WO2015074297A1 - Heat-resistant abs resin composition formed by blow molding and preparation method therefor - Google Patents
Heat-resistant abs resin composition formed by blow molding and preparation method therefor Download PDFInfo
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- WO2015074297A1 WO2015074297A1 PCT/CN2013/088527 CN2013088527W WO2015074297A1 WO 2015074297 A1 WO2015074297 A1 WO 2015074297A1 CN 2013088527 W CN2013088527 W CN 2013088527W WO 2015074297 A1 WO2015074297 A1 WO 2015074297A1
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- resin composition
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 73
- 239000011342 resin composition Substances 0.000 title claims abstract description 71
- 238000000071 blow moulding Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001125 extrusion Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229920000578 graft copolymer Polymers 0.000 claims description 77
- 239000003795 chemical substances by application Substances 0.000 claims description 44
- 229920001577 copolymer Polymers 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 33
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 25
- 229920001971 elastomer Polymers 0.000 claims description 23
- 239000005060 rubber Substances 0.000 claims description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 21
- 229920002857 polybutadiene Polymers 0.000 claims description 19
- 230000009477 glass transition Effects 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 230000000379 polymerizing effect Effects 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 9
- 229920006029 tetra-polymer Polymers 0.000 claims description 8
- 229920001890 Novodur Polymers 0.000 claims description 6
- 238000012662 bulk polymerization Methods 0.000 claims description 6
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 229920001893 acrylonitrile styrene Polymers 0.000 claims description 2
- RPVQALVQDWBYJO-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione;prop-1-en-2-ylbenzene Chemical group CC(=C)C1=CC=CC=C1.O=C1C=CC(=O)N1C1=CC=CC=C1 RPVQALVQDWBYJO-UHFFFAOYSA-N 0.000 claims 1
- 238000005453 pelletization Methods 0.000 claims 1
- DXDLUSAGXYTADH-UHFFFAOYSA-N C=CC1=CC=CC=C1.CC(C#N)=CC=CC1=CC=CC=C1.C1(=CC=CC=C1)N1C(C=CC1=O)=O Chemical compound C=CC1=CC=CC=C1.CC(C#N)=CC=CC1=CC=CC=C1.C1(=CC=CC=C1)N1C(C=CC1=O)=O DXDLUSAGXYTADH-UHFFFAOYSA-N 0.000 abstract description 7
- 238000012805 post-processing Methods 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 26
- 239000002994 raw material Substances 0.000 description 9
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- JDCCCHBBXRQRGU-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile Chemical compound N#CC=CC=CC1=CC=CC=C1 JDCCCHBBXRQRGU-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000007591 painting process Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QDOXQIRWYQMOKT-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione;styrene Chemical compound C=CC1=CC=CC=C1.O=C1C=CC(=O)N1C1=CC=CC=C1 QDOXQIRWYQMOKT-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- JCJIZBQZPSZIBI-UHFFFAOYSA-N 2-[2,6-di(propan-2-yl)phenyl]benzo[de]isoquinoline-1,3-dione Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C1=O)C(=O)C2=C3C1=CC=CC3=CC=C2 JCJIZBQZPSZIBI-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- 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
Definitions
- the components and parts by weight of the monomer mixture are as follows, in terms of 100 parts by weight: 10 30 parts by weight of acrylonitrile and 70 parts by weight of a styrene component;
- Blow molded article surface quality A cylindrical blow molded article having a diameter of 100 ⁇ m and a length of 5 mm and a thickness of 5 mm was prepared using a blow molding machine.
- the blow molding conditions were a parison temperature of 240 ° C, a screw rotation speed of 50 rpm, and a mold temperature of 70 ° C.
- the surface condition of the entire cylindrical blow molded article was visually observed, and the number of uneven positions of the surface, that is, the number of pockmarks (the size of the pitting point was 0.02 mm or more) was counted. Evaluation based on the following criteria: O : the number of pittings is less than 10;
Abstract
The present invention relates to a heat-resistant ABS resin composition formed by blow molding and a preparation method therefor. The composition comprises styrene resin composition A in 100 parts by weight and a heat-resistant agent B in 20 to 40 parts by weight, the heat-resistant agent B being N-phenylmaleimide-α-methylstyrene-acrylonitrile-styrene quadripolymer. The preparation method for the ABS resin composition comprises the following steps: weighing the components in parts by weight; thoroughly mixing the components in a high-speed mixer, to obtain a mixture; the mixture entering a double-screw extruder from a main feed port, and undergoing melt extrusion, cooling, drying, and dicing, to obtain the ABS resin composition. A product prepared by blow molding in the present invention has desirable surface quality and heat-resistant performance, the vicat softening temperature reaches above 110°C, and therefore, the product can meet the heat-resistance requirement of the paint-spraying post-processing technique for auto parts and can be used in a harsh environment; moreover, the product prepared by blow molding is highly impact-resistant.
Description
适于吹塑成型的高耐热 ABS树脂组合物及其制备方法 技术领域 High heat-resistant ABS resin composition suitable for blow molding and preparation method thereof
本发明属于高分子技术领域，具体涉及一种适于吹塑成型的高耐热 ABS树脂组 合物及其制备方法。 The invention belongs to the technical field of polymers, and in particular relates to a high heat resistant ABS resin composition suitable for blow molding and a preparation method thereof.
背景技术 Background technique
ABS树脂具有优良的综合性能， 可应用于注塑、 挤出、 真空、 吹塑及辊压等多种成 型方法。 在吹塑成型过程中， 当聚合物通过狭小的口模时， 由于受到高剪切力作用， 挤 出的型坯在自重作用下会呈现熔垂现象， 过度的垂縮会导致制件的壁厚不均匀， 严重时 甚至不能成型。 因此， 在选择适合吹塑的聚合物时， 必须弄清其剪切的粘弹特性。 适用 于吹塑成型的 ABS树脂除了具有高熔体强度外，要求其熔体粘度的敏感性对剪切速率小， 即熔体粘度随剪切速率的变化小。 ABS resin has excellent comprehensive properties and can be applied to various molding methods such as injection molding, extrusion, vacuum, blow molding and rolling. During the blow molding process, when the polymer passes through a narrow die, due to the high shear force, the extruded parison will show a sag under its own weight, and excessive sag will cause the wall of the workpiece. Uneven thickness, even when severe, can not be formed. Therefore, when selecting a polymer suitable for blow molding, it is necessary to clarify the viscoelastic properties of the shear. ABS resins suitable for blow molding require, besides having a high melt strength, the sensitivity of the melt viscosity to a small shear rate, i.e., the change in melt viscosity with shear rate.
吹塑成型的 ABS树脂被广泛应用于汽车用大型制件， 如扰流器、 座背、 保险杠等 制品。 用于制造汽车零部件的 ABS树脂除了必须具有良好的物理机械性能（尤其是冲击 性能），还必须具有高耐热性能， 以满足喷漆等后加工工艺要求和较为苛刻的使用环境。 比如， 满足福特 WSK-M4D906-A1/A2标准的高耐热挤出级 ABS产品的维卡软化温度要求 大于 105°C ; 因此， 要求适用于汽车零部件的吹塑成型用 ABS树脂除了具有良好的可吹 塑性， 必须同时提高树脂的耐热性和冲击性能， 而耐热性能与耐冲击性能和产品的表面 质量是矛盾的； 现有技术中， 可实现维卡软化温度达到 105°C以上， 但是产品的表面质 量和耐冲击性能会变得非常差。 Blow molded ABS resins are widely used in large automotive parts such as spoilers, seat backs, bumpers and more. In addition to having good physical and mechanical properties (especially impact properties), ABS resins used in the manufacture of automotive parts must also have high heat resistance to meet post-processing requirements such as painting and more demanding environments. For example, the high heat-resistant extrusion grade ABS products that meet the Ford WSK-M4D906-A1/A2 standard require a Vicat softening temperature of greater than 105 ° C; therefore, the ABS resin for blow molding suitable for automotive parts is required to have good The blown plasticity must simultaneously improve the heat resistance and impact properties of the resin, and the heat resistance and the impact resistance and the surface quality of the product are contradictory; in the prior art, the Vicat softening temperature can reach 105 ° C. Above, but the surface quality and impact resistance of the product will become very poor.
