KR100232700B1 - Process for preparing styrenic thermoplastic resin - Google Patents
Process for preparing styrenic thermoplastic resin Download PDFInfo
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- KR100232700B1 KR100232700B1 KR1019960015730A KR19960015730A KR100232700B1 KR 100232700 B1 KR100232700 B1 KR 100232700B1 KR 1019960015730 A KR1019960015730 A KR 1019960015730A KR 19960015730 A KR19960015730 A KR 19960015730A KR 100232700 B1 KR100232700 B1 KR 100232700B1
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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
- C08F112/00—Homopolymers 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
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
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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
- 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
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- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 투명성이 우수하며 구조가 복잡하고 얇은 성형물의 사출성형에 적합한 이형성이 우수한 투명한 스티렌계 열가소성 수지의 제조방법을 제공하기 위한 것으로서, 중량평균 분자량이 18만 내지 32만인 스티렌계 열가소성 수지를 제조함에 있어서, 모노 비닐 방향족화합물에 징크-스테아레이트, 메틸페닐실리콘오일을 투입하여 열 또는 개시제에 의한 괴상연속 중합방법에 의하여 제조함을 특징으로 한다.The present invention is to provide a method for producing a transparent styrene-based thermoplastic resin having excellent transparency, complex structure and excellent mold release property suitable for injection molding of a thin molding, to prepare a styrene-based thermoplastic resin having a weight average molecular weight of 180,000 to 320,000 In the process, zinc-stearate and methylphenylsilicone oil are added to the monovinyl aromatic compound to prepare by mass or continuous bulk polymerization by an initiator.
Description
본 발명은 스티렌계 열가소성 수지의 제조방법에 관한 것으로서, 더욱 상세하게는 사출성형시 이형크렉(CRACK)이 발생되지 않는 우수한 이형성이 우수한 투명한 스티렌계 열가소성 수지의 제조방법에 관한 것이다.The present invention relates to a method for producing a styrene-based thermoplastic resin, and more particularly, to a method for manufacturing a transparent styrene-based thermoplastic resin having excellent release properties in which no release crack (CRACK) is generated during injection molding.
일반적으로 모노비닐 방향족화합물을 중합하여 얻어지는 비결정성 폴리스티렌 수지(GPPS)는 우수한 투명성과 강성 및 무독성 등을 지니고 있어서 넓은 범위의 용도로 사용되는 열가소성 수지의 하나이다. 그러나 카세트테이프 케이스 및 CD 케이스 등과 같이 투명성이 요구되면서 구조가 복잡하고 얇은 성형물로 사출성형시에는 이형성 부족으로 인해 이형크랙이 발생되는 문제점이 있다.Generally, amorphous polystyrene resin (GPPS) obtained by polymerizing a monovinyl aromatic compound is one of thermoplastic resins used for a wide range of applications because it has excellent transparency, rigidity and nontoxicity. However, when transparency is required, such as a cassette tape case and a CD case, there is a problem in that a release crack occurs due to a lack of release property when injection molding into a complex and thin molding.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로서, 투명성이 우수하여 구조가 복잡하고 엷은 성형물의 사출성형에 적합한 이형성이 우수한 투명한 스티렌계 열가소성 수지의 제조방법을 제공함을 그 목적으로 한다.An object of the present invention is to provide a method for producing a transparent styrene-based thermoplastic resin having excellent transparency and excellent releasability suitable for injection molding of a thin molding having excellent transparency.
즉, 본 발명은 모노비닐 방향족화합물 100중량부에 대하여 고급 지방산의 금속염으로 징크-스테아레이트 0.01 내지 1.0중량부와 메틸페닐실리콘오일 0.02 내지 0.2중량부를 첨가하여 열 또는 개시제에 의한 괴상연속중합에 의해 중량평균 분자량이 18만 내지 32만인 스티렌계 열가소성 수지를 제조함을 특징으로 한다.That is, the present invention adds 0.01 to 1.0 parts by weight of zinc-stearate and 0.02 to 0.2 parts by weight of methylphenylsilicone oil as a metal salt of a higher fatty acid based on 100 parts by weight of a monovinyl aromatic compound to be weighed by bulk or continuous polymerization by an initiator. It is characterized by producing a styrene-based thermoplastic resin having an average molecular weight of 180,000 to 320,000.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서 사용하는 모노비닐 방향족화합물로는 스티렌, α-메틸스티렌, α-에틸스티렌, ρ-메틸스티렌 등을 들 수 있다.Examples of the monovinyl aromatic compound used in the present invention include styrene, α-methylstyrene, α-ethylstyrene, and ρ-methylstyrene.
