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WO2018107969A1 - Pc/abs composition, preparation method therefor and use thereof - Google Patents

Pc/abs composition, preparation method therefor and use thereof Download PDF

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Publication number
WO2018107969A1
WO2018107969A1 PCT/CN2017/113751 CN2017113751W WO2018107969A1 WO 2018107969 A1 WO2018107969 A1 WO 2018107969A1 CN 2017113751 W CN2017113751 W CN 2017113751W WO 2018107969 A1 WO2018107969 A1 WO 2018107969A1
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Prior art keywords
abs
acrylonitrile
abs composition
butadiene
melt
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PCT/CN2017/113751
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French (fr)
Chinese (zh)
Inventor
卢朝亮
王琪
林荣涛
杨波
李文龙
郭涛
罗忠富
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金发科技股份有限公司
上海金发科技发展有限公司
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Publication of WO2018107969A1 publication Critical patent/WO2018107969A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • C08K5/134Phenols containing ester groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472Five-membered rings
    • C08K5/3475Five-membered rings condensed with carbocyclic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/521Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions 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
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/08Copolymers of styrene
    • C08L25/14Copolymers of styrene with unsaturated esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a PC/ABS composition and a preparation method and application thereof.
  • PC/ABS alloy non-crystalline plastic, with high rigidity, high strength, easy processing, etc.
  • PC/ABS materials are easily absorbed by water during processing due to the influence of terminal hydroxyl groups in the PC, which leads to degradation, resulting in deterioration of material properties and appearance defects.
  • PC/ABS alloy is a partially compatible system, usually There is a phenomenon in which the phase distribution is not uniform and the domain size is too large, resulting in a decrease in impact resistance and instability, and a safety hazard in the use of the automobile interior.
  • CN201410186085 uses MBS as a toughening agent and uses a polymer containing maleic anhydride or epoxy as a compatibilizer to improve the impact properties of the material by using a low molecular weight AS synergistically to improve the phase interface of the PC/ABS.
  • CN03142022 uses ABS/PP-MAH as a compatibilizer to improve the comprehensive mechanical properties of the material; CN201310713277 uses a composite of GMA and MAH as a compatibilizer and toughened with a toughening agent to improve the low temperature impact properties of the material. And multi-axis impact.
  • a primary object of the present invention is to overcome the deficiencies of the prior art described above and to provide a PC/ABS composition having high impact resistance.
  • Another object of the present invention is to provide a process for the preparation of the above PC/ABS composition.
  • a PC/ABS composition by weight, comprising the following components:
  • the polycarbonate resin is a bisphenol A type polycarbonate, and the melt mass flow rate is at 300 ° C, 5 Kg load.
  • MFR is 8g/10min-10g/10min;
  • the acrylonitrile-butadiene-styrene resin has a melt mass flow rate MFR of 15 g/10 min to 20 g/10 min at 220 ° C under a load of 10 kg.
  • the acrylonitrile-butadiene-styrene resin is an emulsion method ABS, the rubber size of which is controlled within a particle diameter of 300 nm, and the particle diameter exhibits a bimodal distribution based on the total weight of the acrylonitrile-butadiene-styrene resin.
  • the weight of rubber is 18-22%.
  • the compatibilizer is maleic anhydride (MAH) grafted ABS, styrene-acrylonitrile-glycidyl methacrylate (GMA) copolymer or methyl methacrylate (MMA)-glycidyl methacrylate ( GMA) one or more of the copolymers, wherein maleic anhydride (MAH), glycidyl methacrylate (GMA), methyl methacrylate (MMA) functional group content is 1g / mol -5g / mol .
  • the compatibilizer can be distributed on the interface between PC and ABS to improve the compatibility of the two phases and to refine the domain size. The role.
  • the PC/ABS composition of the present invention further comprises 0.2-1 parts of an auxiliary agent, which is an antioxidant, a light stabilizer or a lubricant, without impairing the effects of the present invention. At least one of them.
  • the antioxidant is a hindered phenol and a phosphite antioxidant, specifically one of 1010, 1076, 3114, 168, PEP-36 or a mixture of two or more;
  • the light stabilizer is a hindered amine light stabilizer, specifically one of UV-3808PP5, LA-402XP, LA-402AF, 770, 944, 234 or a mixture of two or more;
  • the lubricant is one or a mixture of two or more of silicones, esters, amides, polyethylenes, stearic acids, fatty acids and esters;
  • the preparation method of the above PC/ABS composition of the present invention comprises the following steps:
  • the acrylonitrile-butadiene-styrene copolymer and the compatibilizer are mixed in proportion and then added to the twin-screw extruder for melt-kneading, the melt-kneading temperature is 210-220 ° C, and the screw rotation speed is 350-450 rpm, extrusion granulation, to obtain ABS composition;
  • ABS composition is uniformly mixed with the polycarbonate resin and the auxiliary agent, and then added to the twin-screw extruder for melt-kneading, the melt-kneading temperature is 250-260 ° C, and the screw rotation speed is 350-450 rpm.
