WO2016175423A1 - 내열 san 수지, 이의 제조방법 및 이를 포함하는 내열 san 수지 조성물 - Google Patents
내열 san 수지, 이의 제조방법 및 이를 포함하는 내열 san 수지 조성물 Download PDFInfo
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- WO2016175423A1 WO2016175423A1 PCT/KR2015/013674 KR2015013674W WO2016175423A1 WO 2016175423 A1 WO2016175423 A1 WO 2016175423A1 KR 2015013674 W KR2015013674 W KR 2015013674W WO 2016175423 A1 WO2016175423 A1 WO 2016175423A1
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- resistant san
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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
- C08F212/00—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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
- C08F212/10—Styrene with nitriles
-
- 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
- C08F212/00—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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
-
- 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
-
- 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
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- 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
- C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/01—High molecular weight, e.g. >800,000 Da.
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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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Definitions
- the present invention relates to a heat-resistant SAN resin, a method for manufacturing the same, and a heat-resistant SAN resin composition comprising the same, and more particularly, a heat-resistant SAN resin and a method for producing the same, which improves the polymerization conversion rate and increases the weight average molecular weight while maintaining the heat resistance; It is related with the heat resistant SAN resin composition which is excellent in chemical resistance and excellent mechanical property and a balance of physical properties including these.
- SAN resin a copolymer resin made by polymerizing styrene and acrylonitrile, is well known as a resin having excellent transparency, chemical resistance, and rigidity.
- ABS resins acrylonitrile-butadiene-styrene (ABS) resins and are widely used in automobile interior materials, home appliance housings, and the like. In particular, since automotive interior materials are always exposed to high heat and chemical environments, high heat resistance and chemical resistance are required.
- alpha-methylstyrene monomers are generally used.
- the polymerization temperature is increased due to the low depolymerization temperature of alpha-methylstyrene, the oligomers are generated and heat resistance is lowered.
- the polymerization temperature is lowered.
- excessively lowering the polymerization temperature causes a problem that the polymerization rate and the polymerization conversion rate decrease.
- Patent Documents 1.US5254650 A
- Patent Documents 2.US4874829 A
- An object of this invention is to provide the heat resistant SAN resin which improved the polymerization conversion rate and increased the weight average molecular weight, maintaining heat resistance.
- an object of this invention is to provide the manufacturing method of the said heat resistant SAN resin.
- an object of the present invention is to provide a heat-resistant SAN resin composition, including the heat-resistant SAN resin is excellent in chemical resistance, excellent mechanical properties and balance of physical properties.
- the present invention provides a polymerized heat-resistant SAN resin including 52 to 78% by weight of alpha-methylstyrene, 20 to 40% by weight of vinyl cyan compound and 2 to 8% by weight of hydroxyalkyl (meth) acrylate. To provide.
- the present invention also provides a heat-resistant SAN resin comprising 52 to 78% by weight of alpha-methylstyrene, 20 to 40% by weight of vinyl cyan compound and 2 to 8% by weight of hydroxyalkyl (meth) acrylate. Provide a method.
- the present invention also provides a polymerized heat-resistant SAN resin including 52 to 78% by weight of alpha-methylstyrene, 20 to 40% by weight of vinyl cyan compound and 2 to 8% by weight of hydroxyalkyl (meth) acrylate; It provides a heat-resistant SAN resin composition comprising; and ABS resin.
- hydroxyalkyl (meth) acrylate which is a new hydrophilic monomer
- a polymerized SAN resin including a copolymer of alpha-methylstyrene and vinylcyan compound the properties of the conventional heat-resistant styrene resin are maintained. While it was confirmed that the polymerization conversion rate is improved, and the weight average molecular weight is increased, the SAN resin composition including the same has excellent chemical resistance, and it is confirmed that the mechanical and the physical property balance are excellent, thereby completing the present invention.
- the heat-resistant SAN resin is characterized in that the polymerized including 52 to 78% by weight of alpha-methylstyrene, 20 to 40% by weight of vinyl cyan compound and 2 to 8% by weight of hydroxyalkyl (meth) acrylate.
- the content of the alpha-methylstyrene may be, for example, 58 to 72% by weight, or 63 to 69% by weight, and has excellent heat resistance within this range and does not lower the polymerization conversion rate.
