WO2022095363A1 - 一种聚碳酸酯合金组合物及其制备方法和应用 - Google Patents

一种聚碳酸酯合金组合物及其制备方法和应用 Download PDF

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WO2022095363A1
WO2022095363A1 PCT/CN2021/090755 CN2021090755W WO2022095363A1 WO 2022095363 A1 WO2022095363 A1 WO 2022095363A1 CN 2021090755 W CN2021090755 W CN 2021090755W WO 2022095363 A1 WO2022095363 A1 WO 2022095363A1
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alloy composition
polycarbonate
polycarbonate alloy
parts
polyurethane
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PCT/CN2021/090755
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French (fr)
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梁惠强
岑茵
黄险波
艾军伟
李明昆
张志铭
丁超
叶南飚
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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention belongs to the field of engineering plastics, and particularly relates to a polycarbonate alloy composition, a preparation method and application thereof.
  • Polycarbonate alloy (polycarbonate and polyolefin) is a new type of high-performance alloy with beneficial characteristics such as high surface gloss, good toughness, and good processing fluidity.
  • the addition of polyolefin can greatly improve polycarbonate.
  • the chemical resistance is extended to various fields, especially in the fields of engineering plastics technology in electronic appliances, transportation, building materials and other fields.
  • polycarbonate alloys with low dielectric properties have great application potential;
  • the gloss will make the visual sensory effect of the product softer and more durable, and meet the increasingly high requirements for the diversification of material appearance. Therefore, polycarbonate alloys with lower dielectric constant and satisfactory matte appearance have better application prospects.
  • the surface of the material can also have a certain roughness through the pattern design of the injection mold, so as to achieve a matte effect.
  • the purpose of the present invention is to overcome the defects or deficiencies of high gloss and poor dielectric properties of polycarbonate alloy compositions in the prior art, and to provide a polycarbonate alloy composition.
  • the invention can greatly reduce the gloss of the polycarbonate alloy composition, and can achieve satisfactory matte effect in both injection molding and extrusion processes. Better dielectric properties.
  • Another object of the present invention is to provide a method for preparing the above-mentioned polycarbonate alloy composition.
  • Another object of the present invention is to provide the application of the above-mentioned polycarbonate alloy composition in the preparation of engineering plastics.
  • a polycarbonate alloy composition comprising the following components in parts by weight:
  • Polyolefin has relatively low gloss (compared to polycarbonate), polycarbonate and polyolefin are compounded as base resins, resulting in a resin system with relatively low gloss (compared to polycarbonate); acrylic shell Silicone rubber has good compatibility with polycarbonate (PC). The addition of acrylic shell silicone rubber with a certain particle size will partially reduce the gloss of polyolefin alloys and achieve a weak matte effect; polyurethane (PU) It has a shape memory function, which can adjust the compatibility between polycarbonate and other components, so that the rubber particles in the system can be micro-shrinked and fixed on the surface of the composition more easily. It has a synergistic effect and gives polyolefin alloys a better matte effect.
  • polyolefin can improve the dielectric properties of the polycarbonate alloy composition
  • acrylic shell silicone rubber has better weather resistance
  • polyurethane can impart excellent processability to the material.
  • the synergistic effect of olefins can achieve satisfactory dielectric properties with lower dielectric constants.
  • the polycarbonate alloy composition provided by the present invention has an injection glossiness of less than 15, an extrusion glossiness of less than 20, and has a relatively low dielectric constant, which can meet the matte effect requirements of different processing techniques (extrusion, injection molding, etc.). .
  • the polycarbonate alloy composition comprises the following components in parts by weight:
  • Polycarbonates, polyolefins, tougheners, antioxidants and lubricants conventionally used in the art to prepare polycarbonate alloy compositions can be used in the present invention.
  • the weight-average molecular weight of the polycarbonate is 40,000-52,000, and the content of terminal hydroxyl groups is less than 100 ppm.
  • the content of terminal hydroxyl groups is measured by the following method: take a specific content of the test sample to prepare a 1% concentration (mass concentration) clear solution, rinse with neutral ethanol, add quantitative phenolphthalein indicator, and titrate with 0.5mol/L hydrochloric acid solution The content of terminal hydroxyl group is obtained according to the consumption of hydrochloric acid.
  • the polyolefin is one or more of polyethylene (PE) or polypropylene (PP).