目前， 用于 ABS树脂的耐热改性剂主要是基于马来酰亚胺的共聚物和基于 α -烷基 苯乙烯的共聚物。 由于合成方法的局限性， 单独使用这两类耐热剂用于制备吹塑 ABS树 脂都存在或多或少的不足： （1 ) 专利 CN 101250314和 CN 103013025A都公开了使用 Ν- 苯基马来酰亚胺 （ΡΜΙ ) 与马来酸酐 （ΜΑΗ) 、 苯乙烯 （St ) 的三元共聚物作为耐热剂制 备了适于吹塑成型的耐热 ABS树脂组合物。 必须注意的是， 为了提高树脂的耐热性， 基 于马来酰亚胺共聚物的耐热剂包含了大量马来酰亚胺组分（一般〉40重量份）， 耐热剂
的玻璃化转变温度很高， CN 101250314 选用的 PMI_St_MAH 共聚物的玻璃化温度高达 160-210°C， 而 ABS吹塑成型时的加工温度一般在 180_210°C。 因此， 很容易引起树脂塑 化不良， 制品表面光洁度差等缺陷， 增加了后续砂磨的成本； 其次， 耐热剂中同时引入 了遇热 /遇水极易分解的马来酸酐组分， 致使树脂的热稳定性随 MAH含量的增加而趋于 不稳定；第三，由于引入大量 NPMI组分严重削弱了 ABS树脂的抗冲击性能， CN 103013025A 专利同时复配了橡胶粉， 用于增韧， 进一步提高了材料成本； 第四， 当基于马来酰亚胺 的共聚物具有高马来酰亚胺含量时， 由于相当高的熔体粘度， 通常采用溶液聚合方法制 备， 制造成本很高， 因此， 基于马来酰亚胺共聚物的耐热剂的价格都比较昂贵； （2 ) 基于 α -烷基苯乙烯的共聚物的耐热剂的耐热改性幅度有限。 同时， 制备 α -烷基苯乙烯 的共聚物通常利用自由基乳液聚合， 合成过程很难完全消除低分子量乳化剂、 凝聚剂等 其他添加剂给产品带来的杂质，产品的 V0C含量较高，吹塑过程树脂容易产生分解气体， 影响制品表面外观和后续的喷漆良率。此外，亦有将 ABS与 PC等耐热级工程塑料共混 改性， 可以同时提高 ABS耐热性和抗冲击性能， 但缺点在于降低了 ABS树脂的可吹 塑性， 且 PC容易水解造成产品不稳定。 发明内容 Currently, heat-resistant modifiers for ABS resins are mainly copolymers based on maleimide and copolymers based on α-alkylstyrene. Due to the limitations of the synthesis method, the use of these two types of heat-resistant agents alone for the preparation of blown ABS resins has more or less disadvantages: (1) Both patents CN 101250314 and CN 103013025A disclose the use of Ν-phenyl Malay. A heat-resistant ABS resin composition suitable for blow molding was prepared as a heat-resistant agent of a ternary copolymer of imide (ΡΜΙ) with maleic anhydride (ΜΑΗ) and styrene (St). It must be noted that in order to improve the heat resistance of the resin, the heat-resistant agent based on the maleimide copolymer contains a large amount of a maleimide component (generally > 40 parts by weight), a heat-resistant agent. The glass transition temperature is very high, and the glass transition temperature of the PMI_St_MAH copolymer selected in CN 101250314 is as high as 160-210 ° C, while the processing temperature in ABS blow molding is generally 180-210 ° C. Therefore, it is easy to cause defects such as poor plasticization of the resin and poor surface finish of the product, which increases the cost of subsequent sanding. Secondly, the heat-resistant agent simultaneously introduces a maleic anhydride component which is easily decomposed by heat/water, resulting in The thermal stability of the resin tends to be unstable with the increase of the MAH content. Thirdly, the introduction of a large amount of NPMI component severely impairs the impact resistance of the ABS resin, and the CN 103013025A patent is also compounded with rubber powder for toughening, Further increasing the material cost; Fourth, when the maleimide-based copolymer has a high maleimide content, it is usually prepared by a solution polymerization method because of a relatively high melt viscosity, and the manufacturing cost is high. The heat-resistant agent based on maleimide copolymer is relatively expensive; (2) The heat-resistant modification of the heat-resistant agent based on the α-alkylstyrene copolymer is limited. At the same time, the copolymer for preparing α-alkylstyrene is usually subjected to radical emulsion polymerization, and it is difficult to completely eliminate the impurities brought by the low molecular weight emulsifier, coagulant and other additives to the product during the synthesis process, and the V0C content of the product is high, blowing Plastic process resins are prone to decomposition gases, affecting the surface appearance of the product and subsequent paint yield. In addition, ABS and PC are also blended with heat-resistant engineering plastics, which can improve the heat resistance and impact resistance of ABS at the same time, but the disadvantage is that the blowability of ABS resin is reduced, and PC is easily hydrolyzed to cause products. Unstable. Summary of the invention
本发明的目的在于克服现有技术的不足， 提供一种适于吹塑成型的高耐热 ABS 树脂组合物及其制备方法。 本发明的方法通过复配使用特定比例的耐热剂和高胶 粉， 制备适于吹塑成型的高耐热 ABS树脂， 以解决现有技术中制备吹塑成型用耐热 级 ABS树脂时在成本、 成型、 表面质量、 耐热性能 /冲击性能以及制品后加工等方面 造成的不足。 本发明是通过以下的技术方案实现的，本发明涉及一种适于吹塑成型的高耐热 ABS树脂组合物及其制备方法： 第一方面， 本发明涉及一种适于吹塑成型的高耐热 ABS树脂组合物， 所述组合 物包含： 100重量份的苯乙烯类树脂组合物 A和 20〜40重量份的耐热剂 B; SUMMARY OF THE INVENTION An object of the present invention is to overcome the deficiencies of the prior art and to provide a high heat resistant ABS resin composition suitable for blow molding and a method of preparing the same. The method of the present invention prepares a high heat-resistant ABS resin suitable for blow molding by compounding a specific ratio of a heat resistant agent and a high rubber powder to solve the problem of preparing a heat resistant grade ABS resin for blow molding in the prior art. Defects in cost, molding, surface quality, heat resistance/impact performance, and post-processing of the product. The present invention is achieved by the following technical solutions, and relates to a high heat resistant ABS resin composition suitable for blow molding and a preparation method thereof: In a first aspect, the present invention relates to a high temperature suitable for blow molding a heat resistant ABS resin composition, the composition comprising: 100 parts by weight of a styrenic resin composition A and 20 to 40 parts by weight of a heat resistant agent B;
(a)所述苯乙烯类树脂组合物 A的组分及重量份数如下， 按 100重量份计： 接枝共聚物 A- 1 10〜40重量份； 接枝共聚物 A-2 0〜30重量份； 共聚物 A-3 55〜80重量份；
(b)所述接枝共聚物 A-1的制备方法包括如下步骤： 按 100重量份计， 在 10 70重量份的橡胶型聚合物存在下， 通过 90 30重量份的单体混合物聚合而制得的 接枝共聚物； (a) The components and parts by weight of the styrenic resin composition A are as follows, based on 100 parts by weight: graft copolymer A-1 10 to 40 parts by weight; graft copolymer A-2 0 to 30 Parts by weight; copolymer A-3 55~80 parts by weight; (b) The method for producing the graft copolymer A-1 comprises the steps of: polymerizing 90 parts by weight of a monomer mixture in the presence of 10 70 parts by weight of a rubber-type polymer in terms of 100 parts by weight The resulting graft copolymer;
其中， 所述单体混合物的组分及重量份数如下， 按 100重量份计： 35 75重量 份的 α _甲基苯乙烯、 5 45重量份的苯乙烯、 10 25重量份的丙烯腈组分； Wherein, the components and parts by weight of the monomer mixture are as follows, based on 100 parts by weight: 35 75 parts by weight of α-methylstyrene, 5 45 parts by weight of styrene, and 10 25 parts by weight of acrylonitrile group Minute;
(c)所述接枝共聚物 Α-2的制备方法包括如下步骤： 按 100重量份计， 在 10 70重量份的橡胶型聚合物存在下， 通过 90 30重量份的单体混合物聚合而制得的 接枝共聚物； (c) The method for producing the graft copolymer oxime-2 comprises the steps of: polymerizing 90 parts by weight of a monomer mixture in the presence of 10 70 parts by weight of a rubber-type polymer in terms of 100 parts by weight The resulting graft copolymer;
其中， 所述单体混合物的组分及重量份数如下， 按 100重量份计： 10 30重量 份的丙烯腈和 70 90重量份的苯乙烯组分； Wherein the components and parts by weight of the monomer mixture are as follows, in terms of 100 parts by weight: 10 30 parts by weight of acrylonitrile and 70 parts by weight of a styrene component;
(d)所述共聚物 A-3 的制备方法包括如下步骤： 通过单体混合物聚合而制得的 共聚物； 其中， 所述单体混合物的组分及重量份数如下， 按 100重量份计： 18 48 重量份的丙烯腈单体和 52 82重量份的苯乙烯单体。 (d) The preparation method of the copolymer A-3 includes the following steps: a copolymer obtained by polymerizing a monomer mixture; wherein the components and parts by weight of the monomer mixture are as follows, based on 100 parts by weight : 18 48 parts by weight of acrylonitrile monomer and 52 82 parts by weight of styrene monomer.
优选地， 耐热剂 B和接枝共聚物 A-1的复配比例、 以及接枝共聚物 A- 1中耐热 组分 α -甲基苯乙烯的重量份可根据产品的具体耐热要求可调； 优选地， 接枝共聚 物 A-1中耐热组分 α -甲基苯乙烯组分选用 50 75重量份， 此时， 高耐热 ABS树脂 组合物包括所述接枝共聚物 A-1 20 40重量份， 耐热剂 Β 20 35重量份； 从而可 以保证产品具有优异耐热性的同时兼顾产品的表面质量和冲击性能。 Preferably, the compounding ratio of the heat resistant agent B and the graft copolymer A-1, and the weight fraction of the heat resistant component α-methylstyrene in the graft copolymer A-1 may be according to specific heat resistance requirements of the product. Preferably, the heat-resistant component α-methylstyrene component of the graft copolymer A-1 is selected from 50 75 parts by weight, and at this time, the high heat-resistant ABS resin composition includes the graft copolymer A -1 20 40 parts by weight, heat-resistant agent Β 20 35 parts by weight; thereby ensuring excellent heat resistance of the product while taking into consideration the surface quality and impact properties of the product.
优选地， 所述接枝共聚物 A-1以及接枝共聚物 Α-2制备中采用的橡胶型聚合物 为聚丁二烯橡胶、 丁苯橡胶、 丙烯酸酯橡胶、 丁腈橡胶中的一种或几种的混合。 Preferably, the rubber-type polymer used in the preparation of the graft copolymer A-1 and the graft copolymer Α-2 is one of polybutadiene rubber, styrene-butadiene rubber, acrylate rubber, and nitrile rubber. Or a mixture of several.
优选地， 所述接枝共聚物 A-1以及接枝共聚物 Α-2的凝胶含量均大于等于 85% 优选地， 所述接枝共聚物 A-1以及接枝共聚物 Α-2的凝胶含量均大于等于 90% 优选地， 所述接枝共聚物 A-1 以及接枝共聚物 Α-2 的橡胶粒径均小于等于 400 Preferably, the graft copolymer A-1 and the graft copolymer Α-2 have a gel content of 85% or more. Preferably, the graft copolymer A-1 and the graft copolymer Α-2 The gel content is 90% or more. Preferably, the graft copolymer A-1 and the graft copolymer Α-2 have a rubber particle diameter of less than or equal to 400.
优选地， 所述接枝共聚物 A-1 以及接枝共聚物 Α-2 的橡胶粒径均小于等于
300 Preferably, the graft copolymer A-1 and the graft copolymer Α-2 have a rubber particle diameter of less than or equal to 300
优选地， 所述共聚物 A-3的分子量为 100, 000 300, 000 Preferably, the copolymer A-3 has a molecular weight of 100,000,300,000
优选地， 所述共聚物 A-3的分子量为 180, 000 300, 000 Preferably, the copolymer A-3 has a molecular weight of 180,000,300,000
优选地， 所述耐热剂 B为 N-苯基马来酰亚胺- α -甲基苯乙烯-丙烯腈 -苯乙烯四元 共聚物， 采用连续本体聚合法合成。 Preferably, the heat resistant agent B is an N-phenylmaleimide-α-methylstyrene-acrylonitrile-styrene quaternary copolymer synthesized by a continuous bulk polymerization method.
优选地， 所述耐热剂 Β的组分及重量份数如下， 按 100重量份计， 其中， Ν-苯 基马来酰亚胺组分 20 30重量份， α -甲基苯乙烯组分 30 50重量份， 苯乙烯组 分 10 40重量份， 丙烯腈组分 20 40重量份。 Preferably, the components and parts by weight of the heat resistant agent bismuth are as follows, wherein, based on 100 parts by weight, wherein the fluorenyl-phenylmaleimide component 20 is 30 parts by weight, the α-methylstyrene component 30 50 parts by weight, styrene component 10 40 parts by weight, acrylonitrile component 20 40 parts by weight.
优选地， 所述耐热剂 Β的玻璃化转变温度为 140 160°C Preferably, the heat resistant agent has a glass transition temperature of 140 160 ° C
进一步优选地， 所述耐热剂 B中， 各单体的含量可以根据具体的耐热要求进行 调整，优选地， N-苯基马来酰亚胺组分在 20 30重量份， α -甲基苯乙烯组分在 35 45重量份， 苯乙烯组分在 10 40重量份， 丙烯腈组分在 20 40重量份； 进而， 所 述耐热剂的玻璃化转变温度优选为 145 155°C Further preferably, in the heat resistant agent B, the content of each monomer can be adjusted according to specific heat resistance requirements, preferably, the N-phenylmaleimide component is 20 30 parts by weight, α-A The styrene component is 35 45 parts by weight, the styrene component is 10 40 parts by weight, and the acrylonitrile component is 20 40 parts by weight; further, the heat resistant agent preferably has a glass transition temperature of 145 155 ° C.