- the vinyl cyan compound may be at least one selected from the group consisting of, for example, acrylonitrile, methacrylonitrile, and ethacrylonitrile.
- the content of the vinyl cyan compound may be, for example, 25 to 35% by weight, or 27 to 33% by weight, and within this range, there is an excellent effect of polymerization conversion, heat resistance, chemical resistance, and impact resistance.
- the hydroxyalkyl (meth) acrylate is, for example, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxypentyl acrylate, 6-hydroxynonyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, It may be at least one selected from the group consisting of 2-hydroxypentyl methacrylate, 5-hydroxypentyl methacrylate, 7-hydroxyheptyl methacrylate and 5-hydroxydecyl methacrylate.
- the hydroxyalkyl (meth) acrylate may be hydroxyethyl acrylate or hydroxyethyl methacrylate.
- the content of the hydroxyalkyl (meth) acrylate may be 3 to 7% by weight, for example, it is possible to polymerize a copolymer having a high weight average molecular weight within this range, the effect of excellent polymerization conversion and chemical resistance have.
- the heat-resistant SAN resin may be an oligomer content of 0.1 to 0.8% by weight, 0.3 to 0.6% by weight, or 0.4 to 0.5% by weight, for example, there is an excellent heat resistance in this range.
- the heat resistant SAN resin may be, for example, a weight average molecular weight of 79,000 g / mol or more, 79,000 to 95,500 g / mol, or 80,000 to 93,000 g / mol, and has excellent impact resistance and heat resistance within this range.
- the heat resistant SAN resin may have a glass transition temperature (Tg) of 124.3 ° C. or higher, 125 to 135 ° C., or 125.1 to 130 ° C., for example, and a balance of heat resistance and impact resistance of the heat resistant SAN resin composition within this range. This has an excellent effect.
- Tg glass transition temperature
- the heat-resistant SAN resin manufacturing method according to the present invention is as follows.
- the method for producing a heat-resistant SAN resin includes the step of bulk polymerization including 52 to 78% by weight of alpha-methylstyrene, 20 to 40% by weight of vinyl cyan compound and 2 to 8% by weight of hydroxyalkyl (meth) acrylate. It features.
- the bulk polymerization can be, for example, continuous polymerization.
- the continuous polymerization means that the entire polymerization process is continuously performed including injection of each monomer and extraction of the polymerized heat-resistant SAN resin.
- the bulk polymerization may have a polymerization conversion of 63 to 76%, 64 to 73%, or 65 to 72%. Within this range, a rapid increase in viscosity in the reactor is suppressed, thereby facilitating the process and providing excellent productivity. have.
- the bulk polymerization may be performed at 105 to 120 ° C., 108 to 117 ° C., or 110 to 115 ° C., and has excellent effects of polymerization conversion and heat resistance within this range.
- the heat-resistant SAN resin manufacturing method is for example 100 parts by weight of the monomer mixture consisting of 52 to 78% by weight of the alpha-methylstyrene, 20 to 40% by weight of vinyl cyan compound and 2 to 8% by weight of hydroxyalkyl (meth) acrylate. It may include the step of adding 0.1 to 50 parts by weight, 0.1 to 30 parts by weight, or 0.1 to 10 parts by weight of the hydrocarbon solvent before the polymerization, there is an effect of suppressing excessive viscosity increase and conversion rate reduction during polymerization within this range. .
- the hydrocarbon solvent is not particularly limited as long as it is a solvent that can be used when the SAN resin is prepared by bulk polymerization.
- the hydrocarbon solvent may be at least one selected from the group consisting of toluene, ethylbenzene, xylene, methylethylketone, and xylene.
- the method for producing a heat-resistant SAN resin may include a step of polymerizing 100 parts by weight of the monomer mixture, for example, 0.01 to 1 parts by weight, 0.05 to 0.5 parts by weight, or 0.1 to 0.3 parts by weight to polymerize, within this range The weight average molecular weight in the effect is raised.
