WO2022077860A1 - Polycarbonate composition, preparation method therefor and application thereof - Google Patents

Polycarbonate composition, preparation method therefor and application thereof Download PDF

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WO2022077860A1
WO2022077860A1 PCT/CN2021/082010 CN2021082010W WO2022077860A1 WO 2022077860 A1 WO2022077860 A1 WO 2022077860A1 CN 2021082010 W CN2021082010 W CN 2021082010W WO 2022077860 A1 WO2022077860 A1 WO 2022077860A1
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polycarbonate
maleic anhydride
polycarbonate composition
parts
styrene
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PCT/CN2021/082010
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French (fr)
Chinese (zh)
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王培涛
黄险波
叶南飚
艾军伟
岑茵
丁超
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金发科技股份有限公司
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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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer 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 polycarbonate composition and a preparation method and application thereof.
  • Polycarbonate (PC for short) is a high molecular polymer containing carbonate groups in the molecular chain. According to the structure of the ester groups, it can be divided into aliphatic, aromatic, aliphatic-aromatic and other types. Due to the special structure of polycarbonate, it has become the fastest growing general engineering plastic among the five major engineering plastics. Polycarbonate is a synthetic material developed in the late fifties. Polycarbonate resin has outstanding impact resistance, creep resistance and dimensional stability, and is widely used in electronic appliances, rail transit and aerospace fields.
  • the intermolecular force is relatively strong and the rigidity is relatively large, and a certain amount of toughening agent needs to be added.
  • the styrene-maleic anhydride random copolymer is a commonly used toughening agent.
  • the technical defect of high internal stress of polycarbonate cannot be changed after adding styrene-maleic anhydride random copolymer.
  • the main chain of the polycarbonate molecule is relatively rigid, and the adjustment of the molecular chain during the injection molding process is relatively slow, resulting in a high internal stress.
  • the purpose of the present invention is to overcome the above technical defects and provide a polycarbonate composition with strong toughness and low internal stress.
  • Another object of the present invention is to provide a method for preparing the above-mentioned polycarbonate composition.
  • a polycarbonate composition by weight, comprising the following components:
  • the content of maleic anhydride in the styrene-maleic anhydride random copolymer is 10-20 wt%.
  • Carboxylic acid group ionomer 10-21 parts Carboxylic acid group ionomer 10-21 parts.
  • Polycarbonates are branched thermoplastic polymers or copolymers obtained from the reaction of dihydroxy compounds or a small amount of polyhydroxy compounds with phosgene or carbonic acid diesters.
  • Polycarbonate resins can be produced by a phosgene method (interfacial polymerization method) or a melt method (transesterification method).
  • the polycarbonate resin is also provided by subjecting the polycarbonate resin produced by the melt method to a post-treatment to adjust the amount of terminal hydroxyl groups.
  • the embodiment of the present invention adopts a polycarbonate obtained by polymerizing bisphenol A (BPA) and diphenyl carbonate (DPC) by a melt transesterification method.
  • Styrene-maleic anhydride random copolymer is a polymer with excellent toughness, but it also has two defects: 1. It cannot effectively reduce the internal stress resistance of polycarbonate; 2. If styrene-maleic anhydride random copolymer If the content of the copolymer is too large, the internal stress of the polycarbonate will be further increased.
  • the present invention selects a styrene-maleic anhydride random copolymer with a maleic anhydride content of 10-20 wt%, which can further improve the toughness and reduce the internal stress of the polycarbonate composition. Furthermore, adding a certain amount of carboxylic acid-based ionomer into the composition can not only reduce the internal stress of the polycarbonate composition, but also further improve the toughness.
  • the melt index of the styrene-maleic anhydride random copolymer is 3-40g/10min, 230°C, 2.16kg.
  • the melt index is a conventional parameter of the styrene-maleic anhydride random copolymer, and the technical effect of the present invention can be achieved within the above range of the melt index.
  • the carboxylic acid group ionomer is an ethylene/methacrylic acid copolymer, wherein 40mol%-90mol% of the carboxyl groups in the methacrylic acid unit are neutralized by metal ions, and the melt index range is 0.5-15g/10min. Test The conditions were 190° C., 2.16 kg.
  • the metal ion is selected from at least one of sodium ion, zinc ion, magnesium ion and potassium ion.
  • the molecular weight of the carboxylic acid-based ionomer is relatively larger than that of polycarbonate and styrene-maleic anhydride random copolymer, and the molecular chain is flexible, and there are many entanglement points between the molecules.
  • the ions in the ionomer can increase the physical entanglement. point to increase the toughness of the material.
  • high molecular weight can reduce the internal stress
  • second the ionomer molecular chain has a high degree of flexibility, and the internal stress is much smaller than that of polycarbonate materials during the molding process, reducing the risk of stress cracking, and finally ionomerization.