  • the pellets were extruded and granulated to obtain a PC/ABS composition.
  • the present invention also provides the use of the above PC/ABS composition in automotive interiors.
  • the invention has the following beneficial effects:
  • the invention can obtain a nano-scale bicontinuous phase structure by controlling the PC/ABS ratio and matching the viscosity of PC and ABS, which can effectively improve the high-speed impact resistance of the material, and the multiaxial impact performance is toughness.
  • the fracture and the safety of use are improved, and the prepared PC/ABS composition has good toughness and safety at high speed impact while ensuring rigidity of the material, and can be widely used for preparing automotive interior parts.
  • the invention adopts a secondary over-machine process, that is, the compatibilizer is pre-mixed with ABS first, which is favorable for uniform distribution of ABS and PC, and the formed double continuous structure is more stable and more uniform, and is favorable for stabilizing materials. High speed impact resistance.
  • the raw materials used in the present invention are all commercially available, as follows:
  • melt mass flow rate MFR is 9g/10min
  • melt mass flow rate MFR is 20g/10min
  • melt mass flow rate MFR is 2g/10min
  • ABS-1 emulsion method
  • its rubber size is within 300nm
  • the particle size shows a bimodal distribution
  • the weight content of rubber is 20%
  • the melt mass flow rate MFR is 15g/10min under 220°C and 10kg load.
  • ABS-2 emulsion method
  • the rubber size is within the particle size of 300nm, the particle size shows a bimodal distribution, the weight content of the rubber is 20%, the melt mass flow rate MFR is 8.7 at 220 ° C, 10kg load G/10min;
  • the rubber size is the particle size within 300nm, the particle size shows a bimodal distribution, the weight content of the rubber is 20%, the melt mass flow rate MFR is 30g at 220 °C, 10kg load /10min;
  • ABS-4 the bulk method, the rubber size is more than 1um, the weight content of the rubber is 25%, the melt mass flow rate MFR is 15g/10min under the load of 220 ° C, 10kg;
  • MAH Maleic anhydride
  • styrene-acrylonitrile-glycidyl methacrylate (GMA) copolymer having a GMA functional group content of 2 g/mol;
  • Antioxidant antioxidant 1076, antioxidant PEP-36;
  • Light stabilizer light stabilizer 234;
  • the detection method or standard used in the present invention is:
  • the damage forms of materials in ASTM D3763 are divided into two types, toughness and brittleness.
  • toughness When no break occurred in 3 or more of the 5 plates tested, it was judged to be tough, and the fracture form of the material was described as toughness; when 1-2 of the 5 plates tested showed fracture, it was judged to be close toughness.
  • the fracture form of the material is described as being close to toughness; when the five plates tested are judged to be brittle, the fracture form of the material is described as brittle.
  • the acrylonitrile-butadiene-styrene copolymer and the compatibilizer are mixed in proportion and then added to the twin-screw extruder for melt-kneading.
  • the melt-kneading temperature is 210-220. °C, screw rotation speed is 350-450 rpm, extrusion granulation, to obtain ABS composition;
  • ABS composition, polycarbonate resin, auxiliary agent are mixed uniformly in proportion and then added to twin-screw extruder for melt mixing
  • the refining, melt-kneading temperature was 250-260 ° C, the screw rotation speed was 350-450 rpm, and extrusion granulation was carried out to obtain a PC/ABS composition.
  • the polycarbonate resin, acrylonitrile-butadiene-styrene copolymer, compatibilizer and auxiliary agent are mixed uniformly in proportion and then added to a twin-screw extruder for melt-kneading and melting.
  • the kneading temperature was 250-260 ° C
  • the screw rotation speed was 350-450 rpm
  • extrusion granulation was carried out to obtain a PC/ABS composition.
  • the prepared PC/ABS composition was injection molded into a mechanical spline for testing the cantilever beam notched impact strength and flexural modulus, bending strength, and melt index.
  • the composition was injection molded into 10 ⁇ 10 ⁇ 0.3cm 3 square plate for multiaxial impact testing.
  • the performance parameters obtained by the test are shown in Table 2.
  • Example 1 Compared with Comparative Example 1-2, when the PC in the example was changed to a high-flow PC or a high-flow low-flow PC, the ABS was transferred from the PC due to a mismatch in PC and ABS viscosity. The force is weak, and the ABS is dispersed after molding. The phase form exists, which reduces the high-speed impact resistance of the material.
  • Example 1 Compared with Comparative Example 6, in Example 1, when the ABS content in the comparative example was increased and the PC content was decreased, the ABS was mainly used in the formulation system, and the resulting two-phase structure was PC and the dispersed phase was present in the ABS, which also decreased. The material's resistance to high-speed impact.
  • the present invention optimizes the ratio of PC, ABS, compatibilizer, and by matching the viscosity of PC and ABS, as well as controlling the rubber content of ABS, rubber size, and finally forming PC/ABS double continuous.
  • the structure significantly improves the material's high-speed impact resistance.