- the initiator is, for example, 1,1-bis (t-butyl peroxy) cyclohexane, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butyl peroxyisobutyrate, 2,2-bis (4,4-di-t-butylperoxy cyclohexane) propane, t-hexylperoxyisopropyl monocarbonate, t-butyl peroxylaurate, t-butylperoxy isopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, t-butyl peroxyacetate, 2,2-bis (t-butyl peroxy) butane, t-butyl peroxybenzoate, dicumyl peroxide, 2 At least one member selected from the group consisting of, 5-dimethyl-2,5-bis (t-butyl
- the method for producing a heat-resistant SAN resin may include, for example, volatilizing and removing unreacted monomers and hydrocarbon solvents at 25 torr or less, or 10 to 25 torr after the polymerization, and a low oligomer content and heat resistance within this range. It is highly effective.
- the step of removing the unreacted monomer and the solvent by volatilization may be performed at 200 to 250 ° C., or at 220 to 250 ° C., for example, and the residual monomer and oligomer content may be reduced within this range.
- the heat resistant SAN resin composition by this invention is as follows.
- the heat-resistant SAN resin composition may be polymerized heat-resistant SAN resin including 52 to 78% by weight of alpha-methylstyrene, 20 to 40% by weight of vinyl cyan compound and 2 to 8% by weight of hydroxyalkyl (meth) acrylate; And ABS resin; characterized in that it comprises a.
- the heat-resistant SAN resin may be 60 to 90% by weight, 65 to 85% by weight, or 70 to 80% by weight, for example, there is an effect excellent in heat resistance and chemical resistance within this range.
- the ABS resin may be, for example, 10 to 40% by weight, 15 to 35% by weight, or 20 to 30% by weight, and has excellent impact resistance within this range.
- the ABS resin may be, for example, a vinyl cyan compound-conjugated diene-vinylaromatic compound copolymer.
- the vinylcyan compound-conjugated diene-vinylaromatic compound copolymer may include, for example, 5 to 40% by weight of vinylcyan compound, 30 to 70% by weight of conjugated diene, and 20 to 65% by weight of vinylaromatic compound.
- the vinyl cyan compound may be at least one selected from the group consisting of, for example, acrylonitrile, methacrylonitrile, and ethacrylonitrile.
- the conjugated diene is at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene Can be.
- the vinylaromatic compound may be at least one selected from the group consisting of styrene, alpha-methylstyrene, ortho-ethylstyrene, para-ethylstyrene, and vinyltoluene.
- the heat resistant SAN resin composition may be, for example, a tensile elongation of 23% or more, 23 to 50%, or 25 to 35%.
- the heat resistant SAN resin composition may have an impact strength of 19 J / m or more, 19 to 40 J / m, or 22 to 30 J / m.
- the heat resistant SAN resin composition may be, for example, a melt index (220 ° C., 10 kg) of 5 to 10 g / 10 min, 6 to 10 g / 10 min, or 6 to 9 g / 10 min.
- the heat resistant SAN resin composition has an ESCR (Environmental Stress Cracking Resistance) of 28 seconds or more, which measures the time when cracks are buried by thinner in the specimen using 1% strain Zig. 28 seconds to 100 seconds, or 30 seconds to 90 seconds.
- ESCR Environmental Stress Cracking Resistance
- the heat resistant SAN resin composition may further include an antioxidant, for example.
- the antioxidant may be, for example, a hindered phenol-based antioxidant, a phosphorus-based antioxidant, or a mixture thereof. In this case, there is an effect excellent in heat resistance and chemical resistance.
- the molded article according to the present invention is characterized in that it is produced from the heat resistant SAN resin composition.
- the molded article may be, for example, an automotive interior or a home appliance housing.
- Alpha-methylstyrene (AMS), acrylonitrile (AN) and hydroxyethyl methacrylate (HEMA) are mixed with 100 parts by weight of toluene 3 parts by weight of a monomer mixture consisting of the contents (% by weight) described in Table 1 below. To prepare a mixed solution.
- 0.2 weight part of 1,1-bis (t-butyl peroxy) cyclohexane was added to the mixed solution as an initiator to prepare a polymerization solution, and the polymerization solution was continuously added to a series of reactors at 112 ° C. for 6 hours of polymerization. Thereafter, the unreacted monomer and the solvent were removed from a volatilizer having a temperature of 230 ° C. and a vacuum degree of 15 to 30 Torr, and then a heat-resistant SAN resin in pellet form was measured through a die and a pelletizer to measure physical properties.
