 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Example 1 except that 93.5 parts by weight of styrene, 6.5 parts by weight of polybutadiene rubber, 2.5 parts by weight of flow oil of paraffinic mineral, 0.05 parts by weight of zinc-stearate, and 0.11 parts by weight of tertiary butyl peroxyacetate as an initiator The same procedure was followed. As a result, a polymer having an average particle diameter of 0.5 micron in rubber phase, a graft ratio of 210% in final polymer, and a molecular weight of 160,000 in weight average molecular weight was prepared. The results of the measurement are shown in Table 1 below.
[비교예 4][Comparative Example 4]
스티렌 90.0중량부, 폴리부타디엔 고무 10.0중량부,유동 파라핀계의 미네랄오일 1.5중량부, 징크-스테아레이트 0.06중량부, 개시제인 3급 부틸 퍼옥시아세테이트 0.02중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 고무상의 평균입자 직경이 2.5마이크론, 최종 중합물의 그라프트율이 100퍼센트, 그리고 중량평균 분자량이 19만인 중합물이 제조되었으며 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Example 1 except that 90.0 parts by weight of styrene, 10.0 parts by weight of polybutadiene rubber, 1.5 parts by weight of flowable paraffinic mineral oil, 0.06 parts by weight of zinc-stearate, and 0.02 parts by weight of tertiary butyl peroxyacetate as an initiator The same procedure was followed. As a result, a polymer having an average particle diameter of 2.5 microns in rubber, a graft ratio of 100% in the final polymer, and a weight average molecular weight of 190,000 was prepared. The results are shown in Table 1 below.
[비교예 5][Comparative Example 5]
스티렌 95.0중량부, 폴리부타디엔 고무5.0중량부, 유동 파라핀계의 미네랄오일 5.5중량부, 징크-스테아레이트 0.03중량부, 개시제인 3급 부틸 퍼옥시아세테이트 0.05중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 고무상의 평균입자 직경이 3.0마이크론, 최종 중합물의 그라프트율이 150퍼센트, 그리고 중량평균 분자량이 22만인 중합물이 제조되었으며 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Example 1 except that 95.0 parts by weight of styrene, 5.0 parts by weight of polybutadiene rubber, 5.5 parts by weight of liquid paraffinic mineral oil, 0.03 parts by weight of zinc-stearate, and 0.05 parts by weight of tertiary butyl peroxyacetate as an initiator The same procedure was followed. As a result, a polymer having an average particle diameter of 3.0 microns in rubber, a graft ratio of 150% in the final polymer, and a weight average molecular weight of 220,000 was prepared, and the results are shown in Table 1 below.
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