  • Example 1 Compared with Comparative Example 8, Example 1 compared with Comparative Example 9, using a secondary machine process, when the compatibilizer is premixed with ABS, which is favorable for the uniform distribution of ABS and PC.
  • the double continuous structure is more stable and more uniform, which is beneficial to stabilize the material against high-speed impact performance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed are a PC/ABS composition, a preparation method therefor and the use thereof. The composition comprises the components of: 60-70 parts of a polycarbonate resin; 30-40 parts of an acrylonitrile-butadiene-styrene copolymer; and 0.5-5 parts of a compatilizer, wherein the polycarbonate resin is a bisphenol A-type polycarbonate having a melt mass flow rate (MFR) of 8 g/10 min to 10 g/10 min at 300ºC under a load of 5 kg; and the acrylonitrile-butadiene-styrene resin has a melt mass flow rate (MFR) of 15 g/10 min to 20 g/10 min at 220ºC under a load of 10 kg. In the present invention, a nanoscale bicontinuous phase structure can be obtained by selecting and controlling the PC/ABS ratio and matching the viscosities of PC and ABS, the high-speed impact resistance of a material can be effectively improved, multi-axis impact is presented as a ductile fracture, the safety of use is improved, and the prepared PC/ABS composition has a good toughness and safety during high-speed impact while ensuring the rigidity of the material, and can be widely applied to the preparation of interior automobile parts.

Description

一种PC/ABS组合物及其制备方法和应用PC/ABS composition and preparation method and application thereof 技术领域Technical field
本发明涉及高分子材料技术领域,具体涉及一种PC/ABS组合物及其制备方法和应用。The invention relates to the technical field of polymer materials, in particular to a PC/ABS composition and a preparation method and application thereof.
背景技术Background technique
PC/ABS合金,非结晶性塑料,具有高刚性、高强度、易加工等特点,已成为车用塑料中用量很大一种工程塑料。然而PC/ABS材料由于PC中的端羟基影响,在加工过程中易吸水,从而引发降解,导致材料性能下降以及外观缺陷的产生,另外,由于PC/ABS合金为部分相容体系,通常情况下存在相态分布不均一,相畴尺寸过大的现象,从而导致其抗冲性能的下降以及不稳定性,在汽车内饰的使用上具有安全隐患。PC/ABS alloy, non-crystalline plastic, with high rigidity, high strength, easy processing, etc., has become a kind of engineering plastics in automotive plastics. However, PC/ABS materials are easily absorbed by water during processing due to the influence of terminal hydroxyl groups in the PC, which leads to degradation, resulting in deterioration of material properties and appearance defects. In addition, since PC/ABS alloy is a partially compatible system, usually There is a phenomenon in which the phase distribution is not uniform and the domain size is too large, resulting in a decrease in impact resistance and instability, and a safety hazard in the use of the automobile interior.
为了提升PC/ABS合金在汽车内饰上的适用性,提高其使用安全性,用于替代金属件实现汽车轻量化,常添加大量的弹性体进行增韧。CN201410186085采用MBS作为增韧剂,采用含有马来酸酐或者环氧基的聚合物作为相容剂,利用低分子量AS协同改善PC/ABS的相界面,从而改善材料的冲击性能。CN03142022采用ABS/PP-MAH作为相容剂,改善了材料的综合力学性能;CN201310713277采用含量有GMA及MAH的复合物作为相容剂,并采用增韧剂增韧,从而改善材料的低温冲击性能及多轴冲击。In order to improve the applicability of PC/ABS alloy in automotive interiors and improve the safety of its use, it is used to replace metal parts to achieve lightweight vehicles. It is often added with a large number of elastomers for toughening. CN201410186085 uses MBS as a toughening agent and uses a polymer containing maleic anhydride or epoxy as a compatibilizer to improve the impact properties of the material by using a low molecular weight AS synergistically to improve the phase interface of the PC/ABS. CN03142022 uses ABS/PP-MAH as a compatibilizer to improve the comprehensive mechanical properties of the material; CN201310713277 uses a composite of GMA and MAH as a compatibilizer and toughened with a toughening agent to improve the low temperature impact properties of the material. And multi-axis impact.
然而上述专利公开的PC/ABS抗冲改性中通过相容剂改性的体系,其高速撞击安全性无法保证,抗冲性能仍可进一步提升,而通过复配增韧剂增韧的体系则牺牲了材料的刚性。因此,本领域尚需开发一种制备简单且高效的抗冲改性方法,提升PC/ABS在汽车内饰应用上的优势。However, in the PC/ABS impact modification disclosed in the above patent, the system modified by the compatibilizer cannot guarantee the high-speed impact safety, and the impact resistance can be further improved, and the system which is toughened by the compound toughening agent is Sacrificed the rigidity of the material. Therefore, there is still a need in the art to develop a simple and efficient impact modification method to enhance the advantages of PC/ABS in automotive interior applications.