또한 고급 지방산의 금속염인 징크-스테아레이트는 모노비닐 방향족 화합물 100중량부에 대하여 0.01-1.0중량부 사용하는데, 만일 0.01중량부 미만으로 사용하면 이형성이 나빠지고, 1.0중량부를 초과하여 과량 사용하면 투명성이 떨어지게 된다.In addition, zinc-stearate, a metal salt of higher fatty acids, is used in an amount of 0.01-1.0 parts by weight based on 100 parts by weight of a monovinyl aromatic compound. Will fall.
또한 본 발명에 사용되는 메틸페닐실리콘오일은 -(Si-O-)-로 표시되는 구조단위를 가지며 25℃에서 5 내지 100센티스토크의 점도와 1.5 내지 1.55의 굴절율을 가지는 것으로서, 구조식은 다음 식(Ⅰ)과 같다.In addition, methylphenylsilicone oil used in the present invention has a structural unit represented by-(Si-O-)-and has a viscosity of 5 to 100 centistokes and a refractive index of 1.5 to 1.55 at 25 ° C. Same as I).
여기서, R은 메틸기, 페닐기를 나타내며, n은 상온에서 액상을 유지하는 폴리실록산 단위를 나타내는 정수이다.Here, R represents a methyl group and a phenyl group, n is an integer representing the polysiloxane unit which maintains a liquid phase at normal temperature.
상기의 메틸페닐실리콘오일을 0.02중량부 미만으로 사용하면 이형성이 나빠지고 0.2중량부를 초과하여 사용하면 투명성이 떨어지게 된다.If the methylphenylsilicone oil is used in less than 0.02 parts by weight, the releasability is worsened, and when used in excess of 0.2 parts by weight, transparency becomes poor.
한편 본 발명에서는 상온에서 30 내지 100센티스토크의 점도를 갖는 유동 파라핀계 미네랄오일을 모노비닐 방향족 화합물 100중량부에 대하여 4.5중량부 이하의 양으로 추가 투입할 수 있는데, 만일 4.5중량부를 초과하여 투입하게 되면 내열성이 떨어지게 되므로 좋지 않다.Meanwhile, in the present invention, a liquid paraffinic mineral oil having a viscosity of 30 to 100 centistokes at room temperature may be additionally added in an amount of 4.5 parts by weight or less with respect to 100 parts by weight of a monovinyl aromatic compound. This is not good because the heat resistance is reduced.
최종 중합물의 중량평균 분자량은 18만에서 32만의 범위를 갖는 것이 좋은데, 만일 18만 미만으로 되면 강성이 떨어지게 되며, 32만을 초과하게 되면 유동성이 저하하게 된다.The weight average molecular weight of the final polymer is preferably in the range of 180,000 to 320,000, if less than 180,000, the rigidity is lowered, if it exceeds 320,000, the fluidity is lowered.
본 발명에서 조성물을 제조하기 위한 중합방법으로는 특히 괴상연속 중합방법을 사용하는 것이 좋은데 그것은 대량생산으로 제조원가가 저렴하고 균일한 물성특성을 갖는 제품을 생산하기 쉽기 때문이다.As the polymerization method for preparing the composition in the present invention, it is particularly preferable to use a bulk continuous polymerization method because it is easy to produce a product having low manufacturing cost and uniform physical properties by mass production.
본 발명에 사용되는 개시제로는 3급 부틸퍼옥시아세테이트, 3급 부틸퍼옥시벤조에이트, 아조-비스-이소부틸로니트릴, 벤조일퍼옥사이드 등을 사용할 수 있다.As the initiator used in the present invention, tertiary butyl peroxy acetate, tertiary butyl peroxy benzoate, azo-bis-isobutylonitrile, benzoyl peroxide and the like can be used.
이상과 같은 본 발명에 따른 수지는 사출성형시 투명성과 이형성이 우수하여 카세트테이프 케이스 및 CD 케이스 등과 같이 투명하고 구조가 복잡하며, 얇은 성형품 제조용으로 사용할 수 있다.The resin according to the present invention as described above is excellent in transparency and releasability during injection molding, such as a cassette tape case and a CD case, transparent and complex structure, it can be used for the production of thin molded articles.
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 100중량부에 징크-스테아레이트 1.0중량부, 메틸페닐실리콘오일 0.02중량부, 미네랄오일 1.0중량부를 첨가하고 개시제인 3급 부틸 퍼옥시 벤조에이트를 0.06중량부 첨가하여 괴상연속 중합방법에 의해 중량 평균분자량이 32만이 중합물을 제조하였다.To 100 parts by weight of styrene, 1.0 part by weight of zinc-stearate, 0.02 part by weight of methylphenylsilicone oil, 1.0 part by weight of mineral oil were added and 0.06 part by weight of tertiary butyl peroxy benzoate, which was an initiator, was weight-averaged by the bulk continuous polymerization method. A polymer having a molecular weight of 320,000 was prepared.