  • the ions in the bulk allow the formation of physical cross-linking points between the molecules, which can further reduce the internal stress.
  • the melt index of the polycarbonate is 3-22g/10min, and the test conditions are 300°C and 1.2kg.
  • lubricant In order to improve melt processability, a certain amount of lubricant can be added. In parts by weight, 0-2 parts of lubricant are also included.
  • Described lubricant is selected from at least one in stearate class lubricant, fatty acid class lubricant, stearate class lubricant; Described stearate class lubricant is selected from calcium stearate, At least one in magnesium stearate, zinc stearate; Described fatty acid lubricant is selected from at least one in fatty acid, fatty acid derivative, fatty acid ester; Described stearic ester lubricant is selected from At least one of glycerol monostearate and pentaerythritol stearate.
  • the preparation method of the above-mentioned polycarbonate composition comprises the following steps: according to the proportioning, after uniformly mixing the carboxylic acid group ionomer, polycarbonate and styrene-maleic anhydride random copolymer, extruding through twin-screw Machine extrusion and granulation to obtain a polycarbonate composition, wherein the temperature range of the screw is 200-260° C., and the rotation speed range is 180-500 r/min.
  • the present invention can solve the defect of high internal stress of the polycarbonate composition by introducing the carboxylic acid group ionomer into the polycarbonate composition, and can further improve the toughness of the composition.
  • the internal stress of the polycarbonate composition can be reduced in cooperation with the carboxylic acid-based ionomer.
  • the sources of raw materials used in the present invention are as follows:
  • Carboxylic acid group ionomer A the main chain is ethylene/methacrylic acid copolymer, the melt index is 0.7g/10min, the test condition is 190°C, 2.16kg, 78mol% of the carboxyl group in the methacrylic acid unit is neutralized by sodium ions , commercially available.
  • Carboxylic acid group ionomer B the main chain is ethylene/methacrylic acid copolymer, the melt index is 4.5g/10min, the test condition is 190°C, 2.16kg, 45mol% of the carboxyl group in the methacrylic acid unit is neutralized by zinc ions , commercially available.
  • Carboxylic acid group ionomer C the main chain is ethylene/methacrylic acid copolymer, the melt index is 5.9g/10min, the test condition is 190°C, 2.16kg, 26mol% of carboxyl groups in the methacrylic acid unit are neutralized by zinc ions .
  • Polycarbonate melt index is 5.7g/10min, test condition is 300°C, 1.2kg, brand PC WY-106BR, monomers are bisphenol A (BPA) and diphenyl carbonate (DPC, commercially available);
  • Styrene-maleic anhydride random copolymer A maleic anhydride content is 18 ⁇ 2wt%, SMA-700, melt index is 7-15g/10min, 230°C, 2.16kg, commercially available.
  • Styrene-maleic anhydride random copolymer B maleic anhydride content is 12 ⁇ 2wt%, SMA-700-R50, melt index is 5-10g/10min, 230°C, 2.16kg, commercially available.
  • Styrene-maleic anhydride random copolymer C maleic anhydride content is 23 ⁇ 1wt%, SZ23110, melt index is 20-30g/10min, 230°C, 2.16kg, commercially available.
  • Styrene-maleic anhydride random copolymer D maleic anhydride content is 5 ⁇ 1wt%, SMA EF-80, melt index is 18-25g/10min, 230°C, 2.16kg, commercially available.
  • Zinc stearate ZINC STEARATE (BS-2818), commercially available;
  • Example and comparative example The preparation method of polycarbonate composition, according to the proportion, after mixing ionomer, polycarbonate, styrene-maleic anhydride random copolymer, and lubricant uniformly, it is passed through a twin-screw extruder. Extrusion and granulation are performed to obtain a polycarbonate composition, wherein the temperature of the screw is in the range of 200-260° C., and the rotation speed is in the range of 300-350 r/min.
  • Low temperature notched impact test refer to the standard ISO 180-2000 test, the thickness of the spline is 4.0mm, and the test temperature is -40°C.
  • Notched impact test at room temperature reference standard ISO 180-2000 test, the thickness of the spline is 4.0mm, and the test temperature is 23°C.
  • Table 1 The distribution ratio (parts by weight) and performance test results of each component of the polycarbonate compositions of Examples 1-7
  • the content of polycarbonate is preferably 80 parts
  • the content of carboxylic acid group ionomer is 10-21 parts
  • the content of styrene-maleic anhydride random copolymer is 5-20 parts.