发明内容Summary of the invention
本发明的首要目的在于克服上述现有技术存在的不足,提供一种具有抗高速冲击性能的PC/ABS组合物。SUMMARY OF THE INVENTION A primary object of the present invention is to overcome the deficiencies of the prior art described above and to provide a PC/ABS composition having high impact resistance.
本发明的另一目的在于提供上述PC/ABS组合物的制备方法。Another object of the present invention is to provide a process for the preparation of the above PC/ABS composition.
本发明是通过以下技术方案实现:The invention is achieved by the following technical solutions:
一种PC/ABS组合物,按重量份数计,包括如下组分:A PC/ABS composition, by weight, comprising the following components:
聚碳酸酯树脂          60-70份;Polycarbonate resin 60-70 parts;
丙烯腈-丁二烯-苯乙烯共聚物        30~40份;Acrylonitrile-butadiene-styrene copolymer 30-40 parts;
相容剂           0.5~5份;Compatibilizer 0.5~5 parts;
其中,所述聚碳酸酯树脂为双酚A型聚碳酸酯,在300℃,5Kg负荷下,熔体质量流动速率 MFR为8g/10min-10g/10min;Wherein, the polycarbonate resin is a bisphenol A type polycarbonate, and the melt mass flow rate is at 300 ° C, 5 Kg load. MFR is 8g/10min-10g/10min;
所述丙烯腈-丁二烯-苯乙烯树脂在220℃,10kg负荷下,熔体质量流动速率MFR为15g/10min-20g/10min。The acrylonitrile-butadiene-styrene resin has a melt mass flow rate MFR of 15 g/10 min to 20 g/10 min at 220 ° C under a load of 10 kg.
所述丙烯腈-丁二烯-苯乙烯树脂为乳液法ABS,其橡胶尺寸为粒径控制在300nm以内,且粒径呈现双峰分布,基于丙烯腈-丁二烯-苯乙烯树脂的总重量,橡胶的重量含量在18-22%。本发明通过控制ABS的橡胶含量,橡胶尺寸,有利于最终形成PC/ABS双连续结构,可进一步提升材料的抗高速冲击性能。The acrylonitrile-butadiene-styrene resin is an emulsion method ABS, the rubber size of which is controlled within a particle diameter of 300 nm, and the particle diameter exhibits a bimodal distribution based on the total weight of the acrylonitrile-butadiene-styrene resin. The weight of rubber is 18-22%. By controlling the rubber content of ABS and the rubber size, the invention is beneficial to finally forming a PC/ABS double continuous structure, which can further improve the high-speed impact resistance of the material.
所述相容剂为马来酸酐(MAH)接枝ABS、苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯(GMA)共聚物或甲基丙烯酸甲酯(MMA)-甲基丙烯酸缩水甘油酯(GMA)共聚物中的一种或几种,其中马来酸酐(MAH)、甲基丙烯酸缩水甘油酯(GMA)、甲基丙烯酸甲酯(MMA)功能基团含量为1g/mol-5g/mol。本发明通过选用具有适当官能度的反应性相容剂,并通过添加量控制,可以使相容剂分布于PC与ABS的界面上,提高两相的相容性,起到细化相畴尺寸的作用。The compatibilizer is maleic anhydride (MAH) grafted ABS, styrene-acrylonitrile-glycidyl methacrylate (GMA) copolymer or methyl methacrylate (MMA)-glycidyl methacrylate ( GMA) one or more of the copolymers, wherein maleic anhydride (MAH), glycidyl methacrylate (GMA), methyl methacrylate (MMA) functional group content is 1g / mol -5g / mol . By selecting a reactive compatibilizer with appropriate functionality and controlling the amount of addition, the compatibilizer can be distributed on the interface between PC and ABS to improve the compatibility of the two phases and to refine the domain size. The role.
根据实际性能需要,在不损害本发明效果的基础上,本发明所述的PC/ABS组合物进一步包括0.2-1份的助剂,所述助剂为抗氧剂、光稳定剂或润滑剂中的至少一种。According to actual performance requirements, the PC/ABS composition of the present invention further comprises 0.2-1 parts of an auxiliary agent, which is an antioxidant, a light stabilizer or a lubricant, without impairing the effects of the present invention. At least one of them.