- the properties of the heat-resistant SAN resins prepared in Examples 1 to 5 and Comparative Examples 1 to 4 are shown in Table 2 as measured by the following method, and similarly prepared in Examples 1 to 5 and Comparative Examples 1 to 4 above.
- the properties of the heat resistant SAN resin composition were measured by the following method and shown in Table 3.
- Glass transition temperature (Tg, °C) was measured using Pyris 6 DSC of Perkin Elmer.
- Polymerization conversion total solids content (TSC) ⁇ (parts of monomers and subsidiary materials added) / 100-(parts of subsidiary materials added to the monomer)
- Weight average molecular weight (Mw, g / mol) Relative values for standard polystyrene (PS) samples were determined by gel chromatography (GPC).
- MI Melt index
- Heat deflection temperature (HDT, °C): was measured according to the standard measurement ASTM D648 using the specimen.
- Comparative Example 2 in which alpha-methylstyrene and hydroxyethyl methacrylate were added out of the content range of the present invention, had no improvement effect. It was confirmed that the glass transition temperature has a large impact.
- Comparative Example 2 in which alpha-methylstyrene and hydroxyethyl methacrylate were added out of the content range of the present invention, had no improvement effect, and Comparative Examples 3 and 4 had poor physical property balance, and had a heat distortion temperature indicating heat resistance. It was confirmed that the degradation.
- the heat-resistant SAN resin of the present invention contains a hydrophilic new monomer, hydroxyalkyl (meth) acrylate together with alpha-methyl styrene and vinyl cyan compound, polymerization of the heat-resistant SAN resin while maintaining the properties of the conventional heat-resistant styrene resin
- the conversion rate is improved, and the weight average molecular weight is increased, and the SAN resin composition including the same may have excellent chemical resistance and excellent mechanical and balance properties.
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Abstract
Description
본 출원은 2015년 4월 27일자 한국 특허 출원 제10-2015-0058723호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.
구분 | 실시예 | 비교예 | |||||||
1 | 2 | 3 | 4 | 5 | 1 | 2 | 3 | 4 | |
AMS | 68 | 66 | 64 | 63 | 64 | 71 | 70 | 62 | 60 |
AN | 29 | 29 | 29 | 29 | 28 | 29 | 29 | 29 | 29 |
HEMA | 3 | 5 | 7 | 8 | 8 | 0 | 1 | 9 | 11 |
구분 | 단위 | 실시예 | 비교예 | |||||||
1 | 2 | 3 | 4 | 5 | 1 | 2 | 3 | 4 | ||
유리전이온도 | (℃) | 125.2 | 125.3 | 125.2 | 125.1 | 125.3 | 125.2 | 125.2 | 124.2 | 123.1 |
중합 전환율 | (%) | 65.6 | 67.0 | 70.2 | 72.0 | 71.4 | 62.1 | 62.8 | 73.1 | 76.2 |
중량평균 분자량 | (g/mol) | 83,000 | 89,000 | 92,000 | 93,500 | 93,000 | 78,000 | 78,400 | 93,300 | 96,000 |
올리고머 함량 | (중량%) | 0.5 | 0.5 | 0.4 | 0.4 | 0.4 | 0.6 | 0.6 | 0.4 | 0.4 |
구분 | 단위 | 실시예 | 비교예 | |||||||
1 | 2 | 3 | 4 | 5 | 1 | 2 | 3 | 4 | ||
인장강도 | (MPa) | 580 | 563 | 570 | 556 | 564 | 579 | 570 | 562 | 560 |
인장신율 | (%) | 26 | 29 | 33 | 32 | 31 | 21 | 22 | 36 | 31 |
충격강도 | (J/m) | 24 | 26 | 28 | 28 | 27 | 18 | 18 | 31 | 28 |
용융지수 | (g/10 min) | 9 | 8 | 7 | 6 | 6 | 10 | 10 | 6 | 5 |
열변형온도 | (℃) | 102 | 102 | 102 | 102 | 102 | 102 | 102 | 101 | 99 |
내화학성 | (초) | 34 | 52 | 71 | 76 | 74 | 21 | 27 | 102 | 123 |
Claims (15)
- 알파-메틸스티렌 52 내지 78 중량%, 비닐시안 화합물 20 내지 40 중량% 및 히드록시알킬 (메트)아크릴레이트 2 내지 8 중량%를 포함하여 중합된 것을 특징으로 하는 내열 SAN 수지.