  • PE polyethylene
  • PP polypropylene
  • the crystallinity of the polyolefin is 50-95%.
  • the silica gel content of the acrylic shell silicone rubber is greater than 10%.
  • the rubber D50 of the acrylic shell silicone rubber is 800-1000 nm.
  • the acrylic shell silicone rubber is one or both of S-2130 or S-2100.
  • the Tg temperature of the polyurethane is less than -30°C, the refractive index is 1.52, the oil absorption value is 50-150, and the D50 is 3-40 ⁇ m.
  • the D50 of the polyurethane is 5-8 ⁇ m.
  • the Tg temperature of polyurethane is measured by the following method: take a specific weight of the polyurethane test sample and put it in a differential calorimeter, set the heating rate to 10 °C/min, and the heating range to -60 to 200 °C. Cycle to read the Tg temperature from the analytical curve.
  • the refractive index of the polyurethane was measured directly by an Abbe refractometer with a thickness of 2 mm.
  • the oil absorption value of the polyurethane is measured by the following method: gradually add dioctyl phthalate to the polyurethane of a fixed weight, stir well until no reagent is precipitated, and the oil absorption value of the polyurethane can be obtained according to the quality of the added reagent.
  • the weight ratio of the polyolefin, the acrylic shell silicone rubber and the polyurethane is 1:0.15-0.35:0.15-0.35.
  • the toughening agent is a rubber-containing graft polymer.
  • Rubber-containing graft polymers are generally prepared by emulsion polymerization.
  • component A is grafted onto component B.
  • the dosages of component A and component B are 5-95% of component A and component B based on the weight of the toughening agent; preferably 10-70% of component A and 30-90% of component B; particularly preferably Component A 20 ⁇ 60%, Component B 40 ⁇ 80%.
  • component A consists of the following: vinyl aromatic compounds (eg styrene, alpha-methyl styrene), vinyl aromatic compounds substituted on the ring (eg p-methyl styrene, p-chlorostyrene) and methyl styrene
  • vinyl aromatic compounds eg styrene, alpha-methyl styrene
  • vinyl aromatic compounds substituted on the ring eg p-methyl styrene, p-chlorostyrene
  • methyl styrene At least one monomer of (C1-C8)-alkyl methacrylate (such as methyl methacrylate, ethyl methacrylate) (the amount of which is 65-85% by weight of component A, preferably 70-80%) %), as well as vinyl cyanide (such as unsaturated nitriles such as acrylonitrile and methacrylonitrile), (C1-C8)-alkyl (meth)
  • the B component provides the elastomer graft base.
  • the graft base preferably has a glass transition temperature of ⁇ 0°C, more preferably ⁇ 20°C, particularly preferably ⁇ 60°C.
  • component B can be one or more of the following substances: diene rubber, diene-vinyl block copolymer rubber, EP(D)M rubber, polyurethane rubber, silicone rubber, chloroprene Ethylene rubber, ethylene/vinyl acetate rubber, etc.
  • the toughening agent is one or both of HR-181 or M722.
  • the antioxidants are hindered phenolic antioxidants (such as 1010, 176, etc.), phosphite antioxidants (such as 168, 626, 9228, etc.) or hindered amine antioxidants (such as 1098, etc.) ) one or more of them.
  • hindered phenolic antioxidants such as 1010, 176, etc.
  • phosphite antioxidants such as 168, 626, 9228, etc.
  • hindered amine antioxidants such as 1098, etc.
  • the lubricant is one or more of PETS, GTS, GMS, silicone oil or white oil.
  • the injection gloss of the polycarbonate alloy composition is less than 15; the extrusion gloss is less than 20.
  • the polycarbonate alloy composition provided by the present invention can be obtained by extrusion or injection molding.
  • the preparation method of the above-mentioned polycarbonate alloy composition comprises the following steps: mixing polycarbonate, polyolefin, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant and lubricant, extruding, granulating, namely The polycarbonate alloy composition is obtained.
  • polycarbonate, polyolefin, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant and lubricant are mixed through a high mixer and then added from the main feeding port, and the polyurethane component is separately fed through the side.
  • the material is added in the mouth, extruded, and pelletized to obtain the polycarbonate alloy composition.
  • the heat resistance of the polyurethane component is poor, and adding it through the side feed port can better ensure the performance of the polyurethane.