  • Table 2 The distribution ratio (parts by weight) and performance test results of each component of the polycarbonate composition of Example 8-10
  • Example 8 Example 9 Example 10 polycarbonate 80 80 80 Carboxylic acid group ionomer A twenty one 3 Carboxylic acid group ionomer B twenty one Styrene-maleic anhydride random copolymer A 12 12 Styrene-maleic anhydride random copolymer B 12 lubricant 0.1 0.1 Notched impact strength (-40°C)kJ/m 2 47 41 38 Notched impact strength (23°C)kJ/m 2 71 64 57 Internal stress test Grade 4 Microcracks Grade 5 Microcracks Grade 4 Microcracks
  • Table 3 Composition ratio (parts by weight) and performance test results of each component of the polycarbonate composition of comparative example
  • Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 polycarbonate 80 80 80 80 80 Carboxylic acid group ionomer A twenty one twenty one 33 Styrene-maleic anhydride random copolymer A 12 30 Styrene-maleic anhydride random copolymer C 12 Styrene-maleic anhydride random copolymer D 12 lubricant 0.1 0.1 0.1 0.1 Notched impact strength (-40°C)kJ/m 2 18 15 twenty three 36 Notched impact strength (23°C)kJ/m 2 32 28 39 53 Internal stress test 4th grade big rift Grade 4 Microcracks tier 2 big rift Grade 3 Microcracks

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  • Health & Medical Sciences (AREA)
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Abstract

Disclosed is a polycarbonate composition, comprising the following components in parts by weight: 3-25 parts of a carboxylic acid-based ionomer, 80 parts of polycarbonate and 5-20 parts of a styrene-maleic anhydride random copolymer, the content of maleic anhydride in the styrene-maleic anhydride random copolymer being 5-25 wt%. By adding a carboxylic acid-based ionomer, the technical problem of relatively high internal stress of polycarbonate can be improved, and the toughness of the composition can be further increased.

Description

一种聚碳酸酯组合物及其制备方法及应用A kind of polycarbonate composition and its preparation method and application 技术领域technical field
本发明涉及高分子材料技术领域，特别是涉及一种聚碳酸酯组合物及其制备方法及应用。The invention relates to the technical field of polymer materials, in particular to a polycarbonate composition and a preparation method and application thereof.
背景技术Background technique
聚碳酸酯(简称PC)是分子链中含有碳酸酯基的高分子聚合物，根据酯基的结构可分为脂肪族、芳香族、脂肪族-芳香族等多种类型。由于聚碳酸酯结构上的特殊性，现已成为五大工程塑料中增长速度最快的通用工程塑料。聚碳酸酯是五十年代末开始发展起来的合成材料。聚碳酸酯树脂具有突出的抗冲击能力、耐蠕变、尺寸稳定性，被广泛应用于电子电器、轨道交通及航空航天领域，近年来用量超过尼龙，跃居首位。Polycarbonate (PC for short) is a high molecular polymer containing carbonate groups in the molecular chain. According to the structure of the ester groups, it can be divided into aliphatic, aromatic, aliphatic-aromatic and other types. Due to the special structure of polycarbonate, it has become the fastest growing general engineering plastic among the five major engineering plastics. Polycarbonate is a synthetic material developed in the late fifties. Polycarbonate resin has outstanding impact resistance, creep resistance and dimensional stability, and is widely used in electronic appliances, rail transit and aerospace fields.
但是，聚碳酸酯也因为分子结构中苯环的影响，导致分子间作用力比较强，刚性比较大，需要加入一定量的增韧剂。而苯乙烯-马来酸酐无规共聚物就是常用的增韧剂。但是，加入苯乙烯-马来酸酐无规共聚物后也无法改变聚碳酸酯内应力高的技术缺陷。However, due to the influence of the benzene ring in the molecular structure of polycarbonate, the intermolecular force is relatively strong and the rigidity is relatively large, and a certain amount of toughening agent needs to be added. The styrene-maleic anhydride random copolymer is a commonly used toughening agent. However, the technical defect of high internal stress of polycarbonate cannot be changed after adding styrene-maleic anhydride random copolymer.
关于内应力，聚碳酸酯分子主链刚性较强，在注塑成型的过程中分子链调整相对会慢，导致其成内应力较高。一般的，降低应力的方式主要有以下3种：1.降低聚碳酸酯粘度，但是会导致力学性能的大幅下降；2.通过在成型的过程中调节成型参数来降低应力；3.引入ABS树脂制成PC/ABS合金，但是该合金表面硬度低，耐划擦性能差。Regarding the internal stress, the main chain of the polycarbonate molecule is relatively rigid, and the adjustment of the molecular chain during the injection molding process is relatively slow, resulting in a high internal stress. Generally, there are three main ways to reduce stress: 1. Reduce the viscosity of polycarbonate, but it will lead to a significant drop in mechanical properties; 2. Reduce stress by adjusting molding parameters during the molding process; 3. Introduce ABS resin Made of PC/ABS alloy, but the alloy has low surface hardness and poor scratch resistance.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于，克服上述技术缺陷，提供一种韧性强、内应力低的的聚碳酸酯组合物。The purpose of the present invention is to overcome the above technical defects and provide a polycarbonate composition with strong toughness and low internal stress.