- 제1항에 있어서,상기 비닐시안 화합물은 아크릴로니트릴, 메타크릴로니트릴 및 에타크릴로니트릴로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 내열 SAN 수지.
- 제1항에 있어서,상기 히드록시알킬 (메트)아크릴레이트는 히드록시에틸 아크릴레이트, 2-히드록시프로필 아크릴레이트, 3-히드록시프로필 아크릴레이트, 2-히드록시부틸 아크릴레이트, 4-히드록시부틸 아크릴레이트, 3-히드록시펜틸 아크릴레이트, 6-히드록시노닐 아크릴레이트, 히드록시에틸 메타크릴레이트, 2-히드록시프로필 메타크릴레이트, 3-히드록시프로필 메타크릴레이트, 2-히드록시부틸 메타크릴레이트, 2-히드록시펜틸 메타크릴레이트, 5-히드록시펜틸 메타크릴레이트, 7-히드록시헵틸 메타크릴레이트 및 5-히드록시데실 메타크릴레이트로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 내열 SAN 수지.
- 제1항에 있어서,상기 내열 SAN 수지는 올리고머 함량이 0.1 내지 0.8 중량%인 것을 특징으로 하는 내열 SAN 수지.
- 제1항에 있어서,상기 내열 SAN 수지는 중량평균 분자량이 79,000 g/mol 이상인 것을 특징으로 하는 내열 SAN 수지.
- 알파-메틸스티렌 52 내지 78 중량%, 비닐시안 화합물 20 내지 40 중량% 및 히드록시알킬 (메트)아크릴레이트 2 내지 8 중량%를 포함하여 벌크 중합시키는 단계를 포함하는 것을 특징으로 하는 내열 SAN 수지 제조방법.
- 제6항에 있어서,상기 벌크 중합은 연속 중합인 것을 특징으로 하는 내열 SAN 수지 제조방법.
- 제6항에 있어서,상기 벌크 중합은 중합 전환율이 63 내지 76 %인 것을 특징으로 하는 내열 SAN 수지 제조방법.
- 제6항에 있어서,상기 벌크 중합은 105 내지 120 ℃에서 실시되는 것을 특징으로 하는 내열 SAN 수지 제조방법.
- 알파-메틸스티렌 52 내지 78 중량%, 비닐시안 화합물 20 내지 40 중량% 및 히드록시알킬 (메트)아크릴레이트 2 내지 8 중량%를 포함하여 중합된 내열 SAN 수지; 및 ABS 수지;를 포함하는 것을 특징으로 하는 내열 SAN 수지 조성물.
- 제10항에 있어서,상기 내열 SAN 수지는 60 내지 90 중량%로 포함되고, ABS 수지는 10 내지 40 중량%로 포함되는 것을 특징으로 하는 내열 SAN 수지 조성물.
- 제10항에 있어서,상기 내열 SAN 수지 조성물은 인장신율이 23 % 이상인 것을 특징으로 하는 내열 SAN 수지 조성물.
- 제10항에 있어서,상기 내열 SAN 수지 조성물은 충격강도가 19 J/m 이상인 것을 특징으로 하는 내열 SAN 수지 조성물.
- 제10항에 있어서,상기 내열 SAN 수지 조성물은 1 % 스트레인(strain)의 지그(Zig)를 이용하여 시편 가운데 시너(thinner)를 묻혀 크랙이 발생되는 시간을 측정하는 ESCR(Environmental Stress Cracking Resistance)이 28초 이상인 것을 특징으로 하는 내열 SAN 수지 조성물.
- 제10항 내지 제14항 중 어느 한 항에 따른 내열 SAN 수지 조성물로 제조되는 것을 특징으로 하는 성형품.