  • the process of using the injection molding process to prepare the polycarbonate alloy composition is as follows:
  • the preparation method of the above-mentioned polycarbonate alloy composition comprises the following steps: mixing polycarbonate, polyolefin, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant and lubricant, and injection molding to obtain the polymer Carbonate alloy composition.
  • the preparation method of the invention has the advantages of simple process, strong applicability and easy popularization and application.
  • the application of the polycarbonate alloy composition in the preparation of 5G equipment is preferably, the application of the polycarbonate alloy composition in the preparation of 5G equipment.
  • the present invention has the following beneficial effects:
  • the polycarbonate alloy composition provided by the invention improves the gloss by adding acrylic shell silicone rubber and polyurethane, gives the polycarbonate alloy composition a better matte effect, and can meet the requirements of various processes for gloss; in addition,
  • the dielectric properties of polycarbonate alloy compositions can also be substantially improved by the synergistic effect of acrylic shell silicone rubber, polyurethane and polyolefin.
  • the preparation method of the invention has the advantages of simple process, strong applicability and easy popularization and application.
  • PC resin S-2000F, Shanghai Mitsubishi, the weight average molecular weight is 48000, and the terminal hydroxyl content is 10ppm;
  • PC resin E-1000F, Shanghai Mitsubishi, the weight average molecular weight is 50000, and the terminal hydroxyl content is 25ppm;
  • PP resin, 3EK10, SABIC, crystallinity is 60-90%
  • PE resin HDPE 5000S, Korea Lotte, crystallinity is 70-96%;
  • Acrylic shell silicone rubber S-2130, Japan Mitsubishi Rayon, the content of silica gel is 30%, and the rubber particle size D50 is 800nm;
  • Acrylic shell silicone rubber S-2100, Mitsubishi Rayon, Japan, the content of silica gel is 10%, and the rubber particle size D50 is 850nm;
  • Acrylic shell silicone rubber Sx-006, Mitsubishi Rayon, Japan, the content of silica gel is 10%, and the rubber particle size D50 is 100nm;
  • Polyurethane PC-8 innovative chemical industry, Tg is -48°C, refractive index is 1.52, oil absorption value is 80, D50 is 5 ⁇ m;
  • Polyurethane PC-5 innovative chemical industry, Tg is -35°C, refractive index is 1.52, oil absorption value is 52, D50 is 38 ⁇ m;
  • Tg is -35°C
  • refractive index is 1.52
  • oil absorption value is 40
  • D50 is 38 ⁇ m
  • Antioxidants 1076 and 168, BASF;
  • weathering agent UV360 Tianjin Lianlong.
  • the polycarbonate alloy compositions of the respective examples and comparative examples were prepared by the following methods.
  • Extrusion process Polycarbonate, polyolefin, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant, lubricant and other functional additives (if any) are mixed through a high mixer and then mixed from the main feed.
  • the polyurethane component is separately added through the side feeding port, extruded, and pelletized to obtain the polycarbonate alloy composition.
  • Injection molding process Mix polycarbonate, polyolefin, acrylic shell silicone rubber, polyurethane, toughening agent, antioxidant, lubricant and other functional additives (if any), and then inject it to obtain the polycarbonate alloy combination.
  • Injection gloss According to the ASTM-D523-2014 standard, test the injection molding plate with a thickness of 3.0mm and a diameter of not less than 60mm. Well, when the injection gloss is less than 15° and the extrusion gloss is less than 20°, the comprehensive matte effect is the best.
  • Extrusion gloss The sheet with a film thickness of 3.0mm was formed at an extrusion dimension of 240°C. After cooling at room temperature for 48 hours, the gloss at 60° was tested with a gloss meter according to the ASTM-D523-2014 standard. The gloss was about The smaller, the better the matte finish.
  • Dielectric properties The test conditions are at 2.5GHz, the test thickness is 2.5mm, the length is 100mm, and the width is 100mm.
  • PC)% test where Dk (PC) is the dielectric constant of PC resin, which is 3.0; Dk (composition) is the test value of the dielectric constant of the composition, the greater the dielectric decrease, the better the dielectric properties.
  • This example provides a series of polycarbonate alloy compositions, the components thereof.
  • This example provides a series of polycarbonate alloy compositions, the components and amounts of which are shown in Table 2.