根据需要， 本发明的组合物还可添加常规的填料或加工助剂； 作为一种优选， 所述 ABS树脂组合物还包括如下重量份数的各组分： 0.1 5重量份的滑石、 0.1 5 重量份的聚烯烃类蜡、 0.1 1重量份的抗氧剂。 The composition of the present invention may further contain a conventional filler or processing aid, as needed; as a preferred, the ABS resin composition further comprises the following components by weight: 0.15 parts by weight of talc, 0.1 5 Parts by weight of a polyolefin-based wax, 0.11 part by weight of an antioxidant.
第二方面，本发明还涉及前述适于吹塑成型的高耐热 ABS树脂组合物的制备方法， 包括如下步骤： In a second aspect, the present invention also relates to a method for preparing the aforementioned high heat resistant ABS resin composition suitable for blow molding, comprising the steps of:
步骤 1， 按照重量份数称取各组分； Step 1, weighing each component by weight;
步骤 2， 将各组分在高速混合机中充分混合， 得混合物； Step 2, the components are thoroughly mixed in a high-speed mixer to obtain a mixture;
步骤 3， 将混合物从双螺杆挤出机的主喂料进入， 经过熔融挤出、 冷却、 干燥、 切 粒， 即得所述 ABS树脂组合物。 In step 3, the mixture is introduced from the main feed of the twin-screw extruder, and after melt extrusion, cooling, drying, and dicing, the ABS resin composition is obtained.
优选地， 所述的双螺杆挤出机的螺杆长径比为 30 70， 机筒必须设置至少两处真 空抽排装置， 螺杆料机筒进料段温度为 180 210°C、 塑化段温度为 230 250°C、 均化 段温度为 220 240°C， 螺杆转速为 200 500rpm
本发明同现有技术相比， 具有以下优点和有益效果： Preferably, the twin-screw extruder has a screw length to diameter ratio of 30 70, and the barrel must be provided with at least two vacuum pumping devices, and the screw barrel barrel feed section temperature is 180 210 ° C, the plasticizing section temperature 230 250 ° C, homogenization temperature 220 240 ° C, screw speed 200 500 rpm Compared with the prior art, the present invention has the following advantages and benefits:
( 1 ) 本发明通过向包含特定组分特定量的苯乙烯类树脂组合物中加入特定方法合 成的具有特定组分特定量的耐热剂， 并与树脂组合物中的组分发生协同作用， 进而解决 了现有技术中吹塑成型用耐热级 ABS树脂在成本、 成型、 表面质量、 耐热性能 /冲击性 能等方面存在的问题； (1) The present invention synthesizes a specific amount of a heat-resistant agent having a specific component synthesized by adding a specific method to a specific amount of a styrene-based resin composition containing a specific component, and synergizes with components in the resin composition, Further solving the problems in the prior art in the heat-resistant ABS resin for blow molding in terms of cost, molding, surface quality, heat resistance/impact performance, and the like;
( 2 ) 本发明制备了可吹塑性和耐热性倶佳的吹塑成型用高耐热 ABS树脂组合物， 吹塑制品具有良好的表面质量和耐冲击性能； (2) The present invention prepares a high heat-resistant ABS resin composition for blow molding which is excellent in blown plasticity and heat resistance, and has a good surface quality and impact resistance;
( 3 ) 本发明的树脂组合物的熔体强度高且熔体粘度对剪切速率的敏感性小， 可以 减小吹塑型坯的熔体下垂现象， 且吹塑制品的表面质量好； (3) The resin composition of the present invention has high melt strength and low sensitivity of melt viscosity to shear rate, can reduce melt sag of blown parison, and the surface quality of the blow molded article is good;
( 4)本发明的树脂组合物的耐热高， 维卡软化温度达 11CTC以上， 可以满足汽车零 部件喷漆后加工工艺的耐热要求和较为苛刻的使用环境， 且吹塑制品的耐冲击性能好。 (4) The resin composition of the present invention has high heat resistance, and the Vicat softening temperature is above 11 CTC, which can meet the heat resistance requirements of the post-painting process of automobile parts and the harsh environment, and the impact resistance of the blow molded product. it is good.
对本发明的相应原理进行分析如下，耐热剂 B选用的是 N-苯基马来酰亚胺- α -甲基 苯乙烯-丙烯腈-苯乙烯四元共聚物， 采用连续本体聚合法合成； 应用连续本体聚合方法 有利于聚合产物的高产率和低成本制备；现有技术中没有报道过采用此类耐热剂用于吹 塑成型用耐热级 ABS树脂组合物的制备； 为了避免本体聚合过程熔体粘度过高引起爆聚的问题， 同时实现四元共聚物的高温 热稳定性和耐热性、 加工性能和可共混性的集大成， 聚合过程四种组分的比例要合理控 制， 因此， 本发明中耐热剂 Β中各单体的组分是经过特殊选择的， 具体为 Ν-取代马来酰 亚胺组分在 20〜30重量份， α -甲基苯乙烯组分在 30〜50重量份， 苯乙烯组分在 10〜 40重量份， 丙烯腈组分在 20〜40重量份， 使得四元共聚物的玻璃化转变温度控制在 140〜160°C ; The corresponding principle of the present invention is analyzed as follows. The heat-resistant agent B is selected from N-phenylmaleimide-α-methylstyrene-acrylonitrile-styrene quaternary copolymer and synthesized by continuous bulk polymerization; The use of a continuous bulk polymerization process facilitates high yield and low cost preparation of the polymerization product; the preparation of a heat resistant grade ABS resin composition for blow molding using such a heat resistant agent has not been reported in the prior art; The process melt viscosity is too high to cause the problem of explosion, and at the same time, the high temperature thermal stability and heat resistance of the tetrapolymer, the processing property and the blendability are achieved, and the proportion of the four components in the polymerization process should be reasonably controlled. Therefore, the components of each monomer in the heat-resistant agent in the present invention are specifically selected, specifically, the Ν-substituted maleimide component is 20 to 30 parts by weight, and the α-methylstyrene component is 30 to 50 parts by weight, the styrene component is 10 to 40 parts by weight, and the acrylonitrile component is 20 to 40 parts by weight, so that the glass transition temperature of the tetrapolymer is controlled at 140 to 160 ° C;
本发明中耐热剂 B较低的玻璃化转变温度， 使得其能够非常适合应用于加工温度 相对较低 （具体为 190〜210°C ) 的吹塑成型用 ABS树脂， 同时也决定了其对 ABS树脂 耐热提高幅度的有限性； 因此， 要想实现本发明的发明效果， 必须要将所述耐热剂 B与 接枝共聚物 A-1复配使用， 发挥其协同作用； The lower glass transition temperature of the heat-resistant agent B in the present invention makes it very suitable for application to ABS resin for blow molding at a relatively low processing temperature (specifically, 190 to 210 ° C), and also determines its right The ABS resin has a limited increase in heat resistance; therefore, in order to achieve the effects of the present invention, it is necessary to use the heat-resistant agent B in combination with the graft copolymer A-1 to exert a synergistic effect;
本发明中， 所使用的接枝共聚物 A-1中接枝的 α -甲基苯乙烯组分显著提高了接枝
共聚物的耐热性， 如此以来， 连续本体聚合方法制备的耐热剂 B中， 为了解决较低的马 来酰亚胺含量引起耐热性降低造成的问题， 除了通过四元共聚物中同时引入适量 α -甲 基苯乙烯组分来弥补外，还在 ABS树脂制备过程中选择耐热性提高的接枝共聚物 A-1与 耐热剂 Β复配使用来进一步提高 ABS树脂的耐热性； 然而， 接枝共聚物 A-1中的 α -甲 基苯乙烯的含量必须适量， 为了使得本发明的 ABS 树脂组合物的维卡软化温度达到 110°C， 所述接枝共聚物 A-1中， α -甲基苯乙烯组分必须控制在 35〜75重量份； 为提高 ABS树脂熔体强度和可吹塑性，本发明中的接枝共聚物 A-1和接枝共聚物 Α-2 的凝胶含量需达到 85%以上， 优选在 90%以上； 同时， 橡胶粒径尺寸在 400nm以下， 优 选 300nm以下；橡胶凝胶含量过低或橡胶粒径过大，都不利于提高 ABS树脂的熔体强度， 而在吹塑 ABS中， 高熔体强度是防止吹塑型坯下垂的必要条件。 In the present invention, the grafted α-methylstyrene component of the graft copolymer A-1 used significantly increases the grafting. The heat resistance of the copolymer, so that in the heat-resistant agent B prepared by the continuous bulk polymerization method, in order to solve the problem caused by the lower maleimide content, the heat resistance is lowered, except that the tetrapolymer is simultaneously In addition to the appropriate amount of α-methylstyrene component to compensate, the graft copolymer A-1 with improved heat resistance is selected in the ABS resin preparation process to further improve the heat resistance of the ABS resin. However, the content of α-methylstyrene in the graft copolymer A-1 must be an appropriate amount, and the graft copolymer A is used in order to bring the Vicat softening temperature of the ABS resin composition of the present invention to 110 ° C. -1, the α-methylstyrene component must be controlled at 35 to 75 parts by weight; in order to improve the melt strength and blown plasticity of the ABS resin, the graft copolymer A-1 and the graft copolymer of the present invention The gel content of Α-2 needs to be above 85%, preferably above 90%; at the same time, the rubber particle size is below 400 nm, preferably below 300 nm; the rubber gel content is too low or the rubber particle size is too large, which is not conducive to improvement The melt strength of ABS resin, while in blown ABS, high Melt strength is a necessary condition to prevent the blown parison from sagging.
共聚物 A-3 是具有高分子量的苯乙烯-丙烯腈共聚物， 分子量控制在 100，000〜 300, 000， 优选 180, 000〜300, 000。 复配使用高分子量 SAN也是提高 ABS树脂熔体强度 的重要途径。 但是 SAN分子量太高， 亦容易引起 ABS树脂塑化不良以及其与橡胶型接枝 聚合物的相容性问题。 The copolymer A-3 is a styrene-acrylonitrile copolymer having a high molecular weight, and has a molecular weight of 100,000 to 300,000, preferably 180,000 to 300,000. The use of high molecular weight SANs is also an important way to increase the melt strength of ABS resins. However, the molecular weight of the SAN is too high, which is liable to cause poor plasticization of the ABS resin and compatibility with the rubber-type graft polymer.
具体实施方式 detailed description
下面结合具体实施例对本发明进行详细说明。 以下实施例将有助于本领域的技 术人员进一步理解本发明， 但不以任何形式限制本发明。 应当指出的是， 对本领域 的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。 这些都属于本发明的保护范围。 The invention will now be described in detail in connection with specific embodiments. The following examples are intended to further understand the invention, but are not intended to limit the invention in any way. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the inventive concept. These are all within the scope of protection of the present invention.