本发明的另一目的在于，提供上述聚碳酸酯组合物的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned polycarbonate composition.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
一种聚碳酸酯组合物，按重量份计，包括以下组分：A polycarbonate composition, by weight, comprising the following components:
聚碳酸酯                   80份；80 copies of polycarbonate;
苯乙烯-马来酸酐无规共聚物  5-20份；5-20 parts of styrene-maleic anhydride random copolymer;
羧酸基离聚体               3-25份；Carboxylic acid group ionomer 3-25 copies;
苯乙烯-马来酸酐无规共聚物中马来酸酐含量为10-20wt％。The content of maleic anhydride in the styrene-maleic anhydride random copolymer is 10-20 wt%.
优选的，按重量份计，包括以下组分：Preferably, in parts by weight, the following components are included:
聚碳酸酯                   80份；80 copies of polycarbonate;
苯乙烯-马来酸酐无规共聚物  5-20份；5-20 parts of styrene-maleic anhydride random copolymer;
羧酸基离聚体              10-21份。Carboxylic acid group ionomer 10-21 parts.
聚碳酸酯，为由二羟基化合物或其和少量的多羟基化合物与光气(phosgene)或碳酸二酯的反应获得的支化热塑性聚合物或共聚物。可使用由光气法(界面聚合法)或熔融法(酯交换法)生产聚碳酸酯树脂。聚碳酸酯树脂还通过由熔融法生产的聚碳酸酯树脂经过调节末端羟基的量的后处理来提供。Polycarbonates are branched thermoplastic polymers or copolymers obtained from the reaction of dihydroxy compounds or a small amount of polyhydroxy compounds with phosgene or carbonic acid diesters. Polycarbonate resins can be produced by a phosgene method (interfacial polymerization method) or a melt method (transesterification method). The polycarbonate resin is also provided by subjecting the polycarbonate resin produced by the melt method to a post-treatment to adjust the amount of terminal hydroxyl groups.
本发明实施例采用双酚A(BPA)和碳酸二苯酯(DPC)通过熔融酯交换方法聚合得到的聚碳酸酯。The embodiment of the present invention adopts a polycarbonate obtained by polymerizing bisphenol A (BPA) and diphenyl carbonate (DPC) by a melt transesterification method.
苯乙烯-马来酸酐无规共聚物是一种增韧性优的聚合物，但是也具有两个缺陷：1.无法有效降低聚碳酸酯耐内应力；2.如果苯乙烯-马来酸酐无规共聚物的含量过大，反而会导致聚碳酸酯的内应力进一步提高。本发明特选马来酸酐含量为10-20wt％的苯乙烯-马来酸酐无规共聚物，能够再进一步提升韧性，并且降低聚碳酸酯组合物的内应力。更进一步的，在组合物中加入一定量的羧酸基离聚体，不仅能够降低聚碳酸酯组合物的内应力，而且能够进一步提升韧性。Styrene-maleic anhydride random copolymer is a polymer with excellent toughness, but it also has two defects: 1. It cannot effectively reduce the internal stress resistance of polycarbonate; 2. If styrene-maleic anhydride random copolymer If the content of the copolymer is too large, the internal stress of the polycarbonate will be further increased. The present invention selects a styrene-maleic anhydride random copolymer with a maleic anhydride content of 10-20 wt%, which can further improve the toughness and reduce the internal stress of the polycarbonate composition. Furthermore, adding a certain amount of carboxylic acid-based ionomer into the composition can not only reduce the internal stress of the polycarbonate composition, but also further improve the toughness.
所述的苯乙烯-马来酸酐无规共聚物的熔融指数为3-40g/10min，230℃，2.16kg。熔融指数是苯乙烯-马来酸酐无规共聚物的常规参数，在上述熔融指数范围内都可以实现本发明的技术效果。The melt index of the styrene-maleic anhydride random copolymer is 3-40g/10min, 230°C, 2.16kg. The melt index is a conventional parameter of the styrene-maleic anhydride random copolymer, and the technical effect of the present invention can be achieved within the above range of the melt index.
所述的羧酸基离聚体为乙烯/甲基丙烯酸类共聚物，其中甲基丙烯酸单元中的40mol％-90mol％的羧基被金属离子中和，熔融指数范围是0.5-15g/10min，测试条件为190℃、2.16kg。The carboxylic acid group ionomer is an ethylene/methacrylic acid copolymer, wherein 40mol%-90mol% of the carboxyl groups in the methacrylic acid unit are neutralized by metal ions, and the melt index range is 0.5-15g/10min. Test The conditions were 190° C., 2.16 kg.