  • This comparative example provides a series of polycarbonate alloy compositions whose components are shown in Table 3.
  • Comparative Example 5 developed serious cosmetic defects after extrusion/injection molding.
  • the polycarbonate alloy compositions provided by the various embodiments of the present invention have low dielectric constant and excellent matte properties, and when the addition amount of acrylic shell silicone rubber is 5-10, the addition of polyurethane When the weight ratio of polyolefin, acrylic shell silicone rubber and polyurethane is between 1:0.15-0.35:0.15-0.35, it has better comprehensive performance.
  • the addition amount achieves the appearance of matte effect; in Comparative Example 2, because only polyurethane and polyolefin are added, although the gloss can be reduced, it does not meet the requirements of uniform matte, and the addition of polyurethane alone will cause the polycarbonate resin matrix to have insufficient toughness This leads to application limitations; in Comparative Example 6, because the rubber particle size (D50) of the added acrylic shell silicone rubber is too small, the polycarbonate alloy cannot form rubber particles with sufficient surface quality to achieve a certain diffuse reflection effect and improve gloss. not effectively. In Comparative Example 7, since no polyolefin was added, the gloss of the base resin system was very high, and the matte effect could not be achieved by the synergistic effect of polyurethane and acrylic shell silicone rubber.
  • the synergistic effect of acrylic shell silicone rubber, polyurethane and polyolefin can greatly improve the dielectric properties of the polycarbonate alloy composition. Therefore, the dielectric properties of each example are better than those of Comparative Examples 1-4 and 6-7 due to the lack of olefins.