实施例 1〜5 Example 1~5
( 1 ) 所有实施例与对比例中， 采用的原材料为： (1) In all the examples and comparative examples, the raw materials used were:
接枝共聚物 A- la为聚丁二烯橡胶接枝苯乙烯-丙烯腈 - α -甲基苯乙烯共聚物， 凝胶含量为 85%， 橡胶粒径约 150nm; The graft copolymer A- la is a polybutadiene rubber grafted styrene-acrylonitrile-α-methylstyrene copolymer having a gel content of 85% and a rubber particle size of about 150 nm;
所述接枝共聚物 A-la的制备方法包括如下步骤： 在 45重量份的聚丁二烯橡胶 存在下， 通过 55重量份的单体混合物聚合而制得的接枝共聚物； The preparation method of the graft copolymer A-la comprises the following steps: a graft copolymer prepared by polymerizing 55 parts by weight of a monomer mixture in the presence of 45 parts by weight of a polybutadiene rubber;
其中， 所述单体混合物包含的组分及重量份数如下， 按 100重量份计： 60重量
份的 α _甲基苯乙烯、 16重量份的苯乙烯、 24重量份的丙烯腈组分； 接枝共聚物 A- lb为聚丁二烯橡胶接枝苯乙烯-丙烯腈 - α -甲基苯乙烯共聚物， 凝胶含量为 90%， 橡胶粒径约 200nm; Wherein, the monomer mixture comprises components and parts by weight as follows, in terms of 100 parts by weight: 60 weight Parts of α-methylstyrene, 16 parts by weight of styrene, 24 parts by weight of acrylonitrile component; graft copolymer A- lb is polybutadiene rubber grafted styrene-acrylonitrile-α-methyl a styrene copolymer having a gel content of 90% and a rubber particle size of about 200 nm;
所述接枝共聚物 A-lb的制备方法包括如下步骤： 在 50重量份的聚丁二烯橡胶 存在下， 通过 50重量份的单体混合物聚合而制得的接枝共聚物； The preparation method of the graft copolymer A-lb comprises the following steps: a graft copolymer prepared by polymerizing 50 parts by weight of a monomer mixture in the presence of 50 parts by weight of a polybutadiene rubber;
其中， 所述单体混合物包含的组分及重量份数如下， 按 100重量份计： 70重量 份的 α _甲基苯乙烯、 20重量份的苯乙烯、 10重量份的丙烯腈组分； Wherein, the monomer mixture comprises components and parts by weight as follows, based on 100 parts by weight: 70 parts by weight of α-methylstyrene, 20 parts by weight of styrene, and 10 parts by weight of an acrylonitrile component;
接枝共聚物 A- lc为聚丁二烯橡胶接枝苯乙烯-丙烯腈 - α -甲基苯乙烯共聚物， 凝胶含量为 93%， 橡胶粒径约 250nm; The graft copolymer A- lc is a polybutadiene rubber grafted styrene-acrylonitrile-α-methylstyrene copolymer having a gel content of 93% and a rubber particle size of about 250 nm;
所述接枝共聚物 A-lc的制备方法包括如下步骤： 在 50重量份的聚丁二烯橡胶 存在下， 通过 50重量份的单体混合物聚合而制得的接枝共聚物； The preparation method of the graft copolymer A-lc comprises the following steps: a graft copolymer prepared by polymerizing 50 parts by weight of a monomer mixture in the presence of 50 parts by weight of a polybutadiene rubber;
其中， 所述单体混合物包含的组分及重量份数如下， 按 100重量份计： 50重量 份的 α _甲基苯乙烯、 35重量份的苯乙烯、 15重量份的丙烯腈组分； Wherein, the monomer mixture comprises components and parts by weight as follows, based on 100 parts by weight: 50 parts by weight of α-methylstyrene, 35 parts by weight of styrene, and 15 parts by weight of an acrylonitrile component;
接枝共聚物 A-2a为聚丁二烯橡胶接枝苯乙烯-丙烯腈共聚物，凝胶含量为 85%， 橡胶粒径约 300nm; The graft copolymer A-2a is a polybutadiene rubber grafted styrene-acrylonitrile copolymer having a gel content of 85% and a rubber particle size of about 300 nm;
所述接枝共聚物 A-2a的制备方法包括如下步骤： 在 50重量份的聚丁二烯橡胶 存在下， 通过 50重量份的单体混合物聚合而制得的接枝共聚物； The preparation method of the graft copolymer A-2a comprises the steps of: graft copolymer obtained by polymerizing 50 parts by weight of a monomer mixture in the presence of 50 parts by weight of a polybutadiene rubber;
其中， 所述单体混合物的组分及重量份数如下， 按 100重量份计： 76重量份的 苯乙烯组分和 24重量份的丙烯腈组分； Wherein the components and parts by weight of the monomer mixture are as follows, in terms of 100 parts by weight: 76 parts by weight of the styrene component and 24 parts by weight of the acrylonitrile component;
接枝共聚物 A-2b为聚丁二烯橡胶接枝苯乙烯-丙烯腈共聚物，凝胶含量为 92%， 橡胶粒径约 300nm; The graft copolymer A-2b is a polybutadiene rubber grafted styrene-acrylonitrile copolymer having a gel content of 92% and a rubber particle size of about 300 nm;
所述接枝共聚物 A-2b的制备方法包括如下步骤： 在 60重量份的聚丁二烯橡胶 存在下， 通过 40重量份的单体混合物聚合而制得的接枝共聚物； The preparation method of the graft copolymer A-2b comprises the following steps: a graft copolymer obtained by polymerizing 40 parts by weight of a monomer mixture in the presence of 60 parts by weight of a polybutadiene rubber;
其中， 所述单体混合物的组分及重量份数如下， 按 100重量份计： 70重量份的 苯乙烯组分和 30重量份的丙烯腈组分；
共聚物 A-3a为苯乙烯-丙烯腈共聚物， AN组分重量份为 26%，分子量为 210， 000。 共聚物 A-3b为苯乙烯-丙烯腈共聚物， AN组分重量份为 32%，分子量为 250， 000。 耐热剂 B-la为连续本体法合成的 N-苯基马来酰亚胺 - α -甲基苯乙烯 -丙烯腈- 苯乙烯四元共聚物； 按 100重量份计， 其中 Ν-苯基马来酰亚胺组分重量份为 20重 量份， α -甲基苯乙烯组分重量份为 40重量份， 苯乙烯组分 18重量份， 丙烯腈组 分 22重量份； 玻璃化转变温度为 145 °C。 Wherein, the components and parts by weight of the monomer mixture are as follows, based on 100 parts by weight: 70 parts by weight of the styrene component and 30 parts by weight of the acrylonitrile component; The copolymer A-3a was a styrene-acrylonitrile copolymer having an AN component of 26% by weight and a molecular weight of 210,000. Copolymer A-3b is a styrene-acrylonitrile copolymer having an AN component in an amount of 32% by weight and a molecular weight of 250,000. The heat-resistant agent B-la is a continuous bulk synthesis of N-phenylmaleimide-α-methylstyrene-acrylonitrile-styrene tetrapolymer; wherein, based on 100 parts by weight, Ν-phenyl The maleimide component is 20 parts by weight, the α-methylstyrene component is 40 parts by weight, the styrene component is 18 parts by weight, and the acrylonitrile component is 22 parts by weight; the glass transition temperature is 145 °C.
耐热剂 B-lb为连续本体法合成的 N-苯基马来酰亚胺 - α -甲基苯乙烯 -丙烯腈- 苯乙烯四元共聚物； 按 100重量份计， 其中 Ν-苯基马来酰亚胺组分重量份为 30重 量份， α -甲基苯乙烯组分重量份为 30重量份， 苯乙烯组分 25重量份， 丙烯腈组 分 15重量份； 玻璃化转变温度为 155 °C。 The heat-resistant agent B-lb is a continuous bulk synthesis of N-phenylmaleimide-α-methylstyrene-acrylonitrile-styrene tetrapolymer; wherein, based on 100 parts by weight, Ν-phenyl The maleimide component is 30 parts by weight, the α-methylstyrene component is 30 parts by weight, the styrene component is 25 parts by weight, and the acrylonitrile component is 15 parts by weight; the glass transition temperature is 155 °C.
滑石粉 C的目数为 2500〜5000目。 The mesh number of talc powder C is 2,500 to 5,000 mesh.
聚烯烃类蜡 D为市售的聚乙烯蜡。 The polyolefin wax D is a commercially available polyethylene wax.
抗氧剂 E为市售的受阻单酚、 双酚或多酚化合物与亚磷酸酯类化合物的混合物。 按照表 1所示的重量份数取各组分， 之后采用如下方法制备所述 ABS树脂组合物： 步骤 1， 按照重量份数称取各组分； Antioxidant E is a commercially available hindered monophenol, bisphenol or a mixture of a polyphenolic compound and a phosphite compound. The components were taken in parts by weight as shown in Table 1, and then the ABS resin composition was prepared as follows: Step 1, the components were weighed according to parts by weight;
步骤 2， 将各组分在高速混合机中充分混合 20min， 得混合物； Step 2, the components are thoroughly mixed in a high-speed mixer for 20 minutes to obtain a mixture;
步骤 3， 将混合物从双螺杆挤出机的主喂料进入， 经过熔融挤出、 冷却、 干燥、 切 粒， 即得所述 ABS树脂组合物； 双螺杆挤出机的螺杆直径为 35mm， 长径比为 44。 挤出 机从加料口到口模共有 10个温控区， 其中第 1〜3区 （进料段） 温控为 180〜210°C ; 第 4〜7区 （塑化段） 温控为 230〜250°C ; 第 8〜10区 （均化段） 温控为 220〜240°C ; 挤出机的两个抽真空位置分别设置于第四和第九区， 真空度为 0. 06〜0. 094MPa， 螺杆 转速设为 300〜500rpm。 Step 3, the mixture is fed from the main feed of the twin-screw extruder, and melt-extruded, cooled, dried, and pelletized to obtain the ABS resin composition; the screw diameter of the twin-screw extruder is 35 mm, long The diameter ratio is 44. There are 10 temperature control zones from the feeding port to the die, in which the temperature control of the 1st to 3rd zones (feeding section) is 180~210°C; the zone 4~7 (plasticizing section) temperature control is 230 The temperature is 0. 06~ The temperature is 0. 06~ The temperature is 0. 06~ 0. 094 MPa, the screw rotation speed was set to 300 to 500 rpm.
( 2 ) 对比例 1 ( 2 ) Comparative example 1
为了较好地体现上述用于吹塑成型的耐热 ABS树脂组合物的特点， 在此使用对比 例 1。 在该对比例中， 将耐热剂 （B)组分换成溶液法合成的 N-苯基马来酰亚胺-苯乙烯
-马来酸酐三元共聚物（B1 ) ， N-苯基马来酰亚胺组分重量百分比含量为 55%， 共聚物的 玻璃化转变温度为 196 °C。 原料重量比例见表 1， 制备方法同实施例 1。 In order to better embody the characteristics of the above heat-resistant ABS resin composition for blow molding, Comparative Example 1 was used herein. In this comparative example, the heat-resistant agent (B) component was replaced by a solution-formed N-phenylmaleimide-styrene. - Maleic anhydride terpolymer (B1), the N-phenylmaleimide component has a weight percentage of 55%, and the copolymer has a glass transition temperature of 196 °C. The weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Example 1.