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JP2016541515A JP6211706B2 (ja) | 2015-04-27 | 2015-12-14 | 耐熱san樹脂、その製造方法及びそれを含む耐熱san樹脂組成物 |
US15/106,785 US9777088B2 (en) | 2015-04-27 | 2015-12-14 | Heat-resistant SAN resin, method of producing the same and heat-resistant SAN resin composition comprising the same |
EP15866392.2A EP3127927B1 (en) | 2015-04-27 | 2015-12-14 | Heat resistant san resin, preparation method therefor, and heat resistant san resin composition containing same |
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KR1020150058723A KR101772268B1 (ko) | 2015-04-27 | 2015-04-27 | 내열 san 수지, 이의 제조방법 및 이를 포함하는 내열 san 수지 조성물 |
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EP (1) | EP3127927B1 (ko) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180201707A1 (en) * | 2015-12-07 | 2018-07-19 | Lg Chem, Ltd. | Method of preparing styrene-based resin and styrene-based resin prepared thereby |
US11180590B2 (en) * | 2017-07-28 | 2021-11-23 | Lg Chem, Ltd. | Copolymer and preparation method therefor |
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WO2019022544A1 (ko) * | 2017-07-28 | 2019-01-31 | 주식회사 엘지화학 | 공중합체 및 이의 제조방법 |
KR102367060B1 (ko) | 2019-01-17 | 2022-02-24 | 주식회사 엘지화학 | 도장성이 우수한 열가소성 수지 조성물, 이의 제조방법 및 이를 포함하는 성형품 |
CN114989369B (zh) * | 2022-05-06 | 2023-10-20 | 万华化学集团股份有限公司 | 一种耐热san共聚物及其制备方法与应用 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4721752A (en) * | 1983-10-01 | 1988-01-26 | Stami Carbon Bv | Process for preparing an impact-resistant thermoplastic moulding compound |
US4755576A (en) | 1984-08-24 | 1988-07-05 | Bayer Aktiengesellschaft | Copolymers of alpha-methyl styrene and acrylonitrile |
US4795780A (en) | 1986-08-02 | 1989-01-03 | Bayer Aktiengesellschaft | Process for the preparation of binary α-methylstyrene/acrylonitrile resins by multi-stage bulk polymerization |
US4874829A (en) | 1987-05-22 | 1989-10-17 | Monsanto Company | Process for preparing α-methylstyrene-acrylonitrile polymers |
US5236990A (en) * | 1992-02-28 | 1993-08-17 | General Electric Company | Low gloss polycarbonate/abs blends obtained by using a hydroxy functional rigid polymer |
US5254650A (en) | 1988-07-22 | 1993-10-19 | Kayaku Akzo Corporation | Process for the preparation of styrene or styrene derivative-containing copolymers |
US5302646A (en) * | 1992-02-28 | 1994-04-12 | General Electric Company | Low gloss flame-retarded polycarbonate/ABS blends obtained by using hydroxyalkyl (meth) acrylate functionalized ABS |
US6316527B1 (en) * | 1999-09-16 | 2001-11-13 | Rohm And Haas Company | Modified SAN resin blend compositions and articles produced therefrom |
KR100374673B1 (ko) * | 1996-05-30 | 2003-10-22 | 덴끼 가가꾸 고교 가부시키가이샤 | 열가소성 수지 성형품 및 그의 제조 방법 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3857818A (en) * | 1972-09-18 | 1974-12-31 | Cook Paint & Varnish Co | Blocked polyurethane powder coating compositions |
DE3444788A1 (de) * | 1984-12-08 | 1986-06-12 | Basf Ag, 6700 Ludwigshafen | Copolymere aus einer hauptkette und nebenketten |
JP2533790B2 (ja) * | 1988-04-20 | 1996-09-11 | ダイセル化学工業株式会社 | イミド基含有樹脂組成物 |
JPH06293849A (ja) * | 1993-04-09 | 1994-10-21 | Mitsubishi Petrochem Co Ltd | 熱可塑性樹脂組成物 |
JPH06329852A (ja) * | 1993-05-21 | 1994-11-29 | Mitsubishi Petrochem Co Ltd | 熱可塑性樹脂組成物 |