  • the synergistic effect or synergy of acid shell silicone rubber, polyurethane and polyolefin is not good, and it has a high conductivity constant.

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Abstract

本发明涉及一种聚碳酸酯合金组合物及其制备方法和应用。该聚碳酸酯合金组合物包括聚碳酸酯、聚烯烃、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂等组分。本发明提供的聚碳酸酯合金组合物通过添加丙烯酸壳类硅橡胶和聚氨酯来改善光泽，赋予聚碳酸酯合金组合物较好的哑光效果，可满足多种工艺对光泽度的需求；另外，通过烯酸壳类硅橡胶、聚氨酯和聚烯烃协同作用可大幅改善聚碳酸酯合金组合物的介电性能。

Description

一种聚碳酸酯合金组合物及其制备方法和应用 技术领域
本发明属于工程塑料领域，具体涉及一种聚碳酸酯合金组合物及其制备方法和应用。
背景技术
聚碳酸酯合金(聚碳酸酯和聚烯烃)是一种新型的高性能合金，具有表面光泽度高，韧性好，加工流动性好等有益特点，聚烯烃的加入同时能大幅度改善聚碳酸酯的耐化学性，扩展应用于各个领域当中，特别是电子电器，交通运输，建筑材料等领域工程塑料技术领域。随着行业的发展，在通讯行业，尤其在有5G要求的应用场合，具有低介电性能的聚碳酸酯合金具有较大的应用潜力；另外，在产品的使用过程中具有哑光效果的低光泽度会让产品的视觉感官效果更加柔和和耐久，满足对材料外观多元化的越来越高的要求。因此具有较低的介电常数及具有满意的哑光外观的聚碳酸酯合金具有较好的应用前景。
目前常用哑光技术有以下几种：
1)添加无机材料，如纳米二氧化硅，通过利用填料表面和基体树脂之间的不相容性和不易浸润性，在加工的过程中填料会迁移，形成凹凸不平的的表面，从而产生哑光效果；CN201410177444.2就公开通过添加ACS和纳米二氧化硅来实现哑光效果的PCABS。
2)加入含量较高的橡胶，尤其是粒径较大或者具有一定交联度的橡胶，在加工过程中橡胶和树脂基体会发生分相，通过橡胶发生的微收缩导致材料表面形成粗糙的效果而产生哑光效果；
3)加入环氧类物质，通过环氧基团的引入，降低了ABS和PC树脂之间的相容性，从而降低材料表面的光泽度，从而产生哑光效果；CN201810442932.X就公开了通过添加环氧化物和云母粉来实现哑光效果的PCABS。
4)也可通过注塑模具的纹路设计，使材料表面具有一定的粗糙度，从而实现哑光效果。
以上的哑光技术均具有一定的局限性，如填料的加入会导致基体连续相的不一致，容易引起力学性能和外观等其它性能，尤其是加工过程中熔接线隐患；橡 胶和环氧的大量加入会大幅度影响树脂的流动性，以及降低材料的刚性，因此在一定程度上限制了材料的应用，尤其是薄壁化的行业发展趋势下，较低的流动性将产生较大的弊端；依靠模具设计对材料的加工条件依赖性强，适用性不广。
因此，开发一种具有哑光和低介电常数的聚碳酸酯合金组合物具有重要的研究意义和经济价值。
发明内容
本发明的目的在于克服现有技术中聚碳酸酯合金组合物光泽高，介电性能不佳的缺陷或不足，提供一种聚碳酸酯合金组合物。本发明通过丙烯酸壳类硅橡胶和聚氨酯的协同增效作用，可以大幅度降低聚碳酸酯合金组合物的光泽度，并在注塑和挤出的工艺上均可实现满意的哑光效果，同时具有较佳的介电性能。
本发明的另一目的在于提供上述聚碳酸酯合金组合物的制备方法。
本发明的另一目的在于提供上述聚碳酸酯合金组合物在制备工程塑料中的应用。
为实现上述发明目的，本发明采用如下技术方案：
一种聚碳酸酯合金组合物，包括如下重量份数的组分：
Figure PCTCN2021090755-appb-000001
聚烯烃具有相对较低(与聚碳酸酯相比)的光泽度，聚碳酸酯和聚烯烃复配作为基础树脂，使得树脂体系的光泽度相对较低(与聚碳酸酯相比)；丙烯酸壳类硅橡胶与聚碳酸酯(PC)具有较好的相容性，一定粒径大小丙烯酸壳类硅橡胶的加入会部分降低聚烯烃合金的光泽度，实现微弱的哑光效果；聚氨酯(PU)具有形状记忆功能，可以调节聚碳酸酯和其它组分之间的相容性，从而让体系中的橡胶粒子微收缩在组合物的表面上更加容易固定形成，在光泽上与丙烯酸壳类 硅橡胶起到协同增效作用，赋予聚烯烃合金较好的哑光效果。
另外，聚烯烃的加入可改善聚碳酸酯合金组合物的介电性能，丙烯酸壳类硅橡胶具有较佳的耐候性，聚氨酯可赋予材料优异的加工性，通过丙烯酸壳类硅橡胶、聚氨酯和聚烯烃的协同作用，可实现令人满意的介电性能，具有较低的介电常数。