이를 사출성형시로 사출하여 물성테스트 시편을 제작한 뒤, 다음과 같은 조건으로 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.After the injection molding during injection molding to test the physical properties of the test specimens, the physical properties were measured under the following conditions, and the results are shown in Table 1 below.
1) 투명성 : ASTM D1003, 흐림도(HAZE)1) Transparency: ASTM D1003, HAZE
2) 이형성 평가 : 격자 금형을 이용하여 100회 사출성형하여 성형물(가로×세로×두께 : 10cm×10cm×0.5cm)에 이형크랙(CRACK)이 발생되는 횟수를 측정함.2) Evaluation of mold release property: The number of times that mold cracks are generated in moldings (width × length × thickness: 10cm × 10cm × 0.5cm) by 100 injection molding using a lattice mold is measured.
[실시예 2]Example 2
징크-스테아레이트를 0.01중량부, 메틸페닐실리콘오일을 0.2중량부 사용하고, 미네랄오일을 사용하지 않은 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 18만이 중합물이 제조되었으며 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.The same procedure as in Example 1 was carried out except that 0.01 parts by weight of zinc-stearate and 0.2 parts by weight of methylphenylsilicone oil were used, and no mineral oil was used. As a result, 180,000 polymers having a weight average molecular weight were prepared, and the results are shown in Table 1 below.
[실시예 3]Example 3
징크-스테아레이트를 0.05중량부, 메틸페닐실리콘오일을 0.1중량부, 미네랄오일을 4.5중량부 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과중량부 평균 분자량이 25만이 중합물이 제조되었으며 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Except for using 0.05 parts by weight of zinc-stearate, 0.1 parts by weight of methyl phenyl silicone oil, 4.5 parts by weight of mineral oil was carried out in the same manner as in Example 1. Experimental Results Weight average molecular weight of 250,000 polymer was prepared and the results are shown in Table 1 below.
[비교예 1]Comparative Example 1
메틸페닐실리콘오일을 0.01중량부, 미네랄오일을 0.5중량부 사용하고 징크 스테아레이트를 사용하지 않은 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 using 0.01 weight part of methylphenyl silicone oils, and 0.5 weight part of mineral oils, and not using zinc stearate. 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.
[비교예 2]Comparative Example 2
징크-스테아레이트를 1.5중량부, 미네랄오일을 2.0중량부 사용하고 메틸페닐실리콘오일을 사용하지 않은 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 23만이 중량물이 제조되었으며 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.Except that 1.5 parts by weight of zinc-stearate, 2.0 parts by weight of mineral oil and no methylphenylsilicone oil were used in the same manner as in Example 1. As a result, the weight average molecular weight of 230,000 was prepared and the physical properties were measured and the results are shown in Table 1 below.
[비교예 3]Comparative Example 3
징크-스테아레이트를 0.02중량부, 메틸페닐실리콘오일을 0.3중량부, 미네랄오일을 5.0중량부 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 27만이 중합물이 제조되었으며 물성을 측정하여 그 결과를 다음 표 1에 나타내었다. 실험결과 이형크렉을 발생되지 않았지만 흐림도(HAZE)가 높아 투명성이 떨어져서 좋지 않았다.It carried out similarly to Example 1 except using 0.02 weight part of zinc-stearate, 0.3 weight part of methylphenyl silicone oil, and 5.0 weight part of mineral oil. As a result, a polymer having a weight average molecular weight of 270,000 was prepared, and the physical properties thereof were shown in Table 1 below. As a result of the experiment, no release crack was generated, but the transparency was high due to the high haze.
[비교예 4][Comparative Example 4]
미네랄오일을 2.0중량부 사용하고 징크-스테아레이트와 메틸페닐실리콘오일을 사용하지 않은 것을 제외하고는 실시예 1과 동일하게 실시하였다. 실험결과 중량평균분자량이 25만이 중합물이 제조되었으며 물성을 측정하여 그 결과를 다음 표 1에 나타내었다.The same procedure as in Example 1 was carried out except that 2.0 parts by weight of mineral oil and no zinc stearate and methylphenyl silicone oil were used. As a result of the experiment, a weight average molecular weight of 250,000 was prepared, and the physical properties thereof were shown in Table 1 below.
[표 1]TABLE 1
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| KR100415151B1 (en) * | 2001-10-15 | 2004-01-16 | 주식회사 엘지화학 | Transparent high impact polystyrenic resins composition with good mold release and their prodution method |
| KR20030033236A (en) * | 2001-10-19 | 2003-05-01 | 제일모직주식회사 | Thermoplastic Resin Compositions with Good Transparency and Impact Strength |
| KR100442920B1 (en) * | 2001-10-31 | 2004-08-02 | 주식회사 엘지화학 | Rubber-modified styrene-based transparence resin composition having an excellent enviromental stress crack resistance and method for preparing the same |
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| KR970074805A (en) | 1997-12-10 |
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