JPH071629A (ja) * | 1993-06-18 | 1995-01-06 | Sumitomo Dow Ltd | 発泡ウレタンとの積層体用ゴム強化スチレン系樹脂組成物及びそれと発泡ウレタンからなる積層体 |
KR0154910B1 (ko) | 1994-10-28 | 1998-12-01 | 성재갑 | 내열성 공중합체의 제조방법 |
JPH1025422A (ja) * | 1996-07-08 | 1998-01-27 | Japan Synthetic Rubber Co Ltd | 樹脂組成物 |
JP3256453B2 (ja) * | 1996-12-10 | 2002-02-12 | テクノポリマー株式会社 | 熱安定性の良好な共重合体からなる改質剤 |
JP2005002316A (ja) * | 2003-05-19 | 2005-01-06 | Techno Polymer Co Ltd | 熱可塑性樹脂組成物、成形品及び積層体 |
JP4834991B2 (ja) * | 2004-01-07 | 2011-12-14 | 東レ株式会社 | 熱可塑性樹脂組成物 |
-
2015
- 2015-04-27 KR KR1020150058723A patent/KR101772268B1/ko active IP Right Grant
- 2015-12-14 EP EP15866392.2A patent/EP3127927B1/en active Active
- 2015-12-14 JP JP2016541515A patent/JP6211706B2/ja active Active
- 2015-12-14 WO PCT/KR2015/013674 patent/WO2016175423A1/ko active Application Filing
- 2015-12-14 US US15/106,785 patent/US9777088B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4721752A (en) * | 1983-10-01 | 1988-01-26 | Stami Carbon Bv | Process for preparing an impact-resistant thermoplastic moulding compound |
US4755576A (en) | 1984-08-24 | 1988-07-05 | Bayer Aktiengesellschaft | Copolymers of alpha-methyl styrene and acrylonitrile |
US4795780A (en) | 1986-08-02 | 1989-01-03 | Bayer Aktiengesellschaft | Process for the preparation of binary α-methylstyrene/acrylonitrile resins by multi-stage bulk polymerization |
US4874829A (en) | 1987-05-22 | 1989-10-17 | Monsanto Company | Process for preparing α-methylstyrene-acrylonitrile polymers |
US5254650A (en) | 1988-07-22 | 1993-10-19 | Kayaku Akzo Corporation | Process for the preparation of styrene or styrene derivative-containing copolymers |
US5236990A (en) * | 1992-02-28 | 1993-08-17 | General Electric Company | Low gloss polycarbonate/abs blends obtained by using a hydroxy functional rigid polymer |
US5302646A (en) * | 1992-02-28 | 1994-04-12 | General Electric Company | Low gloss flame-retarded polycarbonate/ABS blends obtained by using hydroxyalkyl (meth) acrylate functionalized ABS |
KR100374673B1 (ko) * | 1996-05-30 | 2003-10-22 | 덴끼 가가꾸 고교 가부시키가이샤 | 열가소성 수지 성형품 및 그의 제조 방법 |
US6316527B1 (en) * | 1999-09-16 | 2001-11-13 | Rohm And Haas Company | Modified SAN resin blend compositions and articles produced therefrom |
Non-Patent Citations (1)
Title |
---|
See also references of EP3127927A4 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20180201707A1 (en) * | 2015-12-07 | 2018-07-19 | Lg Chem, Ltd. | Method of preparing styrene-based resin and styrene-based resin prepared thereby |
US10570229B2 (en) * | 2015-12-07 | 2020-02-25 | Lg Chem, Ltd. | Method of preparing styrene-based resin and styrene-based resin prepared thereby |
US11180590B2 (en) * | 2017-07-28 | 2021-11-23 | Lg Chem, Ltd. | Copolymer and preparation method therefor |
Also Published As
Publication number | Publication date |
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JP6211706B2 (ja) | 2017-10-11 |
US9777088B2 (en) | 2017-10-03 |
KR101772268B1 (ko) | 2017-08-28 |
EP3127927A1 (en) | 2017-02-08 |
JP2017516871A (ja) | 2017-06-22 |
EP3127927A4 (en) | 2017-10-18 |
US20170121436A1 (en) | 2017-05-04 |
KR20160127387A (ko) | 2016-11-04 |
EP3127927B1 (en) | 2020-06-24 |
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