本发明提供的聚碳酸酯合金组合物的注塑光泽度小于15，挤出光泽度小于20，且具有较低的介电常数，可满足不同加工工艺(挤出、注塑等)的哑光效果需求。
优选地，所述聚碳酸酯合金组合物包括如下重量份数的组分：
Figure PCTCN2021090755-appb-000002
本领域常规用来制备聚碳酸酯合金组合物的聚碳酸酯、聚烯烃、增韧剂、抗氧剂和润滑剂均可用于本发明中。
优选地，所述聚碳酸酯的重均分子量为40000～52000，端羟基含量小于100ppm。
端羟基的含量通过如下方法测得：取特定含量的测试样配制1％浓度(质量浓度)的澄清溶液，用中性乙醇冲洗，并加入定量的酚酞指示剂，用0.5mol/L盐酸溶液滴定量至红色消失，根据盐酸消耗量即得到端羟基含量。
优选地，所述聚烯烃为聚乙烯(PE)或聚丙烯(PP)中的一种或几种)。
更为优选地，所述聚烯烃的结晶度为50～95％。
优选地，所述丙烯酸壳类硅橡胶的硅胶含量大于10％。
优选地，所述丙烯酸壳类硅橡胶的橡胶D50为800～1000nm。
优选地，所述丙烯酸壳类硅橡胶为S-2130或S-2100中的一种或两种。
优选地，所述聚氨酯的Tg温度小于-30℃，折射率为1.52，且吸油值在50～150， D50为3～40μm。
更为优选地，所述聚氨酯的D50为5～8μm。
聚氨酯的Tg温度通过如下方法测得：取特定重量的聚氨酯测试样放入示差热量分析仪器中，设定升温速率为10℃/min，升温范围为-60～200℃，氮气氛围并进行两个循环，从分析曲线中读取Tg温度。
聚氨酯的折射率通过厚度为2mm的测试样板阿贝折射仪直接测得。
聚氨酯的吸油值通过如下方法测得：在固定重量的聚氨酯中逐步加入邻苯二甲酸二辛酯，充分搅拌直至无试剂析出，根据添加试剂的质量即可得到聚氨酯的吸油值。
优选地，所述聚烯烃、丙烯酸壳类硅橡胶和聚氨酯的重量比为1:0.15～0.35:0.15～0.35。
优选地，所述增韧剂为含橡胶的接枝聚合物。
含橡胶的接枝聚合物一般通过乳液聚合制备得到。
具体地，由组分A接枝至组分B上。A组分和组分B的用量按增韧剂重量计，为组分A，组分B 5～95％；优选为组分A 10～70％，组分B 30～90％；特别优选为组分A 20～60％，组分B 40～80％。
其中组分A组成如下：乙烯基芳族化合物(例如苯乙烯、α-甲基苯乙烯)、在环上取代的乙烯基芳族化合物(例如对甲基苯乙烯、对氯苯乙烯)和甲基丙烯酸(C1～C8)-烷基酯(例如甲基丙烯酸甲酯、甲基丙烯酸乙酯)的至少一种单体(其用量为组分A重量的65～85％，优选为70～80％)，以及乙烯基氰(例如不饱和腈，如丙烯腈和甲基丙烯腈)、(甲基)丙烯酸(C1～C8)-烷基酯(例如甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯)和不饱和羧酸的衍生物(例如酐和酰亚胺、马来酸酐和N-苯基马来酰亚胺)的至少一种单体(其用量为组分A重量的15～35％，优选为20～30％)。
B组分提供弹性体接枝基础。该接枝基础优选具有<0℃，更优选<-20℃，特别优选<-60℃的玻璃化转变温度。
具体地，组分B可为如下物质中的一种或几种：二烯橡胶、二烯-乙烯基嵌段共聚物橡胶、EP(D)M橡胶、聚氨酯橡胶、硅酮橡胶、氯丁二烯橡胶、乙烯/乙酸乙烯酯橡胶等。
具体地，所述增韧剂为HR-181或M722中的一种或两种。
优选地，所述抗氧剂为受阻酚类抗氧剂(例如1010、176等)、亚磷酸酯类抗氧剂(例如168、626、9228等)或受阻胺类抗氧剂(例如1098等)中的一种或几种。
优选地，所述润滑剂为PETS、GTS、GMS、硅油或白油中的一种或几种。
优选地，所述聚碳酸酯合金组合物的注塑光泽度小于15；挤出光泽度小于20。
本发明提供的聚碳酸酯合金组合物既可挤出得到，也可注塑得到。
利用挤出工艺制备得到聚碳酸酯合金组合物的过程如下：
上述聚碳酸酯合金组合物的制备方法，包括如下步骤：将聚碳酸酯、聚烯烃、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂混合，挤出，造粒，即得所述聚碳酸酯合金组合物。
具体地，将聚碳酸酯、聚烯烃、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂混合通过高混机混合后从主喂料口加入，聚氨酯组分单独通过侧喂料口加入，挤出，造粒，即得所述聚碳酸酯合金组合物。