( 3) 对比例 2 (3) Comparative example 2
为了较好地体现上述用于吹塑成型的耐热 ABS树脂组合物的特点， 在此使用对比 例 2。 在该对比例中， 将耐热剂 （B) 组分换成苯乙烯-马来酸酐二元共聚物 （B2) ， 马 来酸酐组分的重量百分比含量为 23%， 共聚物的玻璃化转变温度为 150°C。 原料重量比 例见表 1， 制备方法同实施例 1。 In order to better embody the characteristics of the above heat-resistant ABS resin composition for blow molding, Comparative Example 2 was used herein. In this comparative example, the heat resistant agent (B) component was replaced by a styrene-maleic anhydride binary copolymer (B2), and the maleic anhydride component was present in a percentage by weight of 23%, and the glass transition of the copolymer The temperature is 150 °C. The weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Example 1.
(4) 对比例 3 (4) Comparative example 3
为了较好地体现上述用于吹塑成型的耐热 ABS树脂组合物的特点，在此使用对比例 2。 在该对比例中， 耐热剂 （B-lc) N-苯基马来酰亚胺 - α -甲基苯乙烯-丙烯腈 -苯乙 烯四元共聚物； 按 100重量份计， 其中 Ν-苯基马来酰亚胺组分重量份为 40重量份， α -甲基苯乙烯组分重量份为 20重量份， 苯乙烯组分 30重量份， 丙烯腈组分 10重 量份； 玻璃化转变温度为 165°C。 原料重量比例见表 1， 制备方法同实施例 1。 In order to better embody the characteristics of the above heat-resistant ABS resin composition for blow molding, Comparative Example 2 was used herein. In the comparative example, a heat-resistant agent (B-lc) N-phenylmaleimide-α-methylstyrene-acrylonitrile-styrene tetrapolymer; based on 100 parts by weight, wherein Ν- The phenyl maleimide component is 40 parts by weight, the α-methylstyrene component is 20 parts by weight, the styrene component is 30 parts by weight, and the acrylonitrile component is 10 parts by weight; The temperature was 165 °C. The weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Example 1.
( 5) 对比例 4 (5) Comparative example 4
为了较好地体现上述用于吹塑成型的耐热 ABS树脂组合物的特点，在此使用对比例 2。 在该对比例中， 将耐热剂 （B) 组分换成 α -甲基苯乙烯-丙烯腈共聚物 （Β3 ) ， 组 分重量份 α -甲基苯乙烯为 70重量份， 丙烯腈组分 30重量份； 玻璃化转变温度为 135°C。 原料重量比例见表 1， 制备方法同实施例 1。 In order to better embody the characteristics of the above heat-resistant ABS resin composition for blow molding, Comparative Example 2 was used herein. In this comparative example, the heat resistant agent (B) component was replaced with an α-methylstyrene-acrylonitrile copolymer (Β3), and the component parts by weight of α-methylstyrene was 70 parts by weight, and the acrylonitrile group was used. 30 parts by weight; glass transition temperature of 135 ° C. The weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Example 1.
(6) 对比例 5 (6) Comparative example 5
为了较好地体现上述用于吹塑成型的耐热 ABS树脂组合物的特点，在此使用对比例 2。 在该对比例中， 接枝共聚物 A-1 为聚丁二烯橡胶接枝苯乙烯-丙烯腈 _ α -甲基苯 乙烯共聚物 （A-ld ) ， 凝胶含量为 80%， 橡胶粒径约 350nm; In order to better embody the characteristics of the above heat-resistant ABS resin composition for blow molding, Comparative Example 2 was used herein. In this comparative example, the graft copolymer A-1 is a polybutadiene rubber grafted styrene-acrylonitrile_α-methylstyrene copolymer (A-ld) having a gel content of 80%, rubber particles. The diameter is about 350nm ;
所述接枝共聚物 A-ld的制备方法包括如下步骤： 在 45重量份的聚丁二烯橡胶 存在下， 通过 55重量份的单体混合物聚合而制得的接枝共聚物； The preparation method of the graft copolymer A-ld comprises the following steps: a graft copolymer obtained by polymerizing 55 parts by weight of a monomer mixture in the presence of 45 parts by weight of a polybutadiene rubber;
其中， 所述单体混合物包含的组分及重量份数如下， 按 100重量份计： 60重量
份的 α _甲基苯乙烯、 16重量份的苯乙烯、 24重量份的丙烯腈组分； 原料重量比例见 表 1， 制备方法同实施例 1。 Wherein, the monomer mixture comprises components and parts by weight as follows, in terms of 100 parts by weight: 60 weight Parts of α-methylstyrene, 16 parts by weight of styrene, and 24 parts by weight of acrylonitrile component; the weight ratio of the raw materials is shown in Table 1, and the preparation method is the same as in Example 1.
( 7) 对比例 6 (7) Comparative example 6
为了较好地体现上述用于吹塑成型的耐热 ABS树脂组合物的特点，在此使用对比例 2。在该对比例中，接枝共聚物 Α-2为聚丁二烯橡胶接枝苯乙烯-丙烯腈共聚物 ( A-2c )， 凝胶含量为 75%， 橡胶粒径约 250nm; In order to better embody the characteristics of the above heat-resistant ABS resin composition for blow molding, Comparative Example 2 was used herein. In this comparative example, the graft copolymer Α-2 is a polybutadiene rubber grafted styrene-acrylonitrile copolymer (A-2c) having a gel content of 75% and a rubber particle size of about 250 nm;
所述接枝共聚物 A-2c的制备方法包括如下步骤： 在 50重量份的聚丁二烯橡胶 存在下， 通过 50重量份的单体混合物聚合而制得的接枝共聚物； The preparation method of the graft copolymer A-2c comprises the following steps: a graft copolymer obtained by polymerizing 50 parts by weight of a monomer mixture in the presence of 50 parts by weight of a polybutadiene rubber;
其中， 所述单体混合物的组分及重量份数如下， 按 100重量份计： 76重量份的 苯乙烯组分和 24重量份的丙烯腈组分； 原料重量比例见表 1， 制备方法同实施例 1。 Wherein, the components and parts by weight of the monomer mixture are as follows, based on 100 parts by weight: 76 parts by weight of the styrene component and 24 parts by weight of the acrylonitrile component; the weight ratio of the raw materials is shown in Table 1, and the preparation method is the same Example 1.
如下表 1所示， 共有 6个配方按照上述制备方法进行熔融挤出、 拉粒冷却、 造粒 制备 ABS树脂组合物， 将物料在 80°C干燥 12h， 保证注塑前树脂的吸水率〈0. 05%， 然后 按照 ISO标准，在同一注塑条件下注塑成样条，测试各个树脂组合物的物理性能。其中， 基于 ISO 179标准测定样条的简支梁缺口冲击强度； 基于 ISO 306标准测定样条的维卡 软化温度 （VST) ， 载荷为 5kg， 升温速率为 50°C/h。 As shown in Table 1 below, a total of 6 formulations were melt extruded, pellet cooled, and granulated according to the above preparation method to prepare an ABS resin composition, and the material was dried at 80 ° C for 12 h to ensure the water absorption of the resin before injection molding was <0. 05%, and then the plastic properties of each resin composition were tested by injection molding into splines under the same injection molding conditions in accordance with the ISO standard. Among them, the notched impact strength of the simply supported beam is determined based on the ISO 179 standard; the Vicat softening temperature (VST) of the spline is determined based on the ISO 306 standard, the load is 5 kg, and the heating rate is 50 ° C / h.
流变性能测试：使用马尔文单筒毛细管流变仪，选取长径比为 16/1、直径为 0. 5mm, 入口角为 180° 的口模。 设定测试温度 240°C， 剪切速率范围 200-50000s-l， 原料塑化 阶段设定为加压到 IMpa然后保温 6min， 再次加压到 IMpa后再次预热 4min。 待设定温 度稳定后， 称取充分干燥的物料约 35g， 分次加入料桶中并压紧压实， 然后开始测试， 记录各个剪切速率下的剪切粘度。 其中表 1中的剪切粘度 1为 200s-l剪切速率时的粘 度， 而剪切粘度 2为 50000S-1剪切速率时的粘度。 Rheological performance test: Using a Malvern single-tube capillary rheometer, a die having a length to diameter ratio of 16/1, a diameter of 0.5 mm, and an inlet angle of 180° was selected. Set the test temperature to 240 °C, the shear rate range is 200-50000 s-l, and the plasticizing stage of the raw material is set to pressurize to IMpa and then keep it for 6 minutes. After pressurizing again to IMpa, preheat it for another 4 minutes. After the set temperature is stable, weigh about 35g of fully dried material, add it to the drum in stages and compact it, then start the test and record the shear viscosity at each shear rate. The shear viscosity 1 in Table 1 is the viscosity at a shear rate of 200 s-l, and the shear viscosity 2 is the viscosity at a shear rate of 50000 S-1.
吹塑制品表面质量： 使用吹塑机制备直径为 lOOirau长度为 500mm且厚度为 5mm的 圆柱形吹塑制品。 吹塑条件为型坯温度为 240°C， 螺杆转速 50rpm， 模具温度为 70°C。 通过目视观察上述整个圆柱形吹塑制品的表面状况， 对表面的不平坦位置即麻点 （计麻 点大小为 0. 02mm或更大） 的数量进行统计。 基于以下标准进行评价：
O : 麻点的数量小于 10; Blow molded article surface quality: A cylindrical blow molded article having a diameter of 100 μm and a length of 5 mm and a thickness of 5 mm was prepared using a blow molding machine. The blow molding conditions were a parison temperature of 240 ° C, a screw rotation speed of 50 rpm, and a mold temperature of 70 ° C. The surface condition of the entire cylindrical blow molded article was visually observed, and the number of uneven positions of the surface, that is, the number of pockmarks (the size of the pitting point was 0.02 mm or more) was counted. Evaluation based on the following criteria: O : the number of pittings is less than 10;
Δ: 麻点的数量不低于 10但低于 20; Δ: the number of pittings is not less than 10 but less than 20;
Ο 麻点的数量不低于 20; 数量 The number of pockmarks is not less than 20;
评价结果是： 麻点数量小， 表明制品表面性能优异。 The evaluation results are as follows: The small number of pitting points indicates that the surface properties of the product are excellent.
表 1 Table 1
0. 5 0. 8 0. 2 1. 5 1. 5 0. 5 0. 5 0. 5 0. 5 0. 5 0. 5 蜡 D 0. 5 0. 8 0. 2 1. 5 1. 5 0. 5 0. 5 0. 5 0. 5 0. 5 0. 5 Wax D
抗氧剂 E 0. 5 0. 2 0. 3 0. 5 0. 5 0. 5 1. 0 0. 5 0. 5 0. 5 1. 0 其他助剂 2 3. 5 0. 5 3 3 2 2 2 2 2 2 剪切粘度 148 Antioxidant E 0. 5 0. 2 0. 3 0. 5 0. 5 0. 5 1. 0 0. 5 0. 5 0. 5 1. 0 Other additives 2 3. 5 0. 5 3 3 2 2 2 2 2 2 Shear viscosity 148
1220 1760 1640 1230 1752 2160 1735 1356 1720 1625 1 ( Pa. S ) 0 1220 1760 1640 1230 1752 2160 1735 1356 1720 1625 1 ( Pa. S ) 0
剪切粘度 Shear viscosity
160 245 226 165 235 229 175 242 176 232 209 2 ( Pa. S ) 160 245 226 165 235 229 175 242 176 232 209 2 ( Pa. S )
Charpy 19. Charpy 19.