所述抗氧剂为受阻酚类和亚磷酸酯类抗氧剂,具体可以是1010、1076、3114、168、PEP-36中的一种或者两种及以上的混合物;The antioxidant is a hindered phenol and a phosphite antioxidant, specifically one of 1010, 1076, 3114, 168, PEP-36 or a mixture of two or more;
所述光稳定剂为受阻胺类光稳定剂,具体可以是UV-3808PP5、LA-402XP、LA-402AF、770、944、234中的一种或者两种及以上的混合物;The light stabilizer is a hindered amine light stabilizer, specifically one of UV-3808PP5, LA-402XP, LA-402AF, 770, 944, 234 or a mixture of two or more;
所述润滑剂为硅酮类、酯类、酰胺类、聚乙烯类、硬脂酸类、脂肪酸及酯类中的一种或者两种及以上的混合物;The lubricant is one or a mixture of two or more of silicones, esters, amides, polyethylenes, stearic acids, fatty acids and esters;
本发明上述的PC/ABS组合物的制备方法,包括如下步骤:The preparation method of the above PC/ABS composition of the present invention comprises the following steps:
a、先将丙烯腈-丁二烯-苯乙烯共聚物与相容剂按比例混合均匀后加入双螺杆挤出机中,进行熔融混炼,熔融混炼温度为210-220℃,螺杆转速为350-450转/分,挤出造粒,得到ABS组合物;a, the acrylonitrile-butadiene-styrene copolymer and the compatibilizer are mixed in proportion and then added to the twin-screw extruder for melt-kneading, the melt-kneading temperature is 210-220 ° C, and the screw rotation speed is 350-450 rpm, extrusion granulation, to obtain ABS composition;
b、将ABS组合物与聚碳酸酯树脂、助剂按比例混合均匀后加入双螺杆挤出机中,进行熔融混炼,熔融混炼温度为250-260℃,螺杆转速为350-450转/分,挤出造粒,得到PC/ABS组合物。b. The ABS composition is uniformly mixed with the polycarbonate resin and the auxiliary agent, and then added to the twin-screw extruder for melt-kneading, the melt-kneading temperature is 250-260 ° C, and the screw rotation speed is 350-450 rpm. The pellets were extruded and granulated to obtain a PC/ABS composition.
本发明还提供了上述的PC/ABS组合物在汽车内饰中的应用。The present invention also provides the use of the above PC/ABS composition in automotive interiors.
本发明与现有技术相比,具有如下有益效果: Compared with the prior art, the invention has the following beneficial effects:
(1)本发明通过选用通过控制PC/ABS配比,并匹配PC与ABS的粘度,可获得具有纳米尺度的双连续相结构,能有效提升材料的抗高速冲击性能,多轴冲击表现为韧性断裂,提高了使用安全性,制备得到的PC/ABS组合物在保证材料刚性的同时,在高速撞击时具有良好的韧性和安全性,可广泛应用于制备汽车内饰件。(1) The invention can obtain a nano-scale bicontinuous phase structure by controlling the PC/ABS ratio and matching the viscosity of PC and ABS, which can effectively improve the high-speed impact resistance of the material, and the multiaxial impact performance is toughness. The fracture and the safety of use are improved, and the prepared PC/ABS composition has good toughness and safety at high speed impact while ensuring rigidity of the material, and can be widely used for preparing automotive interior parts.
(2)本发明通过二次过机工艺,即将相容剂先与ABS预混,有利于ABS与PC共混时的分布均匀,形成的双连续结构更稳定,更均一,有利于稳定材料的抗高速冲击性能。(2) The invention adopts a secondary over-machine process, that is, the compatibilizer is pre-mixed with ABS first, which is favorable for uniform distribution of ABS and PC, and the formed double continuous structure is more stable and more uniform, and is favorable for stabilizing materials. High speed impact resistance.
具体实施方式detailed description
下面通过具体实施方式来进一步说明本发明,以下实施例为本发明较佳的实施方式,但本发明的实施方式并不受下述实施例的限制。The invention is further illustrated by the following detailed description of the preferred embodiments of the invention, but the embodiments of the invention are not limited by the following examples.
本发明所采用的原料均来源于市购,具体如下:The raw materials used in the present invention are all commercially available, as follows:
PC-1,在300℃,5Kg负荷下,熔体质量流动速率MFR为9g/10min;PC-1, at 300 ° C, 5Kg load, melt mass flow rate MFR is 9g/10min;
PC-2,在300℃,5Kg负荷下,熔体质量流动速率MFR为20g/10min;PC-2, at 300 ° C, 5Kg load, melt mass flow rate MFR is 20g/10min;
PC-3,在300℃,5Kg负荷下,熔体质量流动速率MFR为2g/10min;PC-3, at 300 ° C, 5Kg load, melt mass flow rate MFR is 2g/10min;
ABS-1,乳液法,其橡胶尺寸为粒径在300nm以内,粒径呈现双峰分布,橡胶的重量含量在20%,在220℃,10kg负荷下,熔体质量流动速率MFR为15g/10min;ABS-1, emulsion method, its rubber size is within 300nm, the particle size shows a bimodal distribution, the weight content of rubber is 20%, and the melt mass flow rate MFR is 15g/10min under 220°C and 10kg load. ;
ABS-2,乳液法,其橡胶尺寸为粒径粒径在300nm以内,粒径呈现双峰分布,橡胶的重量含量在20%,在220℃,10kg负荷下,熔体质量流动速率MFR为8.7g/10min;ABS-2, emulsion method, the rubber size is within the particle size of 300nm, the particle size shows a bimodal distribution, the weight content of the rubber is 20%, the melt mass flow rate MFR is 8.7 at 220 ° C, 10kg load G/10min;