相较于聚碳酸酯，聚氨酯组分的耐热性较差，通过侧喂料口加入可以更好地保证聚氨酯的性能。
利用注塑工艺制备得到聚碳酸酯合金组合物的过程如下：
上述聚碳酸酯合金组合物的制备方法，包括如下步骤：将聚碳酸酯、聚烯烃、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂混合，注塑，即得所述聚碳酸酯合金组合物。
本发明的制备方法工艺简单，适用性强，易于推广应用。
上述聚碳酸酯合金组合物在制备通讯产品中的应用也在本发明的保护范围内。
优选地，所述聚碳酸酯合金组合物在制备5G设备中的应用。
与现有技术相比，本发明具有如下有益效果：
本发明提供的聚碳酸酯合金组合物通过添加丙烯酸壳类硅橡胶和聚氨酯来改善光泽，赋予聚碳酸酯合金组合物较好的哑光效果，可满足多种工艺对光泽度的需求；另外，还可通过丙烯酸壳类硅橡胶、聚氨酯和聚烯烃协同作用可大幅改 善聚碳酸酯合金组合物的介电性能。
本发明的制备方法工艺简单，适用性强，易于推广应用。
具体实施方式
下面结合实施例进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。下例实施例中未注明具体条件的实验方法，通常按照本领域常规条件或按照制造厂商建议的条件；所使用的原料、试剂等，如无特殊说明，均为可从常规市场等商业途径得到的原料和试剂。本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
本发明各实施例及对比例选用的部分试剂说明如下：
PC树脂，S-2000F，上海三菱，重均分子量为48000，端羟基含量为10ppm；
PC树脂，E-1000F，上海三菱，重均分子量为50000，端羟基含量为25ppm；
聚烯烃：
PP树脂，3EK10，SABIC，结晶度为60～90％；
PE树脂，HDPE 5000S，韩国乐天，结晶度为70～96％；
PP树脂，K7726，燕山石化，结晶度小于10％；
丙烯酸壳类硅橡胶：S-2130，日本三菱丽阳，硅胶含量为30％，橡胶粒径D50为800nm；
丙烯酸壳类硅橡胶：S-2100，日本三菱丽阳，硅胶含量为10％，橡胶粒径D50为850nm；
丙烯酸壳类硅橡胶：Sx-006，日本三菱丽阳，硅胶含量为10％，橡胶粒径D50为100nm；
聚氨酯：PC-8创新化工，Tg为-48℃，折射率为1.52，吸油值为80，D50为5μm；
聚氨酯：PC-5创新化工，Tg为-35℃，折射率为1.52，吸油值为52，D50为38μm；
聚氨酯：PC-3创新化工，Tg为-35℃，折射率为1.52，吸油值为40，D50为38μm；
抗氧剂：1076和168，BASF；
润滑剂：PETS，发基；
增韧剂HR-181，台湾奇美；
其它功能助剂：耐候剂，UV360天津利安隆。
各实施例和对比例的聚碳酸酯合金组合物通过如下方法制备得到。
挤出工艺：将聚碳酸酯、聚烯烃、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂、润滑剂和其它功能助剂(如有)混合通过高混机混合后从主喂料口加入，聚氨酯组分单独通过侧喂料口加入，挤出，造粒，即得所述聚碳酸酯合金组合物。
注塑工艺：将聚碳酸酯、聚烯烃、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂、润滑剂和其它功能助剂(如有)混合，注塑，即得所述聚碳酸酯合金组合物。
本发明各实施例及对比例的聚碳酸酯合金组合物的各项性能的测试方法如下：
注塑光泽度：根据ASTM-D523-2014标准下测试3.0mm厚度直径不小于60mm的注塑板，注塑维度为260℃，用光泽度仪测试60°光泽度大小，光泽度约小，哑光效果越好，当注塑光泽度小于15°，挤出光泽度小于20°的情况下，综合哑光效果最佳。
挤出光泽度：在挤出维度为240℃下成型膜厚为3.0mm的板材，经过室温冷却48h后，按照ASTM-D523-2014标准下用光泽度仪测试60°光泽度大小，光泽度约小，哑光效果越好。
介电性能：测试条件在2.5GHz下，测试厚度为2.5mm长度为100mm宽度为100mm的样板进行测试，通过计算公式：介电降低＝(Dk(PC)-Dk(组合物))/Dk(PC)％进行测试，其中Dk(PC)是PC树脂的介电常数，为3.0；Dk(组合物)是组合物的介电常数测试值，介电降低幅度越大，介电性能越好。
实施例1～13