32. 8 25. 4 28. 7 10. 5 22. 8 15. 4 24. 5 28. 6 26. 6 28. 5 ( Kj/m2 ) 7 32. 8 25. 4 28. 7 10. 5 22. 8 15. 4 24. 5 28. 6 26. 6 28. 5 ( Kj/m 2 ) 7
113. 118. 115. 1 14. 117. 112. 98. 1 16. 107. 1 17. 114. 113. 118. 115. 1 14. 117. 112. 98. 1 16. 107. 1 17. 114.
VST CO VST CO
5 4 3 5 6 1 9 8 6 3 2 表面质量 〇 Δ 〇 〇 〇 Ο Δ Ο Δ Δ Δ 从实施例 1〜4的实验结果可以看出， 依据本发明制备的吹塑成型用 ABS树脂组合 物， 具有优异的可吹塑性和高耐热性， 且吹塑制品具有良好的表面质量和耐冲击性能。 通过复配使用接枝共聚物 （A-1 )和耐热剂 （Β) ， 可使制备的 ABS树脂组合物的维卡软 化温度高达 110°C以上， 完全可以满足汽车零部件喷漆后加工工艺的耐热要求和较为苛 刻的使用环境； 而且， 本发明制备的树脂组合物的初始熔体粘度低， 熔体粘度对剪切速 率的敏感性小，可以减小吹塑型坯由于通过狭窄挤出口模时的高剪切力引起熔体粘度下 降而导致的熔体下垂现象。 5 4 3 5 6 1 9 8 6 3 2 Surface quality 〇Δ 〇〇〇Ο Δ Ο Δ Δ Δ It can be seen from the experimental results of Examples 1 to 4 that the ABS resin composition for blow molding prepared according to the present invention It has excellent blown plasticity and high heat resistance, and the blow molded products have good surface quality and impact resistance. By using the graft copolymer (A-1) and the heat-resistant agent (Β), the Vicat softening temperature of the prepared ABS resin composition can be as high as 110 ° C or more, which can fully satisfy the post-painting process of automobile parts. The heat resistance requirement and the more demanding use environment; moreover, the resin composition prepared by the invention has low initial melt viscosity, low sensitivity of melt viscosity to shear rate, and can reduce blown parison due to narrow extrusion The high shear force at the time of exiting the mold causes a phenomenon of melt sagging caused by a decrease in melt viscosity.
对比例 1， 利用溶液法制备的基于高含量 N-苯基马来酰亚胺组分的耐热剂 B1制备 的树脂组合物， 耐热提高非常明显， 但是由于耐热剂的玻璃化转变温度很高， 组合物的 初始熔体粘度很大， 容易造成塑化不良， 严重影响制品的表面质量； 熔体剪切粘度随剪 切速率的变化大， 容易造成吹塑型坯下垂； 且 Charpy冲击性能明显下降。 Comparative Example 1, the resin composition prepared by the solution method based on the high-content N-phenylmaleimide component-based heat-resistant agent B1, the heat resistance is improved significantly, but due to the glass transition temperature of the heat-resistant agent Very high, the initial melt viscosity of the composition is very large, which is easy to cause poor plasticization, which seriously affects the surface quality of the product; the melt shear viscosity varies greatly with the shear rate, which easily causes the blown parison to sag; and Charpy impact The performance is significantly reduced.
同样地， 对比例 3， 耐热剂 N-苯基马来酰亚胺 - α -甲基苯乙烯-丙烯腈-苯乙烯 四元共聚物中的 Ν-苯基马来酰亚胺含量达到 40重量份时， 吹塑制品的表明质量大 大受到影响。
对比例 2， 利用苯乙烯-马来酸酐共聚物 （B2) 作为耐热剂制备的树脂组合物， 耐 热提高非常有限， 维卡软化温度低； 而且， 由于马来酸酐组分的热稳定性差， 而吹塑制 品的成型周期长， SMA较差的热稳定性极易引起产品表面质量不佳。 Similarly, in Comparative Example 3, the content of fluorenyl-phenylmaleimide in the heat-resistant N-phenylmaleimide-α-methylstyrene-acrylonitrile-styrene quaternary copolymer reached 40. At the time of weight, the quality of the blow molded article is greatly affected. Comparative Example 2, a resin composition prepared by using a styrene-maleic anhydride copolymer (B2) as a heat resistant agent, has a very low heat resistance improvement, a low Vicat softening temperature; and, because of poor thermal stability of a maleic anhydride component However, the molding cycle of blow molded products is long, and the poor thermal stability of SMA is likely to cause poor surface quality of the product.
对比例 4， 使用成 α -甲基苯乙烯-丙烯腈共聚物 （Β3 ) 作为耐热剂制备树脂组 合物时， 耐热提高也非常有限， 维卡软化温度低， 达不到使用要求。 In Comparative Example 4, when a resin composition was prepared by using α-methylstyrene-acrylonitrile copolymer (Β3) as a heat-resistant agent, the heat resistance was also extremely limited, and the Vicat softening temperature was low, which did not meet the requirements for use.
对比例 5， 6， 使用凝胶含量分别为 80%、 75%的 A-1和 Α-2接枝共聚物时， 树脂的 物理性能和表面麻点质量尚可。 但值得注意的是， 其制备的树脂组合物在吹塑成型时的 制件厚度分布不均匀。 Comparative Example 5, 6, When 80% and 75% of the A-1 and Α-2 graft copolymers were used, the physical properties and surface pitting quality of the resin were acceptable. However, it is worth noting that the resin composition prepared by the resin composition has a non-uniform thickness distribution during blow molding.
实施例 6〜9 Example 6~9
( 1 ) 实施例 6〜9 中， 采用的原材料为： 100重量份的苯乙烯类树脂组合物 A 和 20重量份的耐热剂 B; (1) In the examples 6 to 9, the raw materials used are: 100 parts by weight of the styrenic resin composition A and 20 parts by weight of the heat resistant agent B;
所述苯乙烯类树脂组合物 A的组分及重量份数如下， 按 100重量份计： 接枝共聚物 A-lc 30重量份； The components and parts by weight of the styrenic resin composition A are as follows, based on 100 parts by weight: 30 parts by weight of the graft copolymer A-lc;
接枝共聚物 A-2b 10重量份； Graft copolymer A-2b 10 parts by weight;
共聚物 A-3a 60重量份； Copolymer A-3a 60 parts by weight;
其中， 接枝共聚物 A-lc为聚丁二烯橡胶接枝苯乙烯-丙烯腈 _ α -甲基苯乙烯共 聚物， 各单体的配比 （重量份） 如表 2所示； Wherein, the graft copolymer A-lc is a polybutadiene rubber grafted styrene-acrylonitrile_α-methylstyrene copolymer, and the ratio (parts by weight) of each monomer is shown in Table 2;
接枝共聚物 A-2b为聚丁二烯橡胶接枝苯乙烯-丙烯腈共聚物，各单体的配比（重 量份） 如表 2所示； The graft copolymer A-2b is a polybutadiene rubber grafted styrene-acrylonitrile copolymer, and the ratio (parts by weight) of each monomer is shown in Table 2;
共聚物 A-3a为苯乙烯-丙烯腈共聚物， 各单体的配比 （重量份） 如表 2所示； 耐热剂为 B-la为连续本体法合成的 N-苯基马来酰亚胺 - α -甲基苯乙烯-丙烯腈 -苯乙烯四元共聚物， 各单体的配比 （重量份） 如表 2所示； Copolymer A-3a is a styrene-acrylonitrile copolymer, and the ratio (parts by weight) of each monomer is shown in Table 2; the heat resistant agent is B-la, which is a continuous bulk synthesis of N-phenylmaleyl. Imine-α-methylstyrene-acrylonitrile-styrene quaternary copolymer, the proportion (parts by weight) of each monomer is shown in Table 2;
滑石粉 （C) 的目数为 2500〜5000目， 1重量份； The mesh number of talc (C) is 2500~5000 mesh, 1 part by weight;
聚烯烃类蜡 （D) 为市售的聚乙烯蜡， 1重量份； Polyolefin wax (D) is a commercially available polyethylene wax, 1 part by weight;
抗氧剂（Ε) 为市售的受阻单酚、 双酚或多酚化合物与亚磷酸酯类化合物的混合物，
重量份。 Antioxidant (Ε) is a commercially available hindered monophenol, bisphenol or a mixture of a polyphenol compound and a phosphite compound, Parts by weight.
相应树脂组合物的制备方法和性能检测方法均同实施例 1。 The preparation method and the property detection method of the corresponding resin composition were the same as those in Example 1.
表 2 Table 2
VST ( °C ) 111. 4 114. 3 1 12. 4 110. 8 表面质量 Δ 〇 Δ 〇 连续本体聚合方法制备的耐热剂 B中， 为了解决较低的马来酰亚胺含量引起耐热性 降低造成的问题， 除了通过四元共聚物中同时引入适量 α _甲基苯乙烯组分来弥补外， 还在 ABS树脂制备过程中选择耐热性提高的接枝共聚物 A-1与耐热剂 Β复配使用来进一 步提高 ABS树脂的耐热性。 VST ( °C ) 111. 4 114. 3 1 12. 4 110. 8 Surface quality Δ 〇 Δ 耐热 In the heat-resistant agent B prepared by the continuous bulk polymerization method, heat resistance is caused in order to solve the lower maleimide content. The problem caused by the decrease in the properties, in addition to the simultaneous addition of an appropriate amount of α-methylstyrene component in the tetrapolymer, the graft copolymer A-1 with improved heat resistance is also selected during the preparation of the ABS resin. The thermal agent is compounded to further improve the heat resistance of the ABS resin.