所述的金属离子选自钠离子、锌离子、镁离子、钾离子中的至少一种。The metal ion is selected from at least one of sodium ion, zinc ion, magnesium ion and potassium ion.
羧酸基离聚体的分子量相对大于聚碳酸酯和苯乙烯-马来酸酐无规共聚物的分子量，而且分子链柔顺，分子之间缠绕点多，另外离聚体中的离子能增加物理缠绕点，使材料的韧性升高。内应力方面，第一、高分子量能够降低内应力，第二、离聚体分子链柔顺程度高，在成型过程中相比聚碳酸酯材料内应力小很多，降低了应力开裂风险，最后离聚体中的离子使得分子间形成物理交联点可以进一步降低内应力。The molecular weight of the carboxylic acid-based ionomer is relatively larger than that of polycarbonate and styrene-maleic anhydride random copolymer, and the molecular chain is flexible, and there are many entanglement points between the molecules. In addition, the ions in the ionomer can increase the physical entanglement. point to increase the toughness of the material. In terms of internal stress, first, high molecular weight can reduce the internal stress, second, the ionomer molecular chain has a high degree of flexibility, and the internal stress is much smaller than that of polycarbonate materials during the molding process, reducing the risk of stress cracking, and finally ionomerization. The ions in the bulk allow the formation of physical cross-linking points between the molecules, which can further reduce the internal stress.
所述的聚碳酸酯的熔融指数为3-22g/10min，测试条件为300℃、1.2kg。The melt index of the polycarbonate is 3-22g/10min, and the test conditions are 300°C and 1.2kg.
为了提升熔融加工性能，可以加入一定量的润滑剂。按重量份计，还包括0-2份的润滑剂。In order to improve melt processability, a certain amount of lubricant can be added. In parts by weight, 0-2 parts of lubricant are also included.
所述的润滑剂选自硬脂酸盐类润滑剂、脂肪酸类润滑剂、硬脂酸酯类润滑剂中的至少一种；所述的硬脂酸盐类润滑剂选自硬脂酸钙、硬脂酸镁、硬脂酸锌中的至少一种；所述的脂肪酸类润滑剂选自脂肪酸、脂肪酸衍生物、脂肪酸酯中的至少一种；所述的硬脂酸酯类润滑 剂选自单硬脂酸甘油酯、季戊四醇硬脂酸酯中的至少一种。Described lubricant is selected from at least one in stearate class lubricant, fatty acid class lubricant, stearate class lubricant; Described stearate class lubricant is selected from calcium stearate, At least one in magnesium stearate, zinc stearate; Described fatty acid lubricant is selected from at least one in fatty acid, fatty acid derivative, fatty acid ester; Described stearic ester lubricant is selected from At least one of glycerol monostearate and pentaerythritol stearate.
上述的聚碳酸酯组合物的制备方法，包括以下步骤：按照配比，将羧酸基离聚体、聚碳酸酯、苯乙烯-马来酸酐无规共聚物混合均匀后，通过双螺杆挤出机挤出造粒，得到聚碳酸酯组合物，其中，螺杆的温度范围是200-260℃，转速范围是180-500r/min。The preparation method of the above-mentioned polycarbonate composition comprises the following steps: according to the proportioning, after uniformly mixing the carboxylic acid group ionomer, polycarbonate and styrene-maleic anhydride random copolymer, extruding through twin-screw Machine extrusion and granulation to obtain a polycarbonate composition, wherein the temperature range of the screw is 200-260° C., and the rotation speed range is 180-500 r/min.
上述的聚碳酸酯组合物的应用，用于制备表面耐刮的电子电器外壳。The application of the above-mentioned polycarbonate composition is used to prepare a scratch-resistant electrical and electronic casing.
本发明具有如下有益效果The present invention has the following beneficial effects
本发明通过在聚碳酸酯组合物中引入羧酸基离聚体，能够解决聚碳酸酯组合物内应力高的的缺陷，而且能够进一步提升组合物的韧性。同时，通过选取马来酸酐含量为10-20wt％的苯乙烯-马来酸酐无规共聚物，能够协同羧酸基离聚体降低聚碳酸酯组合物内应力。The present invention can solve the defect of high internal stress of the polycarbonate composition by introducing the carboxylic acid group ionomer into the polycarbonate composition, and can further improve the toughness of the composition. At the same time, by selecting a styrene-maleic anhydride random copolymer with a maleic anhydride content of 10-20 wt%, the internal stress of the polycarbonate composition can be reduced in cooperation with the carboxylic acid-based ionomer.
具体实施方式Detailed ways
下面结合具体实施例和对比实施例来进一步说明本发明，以下具体实施例均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，特别并不局限于下述具体实施例中所使用的各组分原料的型号。The present invention will be further described below in conjunction with specific examples and comparative examples. The following specific examples are all preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the following examples, especially not limited to The model of each component raw material used in the following specific examples.