ABS-3,乳液法,其橡胶尺寸为粒径粒径在300nm以内,粒径呈现双峰分布,橡胶的重量含量在20%,在220℃,10kg负荷下,熔体质量流动速率MFR为30g/10min;ABS-3, emulsion method, the rubber size is the particle size within 300nm, the particle size shows a bimodal distribution, the weight content of the rubber is 20%, the melt mass flow rate MFR is 30g at 220 °C, 10kg load /10min;
ABS-4,本体法,其橡胶尺寸为粒径超过1um,橡胶的重量含量在25%,在220℃,10kg负荷下,熔体质量流动速率MFR为15g/10min;ABS-4, the bulk method, the rubber size is more than 1um, the weight content of the rubber is 25%, the melt mass flow rate MFR is 15g/10min under the load of 220 ° C, 10kg;
相容剂:Compatibilizer:
马来酸酐(MAH)接枝ABS,MAH功能基团的含量为5g/mol;Maleic anhydride (MAH) grafted ABS, the content of MAH functional group is 5g / mol;
苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯(GMA)共聚物,GMA功能基团的含量为2g/mol;a styrene-acrylonitrile-glycidyl methacrylate (GMA) copolymer having a GMA functional group content of 2 g/mol;
抗氧剂:抗氧剂1076、抗氧剂PEP-36;Antioxidant: antioxidant 1076, antioxidant PEP-36;
光稳定剂:光稳定剂234;Light stabilizer: light stabilizer 234;
本发明所用的检测方法或标准为:The detection method or standard used in the present invention is:
(1)悬臂梁缺口冲击强度:按照ISO 180测试;(1) Cantilever beam notched impact strength: tested according to ISO 180;
(2)弯曲模量:按照ISO 178测试。(2) Flexural modulus: Tested in accordance with ISO 178.
(3)多轴冲击:按照ASTM D 3763-201进行,测试速度6.7m/s,测试温度为23℃。 (3) Multiaxial impact: According to ASTM D 3763-201, the test speed was 6.7 m/s, and the test temperature was 23 °C.
ASTM D3763中材料的破坏形式分为两种,韧性和脆性。当测试的5块板中3块或以上没有出现断裂,则判定为韧性,则将材料的断裂形式描述为韧性;当测试的5块板中有1-2块出现断裂,则判定为接近韧性,则将材料的断裂形式描述为接近韧性;当测试的5块板均出现断裂,则判定为脆性,则将材料的断裂形式描述为脆性。The damage forms of materials in ASTM D3763 are divided into two types, toughness and brittleness. When no break occurred in 3 or more of the 5 plates tested, it was judged to be tough, and the fracture form of the material was described as toughness; when 1-2 of the 5 plates tested showed fracture, it was judged to be close toughness. The fracture form of the material is described as being close to toughness; when the five plates tested are judged to be brittle, the fracture form of the material is described as brittle.
实施例1-7及对比例1-7Examples 1-7 and Comparative Examples 1-7
按表1所示配方,先将丙烯腈-丁二烯-苯乙烯共聚物与相容剂按比例混合均匀后加入双螺杆挤出机中,进行熔融混炼,熔融混炼温度为210-220℃,螺杆转速为350-450转/分,挤出造粒,得到ABS组合物;将ABS组合物、聚碳酸酯树脂、助剂按比例混合均匀后加入双螺杆挤出机中,进行熔融混炼,熔融混炼温度为250-260℃,螺杆转速为350-450转/分,挤出造粒,得到PC/ABS组合物。According to the formula shown in Table 1, the acrylonitrile-butadiene-styrene copolymer and the compatibilizer are mixed in proportion and then added to the twin-screw extruder for melt-kneading. The melt-kneading temperature is 210-220. °C, screw rotation speed is 350-450 rpm, extrusion granulation, to obtain ABS composition; ABS composition, polycarbonate resin, auxiliary agent are mixed uniformly in proportion and then added to twin-screw extruder for melt mixing The refining, melt-kneading temperature was 250-260 ° C, the screw rotation speed was 350-450 rpm, and extrusion granulation was carried out to obtain a PC/ABS composition.
对比例8-9Comparative Example 8-9
按表1所示配方,将聚碳酸酯树脂、丙烯腈-丁二烯-苯乙烯共聚物、相容剂、助剂按比例混合均匀后加入双螺杆挤出机中,进行熔融混炼,熔融混炼温度为250-260℃,螺杆转速为350-450转/分,挤出造粒,得到PC/ABS组合物。According to the formula shown in Table 1, the polycarbonate resin, acrylonitrile-butadiene-styrene copolymer, compatibilizer and auxiliary agent are mixed uniformly in proportion and then added to a twin-screw extruder for melt-kneading and melting. The kneading temperature was 250-260 ° C, the screw rotation speed was 350-450 rpm, and extrusion granulation was carried out to obtain a PC/ABS composition.
将制备得到的PC/ABS组合物注塑力学样条,用于测试其悬臂梁缺口冲击强度和弯曲模量、弯曲强度、熔融指数。将组合物注塑成10×10×0.3cm3方板,用于测试多轴冲击。测试得到的性能参数如表2所示。The prepared PC/ABS composition was injection molded into a mechanical spline for testing the cantilever beam notched impact strength and flexural modulus, bending strength, and melt index. The composition was injection molded into 10 × 10 × 0.3cm 3 square plate for multiaxial impact testing. The performance parameters obtained by the test are shown in Table 2.