此外，接枝共聚物 A-1中的 α -甲基苯乙烯的含量必须适量， 为了使得本发明的 ABS 树脂组合物的维卡软化温度达到 110°C， 且吹塑制品具有优异的表面质量， 所述接枝共 聚物 A-1中， α -甲基苯乙烯组分必须控制在 35〜75重量份；进一步以实施例 6为基准， 保持其他条件不变，仅调整接枝共聚物 A-1中单体混合物的各组分配比关系， 分别调 整 α -甲基苯乙烯的重量份数为 25和 80重量份， 其结果如表 3所示。 可见， 接枝 共聚物 A-1中， α -甲基苯乙烯〈35重量份， 则 ABS树脂组合物的维卡软化温度难以达 到 11CTC ; 而当 α -甲基苯乙烯〉 75重量份， 则相应的 ABS树脂组合物的耐热较好， 但相 应吹塑制品的表面质量较差。 Further, the content of α-methylstyrene in the graft copolymer A-1 must be an appropriate amount in order to make the Vicat softening temperature of the ABS resin composition of the present invention to 110 ° C, and the blow molded article has an excellent surface quality. , in the graft copolymer A-1, the α-methylstyrene component must be controlled at 35 to 75 parts by weight; further on the basis of Example 6, while maintaining other conditions, only the graft copolymer A is adjusted. The distribution ratio of each group of the monomer mixture in -1 was adjusted to 25 and 80 parts by weight, respectively, of the α-methylstyrene, and the results are shown in Table 3. It can be seen that, in the graft copolymer A-1, the α-methylstyrene is <35 parts by weight, the Vicat softening temperature of the ABS resin composition is difficult to reach 11 CTC; and when the α-methylstyrene is 75 parts by weight, The corresponding ABS resin composition has better heat resistance, but the surface quality of the corresponding blow molded article is poor.
表 3 table 3
以上对实施例的描述中，橡胶型接枝共聚物 A-1和 Α-2中的橡胶仅列举了聚丁二烯 橡胶， 其他几类橡胶： 丁苯橡胶、 丙烯酸酯橡胶、 丁腈橡胶也适用于本发明， 不同的橡
胶能够带来其他不同的效果： 丁苯橡胶可以提高树脂组合物的流动性； 丙烯酸酯橡胶可 以提高树脂组合物的耐候性； 丁腈橡胶可以提高树脂组合物的耐油性。 综上所述，本发明通过向包含特定组分特定量的苯乙烯类树脂组合物中加入特定方 法合成的具有特定组分特定量的耐热剂， 并与树脂组合物中的组分发生协同作用， 进而 解决了现有技术中吹塑成型用耐热级 ABS树脂在成本、 成型、 表面质量、 厚度分布、 耐 热性能 /冲击性能等方面存在的问题； 本发明制备了可吹塑性和耐热性倶佳的吹塑成型 用高耐热 ABS树脂组合物， 吹塑制品具有良好的表面质量和耐冲击性能； 本发明的树脂 组合物的熔体强度高且熔体粘度对剪切速率的敏感性小，可以减小吹塑型坯的熔体下垂 现象，且吹塑制品的表面质量好；本发明的树脂组合物的耐热高，维卡软化温度达 110°C 以上， 可以满足汽车零部件喷漆后加工工艺的耐热要求和较为苛刻的使用环境， 且吹塑 制品的耐冲击性能好。 In the above description of the examples, the rubbers in the rubber-type graft copolymers A-1 and Α-2 are only polybutadiene rubber, and other types of rubber: styrene-butadiene rubber, acrylate rubber, nitrile rubber Suitable for use in the present invention, different oak Glue can bring about other different effects: Styrene-butadiene rubber can improve the fluidity of the resin composition; Acrylate rubber can improve the weather resistance of the resin composition; Nitrile rubber can improve the oil resistance of the resin composition. In summary, the present invention synthesizes a specific amount of a heat-resistant agent having a specific component synthesized by adding a specific method to a specific amount of a styrene-based resin composition containing a specific component, and synergizes with components in the resin composition. The invention further solves the problems in the prior art, such as cost, molding, surface quality, thickness distribution, heat resistance/impact performance, etc. in the heat-resistant ABS resin for blow molding; the invention prepares blowable plasticity and A heat-resistant high heat-resistant ABS resin composition for blow molding, which has good surface quality and impact resistance; the melt strength of the resin composition of the present invention is high and the melt viscosity versus shear rate The sensitivity is small, the melt drooping phenomenon of the blown parison can be reduced, and the surface quality of the blow molded product is good; the resin composition of the invention has high heat resistance, and the Vicat softening temperature is above 110 ° C, which can satisfy the automobile The heat-resisting requirements of the processing technology of the parts after painting and the more demanding use environment, and the impact resistance of the blow molded products is good.
以上仅仅是对本发明的较佳实施例和对比例进行的详细说明， 但是本发明并不限于 以上实施例和对比例。应该理解的是，在不脱离本申请的权利要求的精神和范围情况下， 本领域的技术人员做出的各种修改， 仍属于本发明的范围。
The above is only a detailed description of the preferred embodiments and comparative examples of the present invention, but the present invention is not limited to the above examples and comparative examples. It should be understood that various modifications made by those skilled in the art are still within the scope of the invention, without departing from the spirit and scope of the appended claims.
Claims
1、 一种适于吹塑成型的高耐热 ABS 树脂组合物， 其特征在于， 所述组合物包 含： 100重量份的苯乙烯类树脂组合物 A和 20〜40重量份的耐热剂 B; 1. A high heat-resistant ABS resin composition suitable for blow molding, characterized in that the composition contains: 100 parts by weight of styrenic resin composition A and 20 to 40 parts by weight of heat-resistant agent B ;
(a)所述苯乙烯类树脂组合物 A的组分及重量份数如下， 按 100重量份计： 接枝共聚物 A- 1 10〜40重量份； (a) The components and parts by weight of the styrenic resin composition A are as follows, based on 100 parts by weight: Graft copolymer A-1 10~40 parts by weight;
接枝共聚物 A-2 0〜30重量份； Graft copolymer A-2 0~30 parts by weight;
共聚物 A-3 55〜80重量份； Copolymer A-3 55~80 parts by weight;
(b)所述接枝共聚物 A-1的制备方法包括如下步骤： 按 100重量份计， 在 10〜 70重量份的橡胶型聚合物存在下， 通过 90〜30重量份的单体混合物聚合而制得的 接枝共聚物；其中，所述单体混合物的组分及重量份数如下， 按 100重量份计： 35〜 75重量份的 α -甲基苯乙烯、 5〜45重量份的苯乙烯、 10〜25重量份的丙烯腈组分； (b) The preparation method of the graft copolymer A-1 includes the following steps: polymerizing 90 to 30 parts by weight of a monomer mixture in the presence of 10 to 70 parts by weight of a rubber-type polymer based on 100 parts by weight The obtained graft copolymer; wherein, the components and parts by weight of the monomer mixture are as follows, based on 100 parts by weight: 35~75 parts by weight of α-methylstyrene, 5~45 parts by weight of Styrene, 10 to 25 parts by weight of acrylonitrile component;
(c)所述接枝共聚物 Α-2的制备方法包括如下步骤： 按 100重量份计， 在 10〜 70重量份的橡胶型聚合物存在下， 通过 90〜30重量份的单体混合物聚合而制得的 接枝共聚物；其中，所述单体混合物的组分及重量份数如下， 按 100重量份计： 10〜 30重量份的丙烯腈和 70〜90重量份的苯乙烯组分； (c) The preparation method of the graft copolymer A-2 includes the following steps: based on 100 parts by weight, in the presence of 10 to 70 parts by weight of a rubber-type polymer, polymerizing by 90 to 30 parts by weight of a monomer mixture The obtained graft copolymer; wherein, the components and parts by weight of the monomer mixture are as follows, based on 100 parts by weight: 10 to 30 parts by weight of acrylonitrile and 70 to 90 parts by weight of styrene components ;
(d)所述共聚物 A-3 的制备方法包括如下步骤： 通过单体混合物聚合而制得的 共聚物； 其中， 所述单体混合物的组分及重量份数如下， 按 100重量份计： 18〜48 重量份的丙烯腈单体和 52〜82重量份的苯乙烯单体。 (d) The preparation method of the copolymer A-3 includes the following steps: a copolymer prepared by polymerizing a monomer mixture; wherein, the components and weight parts of the monomer mixture are as follows, based on 100 parts by weight : 18~48 parts by weight of acrylonitrile monomer and 52~82 parts by weight of styrene monomer.
2、 如权利要求 1所述的适于吹塑成型的高耐热 ABS树脂组合物， 其特征在于， 所 述接枝共聚物 A- 1以及接枝共聚物 A-2制备中采用的橡胶型聚合物为聚丁二烯橡胶、 丁苯橡胶、 丙烯酸酯橡胶、 丁腈橡胶中的一种或几种的混合。 2. The high heat-resistant ABS resin composition suitable for blow molding as claimed in claim 1, characterized in that the rubber type used in the preparation of the graft copolymer A-1 and the graft copolymer A-2 The polymer is one or a mixture of polybutadiene rubber, styrene-butadiene rubber, acrylate rubber, and nitrile rubber.
3、 如权利要求 1所述的适于吹塑成型的高耐热 ABS树脂组合物， 其特征在于， 所 述接枝共聚物 A- 1以及接枝共聚物 A-2的凝胶含量均大于等于 85%。 3. The high heat-resistant ABS resin composition suitable for blow molding according to claim 1, wherein the gel content of the graft copolymer A-1 and the graft copolymer A-2 is greater than equal to 85%.
4、 如权利要求 1所述的适于吹塑成型的高耐热 ABS树脂组合物， 其特征在于， 所 述接枝共聚物 A- 1以及接枝共聚物 A-2的凝胶含量均大于等于 90%。
4. The high heat-resistant ABS resin composition suitable for blow molding according to claim 1, wherein the gel content of the graft copolymer A-1 and the graft copolymer A-2 is greater than equal to 90%.
5、 如权利要求 1所述的适于吹塑成型的高耐热 ABS树脂组合物， 其特征在于， 所 述接枝共聚物 A- 1以及接枝共聚物 A-2的橡胶粒径均小于等于 400nm。 5. The high heat-resistant ABS resin composition suitable for blow molding according to claim 1, wherein the rubber particle diameters of the graft copolymer A-1 and the graft copolymer A-2 are both less than Equal to 400nm.
6、 如权利要求 1所述的适于吹塑成型的高耐热 ABS树脂组合物， 其特征在于， 所 述接枝共聚物 A- 1以及接枝共聚物 A-2的橡胶粒径均小于等于 300nm。 6. The highly heat-resistant ABS resin composition suitable for blow molding according to claim 1, wherein the rubber particle diameters of the graft copolymer A-1 and the graft copolymer A-2 are both less than Equal to 300nm.
7、 如权利要求 1所述的适于吹塑成型的高耐热 ABS树脂组合物， 其特征在于， 所 述共聚物 A-3的分子量为 100, 000〜300, 000。 7. The high heat-resistant ABS resin composition suitable for blow molding according to claim 1, wherein the molecular weight of the copolymer A-3 is 100,000~300,000.
8、 如权利要求 1所述的适于吹塑成型的高耐热 ABS树脂组合物， 其特征在于， 所 述共聚物 A-3的分子量为 180, 000〜300, 000。 8. The high heat-resistant ABS resin composition suitable for blow molding according to claim 1, wherein the molecular weight of the copolymer A-3 is 180,000~300,000.
9、 如权利要求 1所述的适于吹塑成型的高耐热 ABS树脂组合物， 其特征在于， 所 述耐热剂 B为 N-苯基马来酰亚胺 - α -甲基苯乙烯-丙烯腈-苯乙烯四元共聚物， 采用连 续本体聚合法合成。 9. The highly heat-resistant ABS resin composition suitable for blow molding as claimed in claim 1, wherein the heat-resistant agent B is N-phenylmaleimide-α-methylstyrene. -Acrylonitrile-styrene tetrapolymer, synthesized by continuous bulk polymerization method.