本发明所用原料来源如下：The sources of raw materials used in the present invention are as follows:
羧酸基离聚体A：主链为乙烯/甲基丙烯酸共聚物，熔融指数0.7g/10min，测试条件为190℃、2.16kg，甲基丙烯酸单元中的78mol％的羧基被钠离子中和，市售。Carboxylic acid group ionomer A: the main chain is ethylene/methacrylic acid copolymer, the melt index is 0.7g/10min, the test condition is 190℃, 2.16kg, 78mol% of the carboxyl group in the methacrylic acid unit is neutralized by sodium ions , commercially available.
羧酸基离聚体B：主链为乙烯/甲基丙烯酸共聚物，熔融指数4.5g/10min，测试条件为190℃、2.16kg，甲基丙烯酸单元中的45mol％的羧基被锌离子中和，市售。Carboxylic acid group ionomer B: the main chain is ethylene/methacrylic acid copolymer, the melt index is 4.5g/10min, the test condition is 190℃, 2.16kg, 45mol% of the carboxyl group in the methacrylic acid unit is neutralized by zinc ions , commercially available.
羧酸基离聚体C：主链为乙烯/甲基丙烯酸共聚物，熔融指数5.9g/10min，测试条件为190℃、2.16kg，甲基丙烯酸单元中的26mol％的羧基被锌离子中和。Carboxylic acid group ionomer C: the main chain is ethylene/methacrylic acid copolymer, the melt index is 5.9g/10min, the test condition is 190℃, 2.16kg, 26mol% of carboxyl groups in the methacrylic acid unit are neutralized by zinc ions .
聚碳酸酯：熔指为5.7g/10min，测试条件为300℃，1.2kg，牌号PC WY-106BR，单体为双酚A(BPA)和碳酸二苯酯(DPC，市售)；Polycarbonate: melt index is 5.7g/10min, test condition is 300℃, 1.2kg, brand PC WY-106BR, monomers are bisphenol A (BPA) and diphenyl carbonate (DPC, commercially available);
苯乙烯-马来酸酐无规共聚物A：马来酸酐含量为18±2wt％，SMA-700，熔融指数为7-15g/10min，230℃，2.16kg，市售。Styrene-maleic anhydride random copolymer A: maleic anhydride content is 18±2wt%, SMA-700, melt index is 7-15g/10min, 230°C, 2.16kg, commercially available.
苯乙烯-马来酸酐无规共聚物B：马来酸酐含量为12±2wt％，SMA-700-R50，熔融指数为5-10g/10min，230℃，2.16kg，市售。Styrene-maleic anhydride random copolymer B: maleic anhydride content is 12±2wt%, SMA-700-R50, melt index is 5-10g/10min, 230°C, 2.16kg, commercially available.
苯乙烯-马来酸酐无规共聚物C：马来酸酐含量为23±1wt％，SZ23110，熔融指数为20-30g/10min，230℃，2.16kg，市售。Styrene-maleic anhydride random copolymer C: maleic anhydride content is 23±1wt%, SZ23110, melt index is 20-30g/10min, 230°C, 2.16kg, commercially available.
苯乙烯-马来酸酐无规共聚物D：马来酸酐含量为5±1wt％，SMA EF-80，熔融指数为18-25g/10min，230℃，2.16kg，市售。Styrene-maleic anhydride random copolymer D: maleic anhydride content is 5±1wt%, SMA EF-80, melt index is 18-25g/10min, 230°C, 2.16kg, commercially available.
硬脂酸锌：ZINC STEARATE(BS-2818)，市售；Zinc stearate: ZINC STEARATE (BS-2818), commercially available;
实施例与对比例聚碳酸酯组合物的制备方法，按照配比，将离聚体、聚碳酸酯、苯乙烯-马来酸酐无规共聚物、润滑剂混合均匀后，通过双螺杆挤出机挤出造粒，得到聚碳酸酯组合物，其中，螺杆的温度范围是200-260℃，转速范围是300-350r/min。Example and comparative example The preparation method of polycarbonate composition, according to the proportion, after mixing ionomer, polycarbonate, styrene-maleic anhydride random copolymer, and lubricant uniformly, it is passed through a twin-screw extruder. Extrusion and granulation are performed to obtain a polycarbonate composition, wherein the temperature of the screw is in the range of 200-260° C., and the rotation speed is in the range of 300-350 r/min.
各项性能测试方法Various performance test methods
(1)低温缺口冲击测试：参考标准ISO 180-2000测试，样条厚度为4.0mm，测试温度为-40℃。(1) Low temperature notched impact test: refer to the standard ISO 180-2000 test, the thickness of the spline is 4.0mm, and the test temperature is -40℃.