表1 实施例及对比例各组分组成及性能结果(重量份) Table 1 Example and Comparative Example Composition and Performance Results (Parts by Weight)
Figure PCTCN2017113751-appb-000001
Figure PCTCN2017113751-appb-000001
续表1:Continued Table 1:
Figure PCTCN2017113751-appb-000002
Figure PCTCN2017113751-appb-000002
表2 性能测试结果Table 2 Performance test results
Figure PCTCN2017113751-appb-000003
Figure PCTCN2017113751-appb-000003
续表2:Continued Table 2:
Figure PCTCN2017113751-appb-000004
Figure PCTCN2017113751-appb-000004
实施例1与对比例1-2相比,当将实施例中的PC换成高流动PC或高冲低流动PC时,则由于PC与ABS粘度不匹配,ABS由于从PC传递过来的剪切力变弱,成型后ABS以分散 相形式存在,降低了材料的抗高速冲击性能。Example 1 Compared with Comparative Example 1-2, when the PC in the example was changed to a high-flow PC or a high-flow low-flow PC, the ABS was transferred from the PC due to a mismatch in PC and ABS viscosity. The force is weak, and the ABS is dispersed after molding. The phase form exists, which reduces the high-speed impact resistance of the material.
实施例1与对比例3相比,当将实施例中的ABS换成低流动ABS,则由于流动性的不匹配会引起ABS与PC相容性变差,成型后ABS以大尺寸分散相形式存在,降低了材料的抗高速冲击性能。Compared with Comparative Example 3, when the ABS in the embodiment was changed to the low-flow ABS, the compatibility of the ABS and the PC was deteriorated due to the mismatch of the fluidity, and the ABS was dispersed in a large-sized form after molding. Existence reduces the high-speed impact resistance of the material.
实施例1与对比例4相比,当将实施例中的ABS换成高流动ABS,则由于PC与ABS粘度不匹配,成型过程中,ABS更倾向于分布于制件表层,导致PC/ABS相态分布不均,内层ABS以分散相形式存在,降低了材料的抗高速冲击性能。Compared with Comparative Example 4, when the ABS in the embodiment was replaced by the high-flow ABS, the ABS was more likely to be distributed on the surface of the part during the molding process due to the mismatch of the viscosity of the PC and the ABS, resulting in PC/ABS. The phase distribution is uneven, and the inner layer ABS exists in the form of a dispersed phase, which reduces the high-speed impact resistance of the material.
实施例2与对比例5相比,当相容剂在低添加量条件下,有利于PC/ABS双连续结构的实现,从而提高材料的抗高速冲击性能,当添加较多含量的相容剂时,则由于材料中PC存在部分交联,与ABS粘度不匹配,会粗化两相相畴尺寸,反而不利于PC/ABS双连续结构的实现。Compared with Comparative Example 5, when the compatibilizer is in a low addition amount, it is advantageous for the realization of the PC/ABS double continuous structure, thereby improving the high-speed impact resistance of the material when a large amount of compatibilizer is added. When the PC is partially crosslinked and does not match the viscosity of the ABS, the two-phase domain size will be coarsened, which is not conducive to the realization of the PC/ABS double continuous structure.
实施例1与对比例6相比,当提升对比例中的ABS含量,降低PC含量,则配方体系中以ABS为主,最终形成的两相结构为PC以分散相存在于ABS当中,也降低了材料的抗高速冲击性能。Compared with Comparative Example 6, in Example 1, when the ABS content in the comparative example was increased and the PC content was decreased, the ABS was mainly used in the formulation system, and the resulting two-phase structure was PC and the dispersed phase was present in the ABS, which also decreased. The material's resistance to high-speed impact.
实施例1与对比例7对比,当提升对比例中的PC含量,降低ABS含量,则配方体系以PC为主,最终形成的两相结构为ABS以分散相存在于PC当中,降低了材料的抗高速冲击性能。Comparing Example 1 with Comparative Example 7, when the PC content in the comparative example was increased and the ABS content was decreased, the formulation system was mainly PC, and the resulting two-phase structure was ABS with a dispersed phase present in the PC, which lowered the material. High speed impact resistance.
由以上对比从而得出,本发明通过优化PC、ABS、相容剂的配比,并通过匹配PC与ABS的粘度,以及控制ABS的橡胶含量,橡胶尺寸,有利于最终形成PC/ABS双连续结构,明显提升了材料的抗高速冲击性能。From the above comparison, it is concluded that the present invention optimizes the ratio of PC, ABS, compatibilizer, and by matching the viscosity of PC and ABS, as well as controlling the rubber content of ABS, rubber size, and finally forming PC/ABS double continuous. The structure significantly improves the material's high-speed impact resistance.