10、 如权利要求 1所述的适于吹塑成型的高耐热 ABS树脂组合物， 其特征在于， 所述耐热剂 Β的组分及重量份数如下， 按 100重量份计， 其中， Ν-苯基马来酰亚胺 组分 20〜30重量份， α -甲基苯乙烯组分 30〜50重量份， 苯乙烯组分 10〜40重量 份， 丙烯腈组分 20〜40重量份。 10. The high heat-resistant ABS resin composition suitable for blow molding according to claim 1, wherein the components and parts by weight of the heat-resistant agent B are as follows, based on 100 parts by weight, wherein, N-phenylmaleimide component 20~30 parts by weight, α-methylstyrene component 30~50 parts by weight, styrene component 10~40 parts by weight, acrylonitrile component 20~40 parts by weight .
11、 如权利要求 1所述的适于吹塑成型的高耐热 ABS树脂组合物， 其特征在于， 所述耐热剂 Β的玻璃化转变温度为 140〜160°C。 11. The high heat-resistant ABS resin composition suitable for blow molding according to claim 1, wherein the glass transition temperature of the heat-resistant agent B is 140~160°C.
12、一种如权利要求 1所述的适于吹塑成型的高耐热 ABS树脂组合物的制备方法， 其特征在于， 包括如下步骤： 12. A method for preparing a high heat-resistant ABS resin composition suitable for blow molding as claimed in claim 1, characterized in that it includes the following steps:
步骤 1， 按照重量份数称取各组分； Step 1: Weigh each component according to parts by weight;
步骤 2， 将各组分在高速混合机中充分混合， 得混合物； Step 2: Mix each component thoroughly in a high-speed mixer to obtain a mixture;
步骤 3， 将混合物从双螺杆挤出机的主喂料进入， 经过熔融挤出、 冷却、 干燥、 切 粒， 即得所述 ABS树脂组合物。 Step 3: Enter the mixture from the main feed of the twin-screw extruder, and undergo melt extrusion, cooling, drying, and pelletizing to obtain the ABS resin composition.
13、 如权利要求 11所述的制备方法， 其特征在于， 步骤 3中， 所述的双螺杆挤出 机的螺杆长径比为 30〜70， 机筒必须设置至少两处真空抽排装置， 螺杆料机筒进料段 温度为 180〜210°C、 塑化段温度为 230〜250°C、 均化段温度为 220〜240 °C， 螺杆转
速为 200〜500rpn
13. The preparation method according to claim 11, wherein in step 3, the screw length-to-diameter ratio of the twin-screw extruder is 30 to 70, and the barrel must be equipped with at least two vacuum evacuation devices. The temperature of the feeding section of the screw barrel is 180~210°C, the temperature of the plasticizing section is 230~250°C, and the temperature of the homogenizing section is 220~240°C. The screw rotates Speed is 200~500rpn
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019121647A1 (en) * | 2017-12-19 | 2019-06-27 | Ineos Styrolution Group Gmbh | Abs thermoplastic molding composition for blow molding |
| CN115044165A (en) * | 2022-08-17 | 2022-09-13 | 山东东临新材料股份有限公司 | ABS resin composition and preparation method thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK3012255T3 (en) * | 2013-06-17 | 2021-12-06 | Taiho Pharmaceutical Co Ltd | STABLE CRYSTAL FORM OF TIPIRACILHYDROCHLORIDE AND ITS CRYSTALLIZATION PROCEDURE |
| KR101811485B1 (en) | 2014-11-28 | 2017-12-21 | 주식회사 엘지화학 | Thermoplastic Resin Composition and Molded Article Thereof |
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| KR102639153B1 (en) * | 2021-12-01 | 2024-02-21 | 금호석유화학 주식회사 | Low odor acrylonitrile-butadiene-styrene based resin composition with excellent antibacterial property |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3111501A (en) * | 1958-12-19 | 1963-11-19 | Us Rubber Co | Gum plastic material comprising alpha-methyl styrene: acrylonitrile resin and graft copolymer of styrene and acrylonitrile on polybutadiene |
| EP0276512A1 (en) * | 1986-12-20 | 1988-08-03 | Dsm N.V. | Thermoplastic polymer mixtures |
| CN1455786A (en) * | 2001-01-08 | 2003-11-12 | Lg化学株式会社 | Method for preparing thermoplastic resin |
| CN1934189A (en) * | 2004-12-31 | 2007-03-21 | Lg化学株式会社 | Plastic resin composition having improved heat resistance, weld strength, chemical resistance, impact strength, elongation, and wettability |
| CN101065413A (en) * | 2004-12-01 | 2007-10-31 | 第一毛织株式会社 | Thermoplastic abs resin composition with improved impact resistance, dimensional stability and blow molding property |
| CN101250314A (en) * | 2007-11-30 | 2008-08-27 | 上海锦湖日丽塑料有限公司 | Heat-proof ABS resin composition for blow-molding and preparation method thereof |
| CN103342874A (en) * | 2013-07-19 | 2013-10-09 | 上海锦湖日丽塑料有限公司 | Heat-resisting ABS (Acrylonitrile-Butadiene-Styrene) resin applicable to electroplating and preparation method thereof |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3367995A (en) * | 1965-02-26 | 1968-02-06 | Kanegafuchi Chemical Ind | Method for preparing graft copolymers of diene rubber, styrene, acrylonitrile and alpha-methyl styrene |
| CN1005633B (en) * | 1984-06-19 | 1989-11-01 | 电气化学工业株式会社 | Thermoplastic resin composition |
| JPH0725964B2 (en) * | 1986-04-07 | 1995-03-22 | 東レ株式会社 | Thermoplastic resin composition |
| JPH0794591B2 (en) * | 1987-10-02 | 1995-10-11 | 日本合成ゴム株式会社 | Thermoplastic resin composition |
| JPH06344430A (en) * | 1993-06-03 | 1994-12-20 | Kanegafuchi Chem Ind Co Ltd | Blow molding method |
| JPH07137117A (en) * | 1993-11-12 | 1995-05-30 | Kanegafuchi Chem Ind Co Ltd | Blow molding method |
| JPH07286085A (en) * | 1994-04-20 | 1995-10-31 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin composition |
| JPH0847963A (en) * | 1994-08-04 | 1996-02-20 | Kanegafuchi Chem Ind Co Ltd | Blow molding machine and method |
| KR100375814B1 (en) * | 1996-11-04 | 2003-07-22 | 주식회사 엘지씨아이 | Method for preparing thermoplastic resin composition having excellent impact resistance |
| JPH1025394A (en) * | 1996-07-11 | 1998-01-27 | Japan Synthetic Rubber Co Ltd | Rubber-reinforced styrene resin composition |
| JPH1036619A (en) * | 1996-07-17 | 1998-02-10 | Japan Synthetic Rubber Co Ltd | Blow-moldable rubber-reinforced styrenic resin composition |
| JPH10265642A (en) * | 1997-03-25 | 1998-10-06 | Kanegafuchi Chem Ind Co Ltd | Abs resin composition for blow molding and blow molded item produced therefrom |
| JPH11116827A (en) * | 1997-10-16 | 1999-04-27 | Techno Polymer Kk | Flame resistant thermoplastic resin composition for blow molding |
| JPH11181224A (en) * | 1997-12-22 | 1999-07-06 | Kanegafuchi Chem Ind Co Ltd | Resin composition and blow molded product using the same |
| JP2001279049A (en) * | 2000-03-28 | 2001-10-10 | Kanegafuchi Chem Ind Co Ltd | Abs-based resin composition for blow molding use and the resultant blow molded product |
| KR100409071B1 (en) * | 2000-07-03 | 2003-12-11 | 주식회사 엘지화학 | Process for preparing thermoplastic resin having superior heat-stability |
| JP2003080596A (en) * | 2001-06-26 | 2003-03-19 | Matsushita Electric Works Ltd | Resin molded article and manufacturing method thereof |
| WO2007135852A1 (en) * | 2006-05-19 | 2007-11-29 | Umg Abs, Ltd. | Thermoplastic resin composition and composite moldings |
| EP2471821B1 (en) * | 2006-09-28 | 2017-02-01 | Korea Kumho Petrochemical Co., Ltd. | Maleimide-alpha-alkylstyrene-based tetrapolymer with low molten viscosity |
| CN101921439B (en) * | 2010-06-29 | 2012-05-30 | 上海达凯塑胶有限公司 | ABS (Acrylonitrile Butadiene Styrene) calendered substrate and preparation method thereof |
| JP5752505B2 (en) * | 2011-07-05 | 2015-07-22 | リケンテクノス株式会社 | Thermoplastic resin composition |
| CN103183762B (en) * | 2011-12-29 | 2015-08-05 | 奇美实业股份有限公司 | Styrene-alpha-methylstyrene-acrylonitrile copolymer and rubber-modified styrene resin |
| CN103333456B (en) * | 2013-07-19 | 2016-08-24 | 上海锦湖日丽塑料有限公司 | A kind of heat-resisting ABS resin with excellent blowing surface and preparation method thereof |
-
2013
- 2013-11-20 CN CN201310590377.2A patent/CN103613877B/en active Active
- 2013-12-04 WO PCT/CN2013/088527 patent/WO2015074297A1/en active Application Filing
- 2013-12-04 JP JP2016533619A patent/JP6364490B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3111501A (en) * | 1958-12-19 | 1963-11-19 | Us Rubber Co | Gum plastic material comprising alpha-methyl styrene: acrylonitrile resin and graft copolymer of styrene and acrylonitrile on polybutadiene |
| EP0276512A1 (en) * | 1986-12-20 | 1988-08-03 | Dsm N.V. | Thermoplastic polymer mixtures |
| CN1455786A (en) * | 2001-01-08 | 2003-11-12 | Lg化学株式会社 | Method for preparing thermoplastic resin |
| CN101065413A (en) * | 2004-12-01 | 2007-10-31 | 第一毛织株式会社 | Thermoplastic abs resin composition with improved impact resistance, dimensional stability and blow molding property |
| CN1934189A (en) * | 2004-12-31 | 2007-03-21 | Lg化学株式会社 | Plastic resin composition having improved heat resistance, weld strength, chemical resistance, impact strength, elongation, and wettability |
| CN101250314A (en) * | 2007-11-30 | 2008-08-27 | 上海锦湖日丽塑料有限公司 | Heat-proof ABS resin composition for blow-molding and preparation method thereof |
| CN103342874A (en) * | 2013-07-19 | 2013-10-09 | 上海锦湖日丽塑料有限公司 | Heat-resisting ABS (Acrylonitrile-Butadiene-Styrene) resin applicable to electroplating and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019121647A1 (en) * | 2017-12-19 | 2019-06-27 | Ineos Styrolution Group Gmbh | Abs thermoplastic molding composition for blow molding |
| CN115044165A (en) * | 2022-08-17 | 2022-09-13 | 山东东临新材料股份有限公司 | ABS resin composition and preparation method thereof |
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| CN103613877B (en) | 2017-09-19 |
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