(2)常温缺口冲击测试：参考标准ISO 180-2000测试，样条厚度为4.0mm，测试温度为23℃。(2) Notched impact test at room temperature: reference standard ISO 180-2000 test, the thickness of the spline is 4.0mm, and the test temperature is 23°C.
(3)内应力测试：将ISO527.2-2012拉伸样条固定在曲率为1.0的夹具上，涂抹甲苯：乙醇＝1:3的溶剂，观察样条开裂时间以及开裂形态。涂抹溶剂后1h内断裂记做1级，1-4h开裂的记做2级，4-12h开裂记做3级，12-24h记做4级，超过24h的均记做5级。开裂形态方面，分为微裂痕和大裂痕两种形态，长度小于2mm为微裂痕，长度大于2mm为大裂痕。(3) Internal stress test: Fix the ISO527.2-2012 tensile spline on a fixture with a curvature of 1.0, apply a solvent of toluene:ethanol=1:3, and observe the cracking time and cracking shape of the spline. The cracks within 1 hour after applying the solvent are recorded as grade 1, the cracks in 1-4 hours are recorded as grade 2, the cracks in 4-12 hours are recorded as grade 3, the cracks in 12-24 hours are recorded as grade 4, and the cracks over 24 hours are recorded as grade 5. In terms of cracking morphology, it is divided into two types: micro-cracks and large cracks. The length is less than 2mm for micro-cracks, and the length is greater than 2mm for large cracks.
表1：实施例1-7聚碳酸酯组合物各组分配比(重量份)及性能测试结果Table 1: The distribution ratio (parts by weight) and performance test results of each component of the polycarbonate compositions of Examples 1-7
Figure PCTCN2021082010-appb-000001
Figure PCTCN2021082010-appb-000001
由实施例1-7可知，优选聚碳酸酯含量80份、羧酸基离聚体含量10-21份、苯乙烯-马来酸酐无规共聚物含量5-20份。It can be seen from Examples 1-7 that the content of polycarbonate is preferably 80 parts, the content of carboxylic acid group ionomer is 10-21 parts, and the content of styrene-maleic anhydride random copolymer is 5-20 parts.
表2：实施例8-10聚碳酸酯组合物各组分配比(重量份)及性能测试结果Table 2: The distribution ratio (parts by weight) and performance test results of each component of the polycarbonate composition of Example 8-10
   实施例8Example 8 实施例9Example 9 实施例10Example 10
聚碳酸酯polycarbonate 8080 8080 8080
羧酸基离聚体ACarboxylic acid group ionomer A    21twenty one 33
羧酸基离聚体BCarboxylic acid group ionomer B 21twenty one      
苯乙烯-马来酸酐无规共聚物AStyrene-maleic anhydride random copolymer A 1212    1212
苯乙烯-马来酸酐无规共聚物BStyrene-maleic anhydride random copolymer B    1212   
润滑剂lubricant 0.10.1 0.10.1   
缺口冲击强度(-40℃)kJ/m 2 Notched impact strength (-40℃)kJ/m 2 4747 4141 3838
缺口冲击强度(23℃)kJ/m 2 Notched impact strength (23℃)kJ/m 2 7171 6464 5757
内应力测试Internal stress test 4级微裂痕Grade 4 Microcracks 5级微裂痕Grade 5 Microcracks 4级微裂痕Grade 4 Microcracks
表3：对比例聚碳酸酯组合物各组分配比(重量份)及性能测试结果Table 3: Composition ratio (parts by weight) and performance test results of each component of the polycarbonate composition of comparative example
   对比例1Comparative Example 1 对比例2Comparative Example 2 对比例3Comparative Example 3 对比例4Comparative Example 4
聚碳酸酯polycarbonate 8080 8080 8080 8080
羧酸基离聚体ACarboxylic acid group ionomer A 21twenty one 21twenty one    3333
苯乙烯-马来酸酐无规共聚物AStyrene-maleic anhydride random copolymer A       1212 3030
苯乙烯-马来酸酐无规共聚物CStyrene-maleic anhydride random copolymer C 1212         
苯乙烯-马来酸酐无规共聚物DStyrene-maleic anhydride random copolymer D    1212      
润滑剂lubricant 0.10.1 0.10.1 0.10.1 0.10.1
缺口冲击强度(-40℃)kJ/m 2 Notched impact strength (-40℃)kJ/m 2 1818 1515 23twenty three 3636
缺口冲击强度(23℃)kJ/m 2 Notched impact strength (23℃)kJ/m 2 3232 2828 3939 5353
内应力测试Internal stress test 4级大裂痕4th grade big rift 4级微裂痕Grade 4 Microcracks 2级大裂痕tier 2 big rift 3级微裂痕Grade 3 Microcracks
由对比例1/2可知，苯乙烯-马来酸酐无规共聚物中马来酸酐含量过高或过低，对于低温冲击性能的提升不足。It can be seen from the comparative example 1/2 that the content of maleic anhydride in the styrene-maleic anhydride random copolymer is too high or too low, and the improvement of low temperature impact performance is insufficient.