实施例1与对比例8相比,实施例3与对比例9相比,采用二次过机工艺,当相容剂先与ABS预混,有利于ABS与PC共混时的分布均匀,形成的双连续结构更稳定,更均一,有利于稳定材料的抗高速冲击性能。 Compared with Comparative Example 8, Example 1 compared with Comparative Example 9, using a secondary machine process, when the compatibilizer is premixed with ABS, which is favorable for the uniform distribution of ABS and PC. The double continuous structure is more stable and more uniform, which is beneficial to stabilize the material against high-speed impact performance.

Claims (6)

  1. 一种PC/ABS组合物,其特征在于,按重量份数计,包括如下组分:A PC/ABS composition characterized by the following components by weight:
    聚碳酸酯树脂               60-70份;Polycarbonate resin 60-70 parts;
    丙烯腈-丁二烯-苯乙烯共聚物        30~40份;Acrylonitrile-butadiene-styrene copolymer 30-40 parts;
    相容剂                  0.5~5份;Compatibilizer 0.5~5 parts;
    其中,所述聚碳酸酯树脂为双酚A型聚碳酸酯,在300℃,5Kg负荷下,熔体质量流动速率MFR为8g/10min-10g/10min;Wherein, the polycarbonate resin is a bisphenol A type polycarbonate, and the melt mass flow rate MFR is 8 g/10 min - 10 g/10 min at 300 ° C under a load of 5 kg;
    所述丙烯腈-丁二烯-苯乙烯树脂为在220℃,10kg负荷下,熔体质量流动速率MFR为15g/10min-20g/10min。The acrylonitrile-butadiene-styrene resin has a melt mass flow rate MFR of 15 g/10 min to 20 g/10 min at 220 ° C under a load of 10 kg.
  2. 根据权利要求1所述的PC/ABS组合物,其特征在于:所述丙烯腈-丁二烯-苯乙烯树脂为乳液法ABS,其橡胶尺寸为粒径控制在300nm以内,同时粒径呈现双峰分布,基于丙烯腈-丁二烯-苯乙烯树脂的总重量,橡胶的重量含量在18-22%。The PC/ABS composition according to claim 1, wherein the acrylonitrile-butadiene-styrene resin is an emulsion method ABS, and the rubber size thereof is controlled within a particle diameter of 300 nm, and the particle diameter is double The peak distribution is based on the total weight of the acrylonitrile-butadiene-styrene resin, and the weight content of the rubber is 18-22%.
  3. 根据权利要求1所述的PC/ABS组合物,其特征在于:所述相容剂为马来酸酐接枝ABS、苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物或甲基丙烯酸甲酯-甲基丙烯酸缩水甘油酯共聚物中的一种或几种,其中马来酸酐、甲基丙烯酸缩水甘油酯、甲基丙烯酸甲酯功能基团含量为1g/mol-5g/mol。The PC/ABS composition according to claim 1, wherein the compatibilizer is maleic anhydride grafted ABS, styrene-acrylonitrile-glycidyl methacrylate copolymer or methyl methacrylate One or more of glycidyl methacrylate copolymers wherein the maleic anhydride, glycidyl methacrylate, methyl methacrylate functional group content is from 1 g/mol to 5 g/mol.
  4. 根据权利要求1所述的PC/ABS组合物,其特征在于:进一步包括0.2-1份的助剂,所述助剂为抗氧剂、光稳定剂或润滑剂中的至少一种。The PC/ABS composition according to claim 1, further comprising 0.2 to 1 part of an auxiliary agent which is at least one of an antioxidant, a light stabilizer or a lubricant.
  5. 根据权利要求1-4任一项所述的PC/ABS组合物的制备方法,其特征在于,包括如下步骤:The method for preparing a PC/ABS composition according to any one of claims 1 to 4, comprising the steps of:
    a、先将丙烯腈-丁二烯-苯乙烯共聚物与相容剂按比例混合均匀后加入双螺杆挤出机中,进行熔融混炼,熔融混炼温度为210-220℃,螺杆转速为350-450转/分,挤出造粒,得到ABS组合物;a, the acrylonitrile-butadiene-styrene copolymer and the compatibilizer are mixed in proportion and then added to the twin-screw extruder for melt-kneading, the melt-kneading temperature is 210-220 ° C, and the screw rotation speed is 350-450 rpm, extrusion granulation, to obtain ABS composition;
    b、将ABS组合物与聚碳酸酯树脂、助剂按比例混合均匀后加入双螺杆挤出机中,进行熔融混炼,熔融混炼温度为250-260℃,螺杆转速为350-450转/分,挤出造粒,得到PC/ABS组合物。b. The ABS composition is uniformly mixed with the polycarbonate resin and the auxiliary agent, and then added to the twin-screw extruder for melt-kneading, the melt-kneading temperature is 250-260 ° C, and the screw rotation speed is 350-450 rpm. The pellets were extruded and granulated to obtain a PC/ABS composition.
  6. 权利要求1-4任一项所述的PC/ABS组合物在汽车内饰中的应用。 Use of the PC/ABS composition of any of claims 1-4 in automotive interiors.
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