由对比例3/4可知，各组分配比不在本发明的范围内，也很难达到本发明的技术效果。It can be seen from the comparative example 3/4 that the distribution ratio of each group is not within the scope of the present invention, and it is difficult to achieve the technical effect of the present invention.

Claims (9)

  1. 一种聚碳酸酯组合物，其特征在于，按重量份计，包括以下组分：A polycarbonate composition, characterized in that, in parts by weight, comprising the following components:
    聚碳酸酯                    80份；80 copies of polycarbonate;
    苯乙烯-马来酸酐无规共聚物    5-20份；5-20 parts of styrene-maleic anhydride random copolymer;
    羧酸基离聚体                3-25份；Carboxylic acid group ionomer 3-25 copies;
    苯乙烯-马来酸酐无规共聚物中马来酸酐含量为10-20wt％。The content of maleic anhydride in the styrene-maleic anhydride random copolymer is 10-20 wt%.
  2. 根据权利要求1所述的聚碳酸酯组合物，其特征在于，按重量份计，包括以下组分：polycarbonate composition according to claim 1, is characterized in that, by weight, comprises the following components:
    聚碳酸酯                    80份；80 copies of polycarbonate;
    苯乙烯-马来酸酐无规共聚物    5-20份；5-20 parts of styrene-maleic anhydride random copolymer;
    羧酸基离聚体                10-21份。Carboxylic acid group ionomer 10-21 parts.
  3. 根据权利要求1或2所述的聚碳酸酯组合物，其特征在于，所述的羧酸基离聚体为乙烯/甲基丙烯酸类共聚物，其中甲基丙烯酸单元中的40mol％-90mol％的羧基被金属离子中和，熔融指数范围是0.5-15g/10min，测试条件为190℃、2.16kg。The polycarbonate composition according to claim 1 or 2, wherein the carboxylic acid group ionomer is an ethylene/methacrylic acid copolymer, wherein 40mol%-90mol% of the methacrylic acid unit The carboxyl group is neutralized by metal ions, the melt index range is 0.5-15g/10min, and the test conditions are 190℃, 2.16kg.
  4. 根据权利要求3所述的聚碳酸酯组合物，其特征在于，所述的金属离子选自钠离子、锌离子、镁离子、钾离子中的至少一种。The polycarbonate composition according to claim 3, wherein the metal ion is selected from at least one of sodium ion, zinc ion, magnesium ion, and potassium ion.
  5. 根据权利要求1或2所述的聚碳酸酯组合物，其特征在于，所述的聚碳酸酯的熔融指数为3-22g/10min，测试条件为300℃、1.2kg。The polycarbonate composition according to claim 1 or 2, wherein the melt index of the polycarbonate is 3-22 g/10min, and the test conditions are 300° C. and 1.2 kg.
  6. 根据权利要求1或2所述的聚碳酸酯组合物，其特征在于，所述的苯乙烯-马来酸酐无规共聚物的熔融指数为3-40g/10min，230℃，2.16kg。The polycarbonate composition according to claim 1 or 2, wherein the styrene-maleic anhydride random copolymer has a melt index of 3-40g/10min, 230°C, 2.16kg.
  7. 根据权利要求1或2所述的聚碳酸酯组合物，其特征在于，按重量份计，还包括0-2份的润滑剂；所述的润滑剂选自硬脂酸盐类润滑剂、脂肪酸类润滑剂、硬脂酸酯类润滑剂中的至少一种。The polycarbonate composition according to claim 1 or 2, characterized in that, in parts by weight, further comprising 0-2 parts of lubricant; the lubricant is selected from stearate lubricants, fatty acids At least one of a type lubricant and a stearate type lubricant.
  8. 权利要求1-7任一项所述的聚碳酸酯组合物的制备方法，其特征在于，包括以下步骤：按照配比，将各组分混合均匀后，通过双螺杆挤出机挤出造粒，得到聚碳酸酯组合物，其中，螺杆的温度范围是200-260℃，转速范围是180-500r/min。The method for preparing a polycarbonate composition according to any one of claims 1-7, characterized in that it comprises the following steps: after mixing the components uniformly according to the ratio, extruding and granulating through a twin-screw extruder , to obtain a polycarbonate composition, wherein the temperature range of the screw is 200-260° C., and the rotational speed range is 180-500 r/min.
  9. 权利要求1-7任一项所述的聚碳酸酯组合物的应用，其特征在于，用于制备表面耐刮的电子电器外壳。The application of the polycarbonate composition according to any one of claims 1 to 7, characterized in that, it is used to prepare an electronic and electrical housing with a scratch-resistant surface.
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