本实施例提供一系列的聚碳酸酯合金组合物，其组分。
表1实施例1～13提供的聚碳酸酯合金组合物的组分(份)
Figure PCTCN2021090755-appb-000003
Figure PCTCN2021090755-appb-000004
实施例14～20
本实施例提供一系列的聚碳酸酯合金组合物，其组分及用量如表2。
表2实施例14～20提供的聚碳酸酯合金组合物的组分(份)
Figure PCTCN2021090755-appb-000005
Figure PCTCN2021090755-appb-000006
对比例1～7
本对比例提供一系列的聚碳酸酯合金组合物，其组分如表3。
表3对比例1～7提供的聚碳酸酯合金组合物的组分(份)
Figure PCTCN2021090755-appb-000007
按上述提及的测试方法对各实施例和对比例的聚碳酸酯合金组合物的性能进行测定，测试结果如表4。
其中，对比例5由于聚氨酯的添加量过大，无法挤出/注塑成型，故无法进行性能测试。对比例4挤出/注塑成型后出现了严重的外观缺陷。
表4各实施例和对比例的聚碳酸酯合金组合物的性能测试结果
Figure PCTCN2021090755-appb-000008
从表4可知，本发明各实施例提供的聚碳酸酯合金组合物具有较低的介电常数和优异的哑光性能，且当丙烯酸壳类硅橡胶的添加量为5～10，聚氨酯的添加量为5～10，聚烯烃、丙烯酸壳类硅橡胶和聚氨酯的重量比在1:0.15～0.35:0.15～0.35之间时，具有更佳的综合性能。
其中，在一定范围内(实施例1、6～9)，丙烯酸壳类硅橡胶的添加量增大时，而且哑光效果越来越明显；但丙烯酸壳类硅橡胶的添加量较大时，由于丙烯酸壳类硅橡胶和聚氨酯的协同配合作用减弱，哑光效果略有降低；如丙烯酸壳类硅橡胶的添加量过大(如对比例4)，会引起材料的严重分层外观缺陷，并且丙烯酸壳类硅橡胶中的橡胶粒子将析出至组合物的表面导致相分离，使得哑光效果相对 于不添加(对比例1)仅略有提升。在一定范围内(实施例1、10～13)，聚氨酯的添加量增大时，哑光效果越来越好，尤其是挤出哑光改善；但聚氨酯的添加量较大时，哑光效果由于丙烯酸壳类硅橡胶和聚氨酯的协同作用减弱也略有降低，且体系的热稳定性降低将导致弯折韧性的下降；如聚氨酯的添加量过大(如对比例5)，会严重降低体系的热稳定性导致韧性的下降，进而出现无法挤出现象；而对比例1由于未对聚碳酸酯合金组合物进行改性处理，和传统的聚碳酸酯合金组合物材料一致是高光泽的效果无法实现哑光的表面质感，通过单一的增韧剂的加入不能实现哑光效果，却带来加工缺陷和相分离的风险；对比例3由于仅添加丙烯酸壳类硅橡胶和聚烯烃，无法通过添加量实现哑光效果的呈现；对比例2由于仅添加聚氨酯和聚烯烃，虽然可以降低光泽度但是不满足均匀的哑光要求，同时单独加入聚氨酯会导致聚碳酸酯树脂基体不具备足够的韧性导致应用局限；对比例6由于添加的丙烯酸壳类硅橡胶的橡胶粒径(D50)过小，聚碳酸酯合金无法形成足够的表面质量的橡胶粒子来达到一定的漫反射效果，对光泽的改善效果不佳。对比例7由于未添加聚烯烃，基础树脂体系的光泽度非常高，通过聚氨酯和丙烯酸壳类硅橡胶的协同作用无法实现哑光效果。
另外，丙烯酸壳类硅橡胶、聚氨酯和聚烯烃协同作用可大幅改善聚碳酸酯合金组合物的介电性能，故各实施例的介电性能较佳对比例1～4和6～7由于缺乏烯酸壳类硅橡胶、聚氨酯和聚烯烃三者的协同作用或协同作用不佳，具有较高的导电常数。
本领域的普通技术人员将会意识到，这里的实施例是为了帮助读者理解本发明的原理，应被理解为本发明的保护范围并不局限于这样的特别陈述和实施例。本领域的普通技术人员可以根据本发明公开的这些技术启示做出各种不脱离本发明实质的其它各种具体变形和组合，这些变形和组合仍然在本发明的保护范围内。

Claims (10)

  1. 一种聚碳酸酯合金组合物，其特征在于，包括如下重量份数的组分：
    聚碳酸酯 10～90份，
    聚烯烃 10～90份，
    丙烯酸壳类硅橡胶 0.5～20份，
    聚氨酯 0.5～20份，
    增韧剂 0.1～20份，
    抗氧剂 0.001～5份，
    润滑剂 0.001～5份，
    所述丙烯酸壳类硅橡胶的橡胶D50不小于350nm。
  2. 根据权利要求1所述聚碳酸酯合金组合物，其特征在于，包括如下重量份数的组分：
    聚碳酸酯 50～70份，
    聚烯烃 30～50份，
    丙烯酸壳类硅橡胶 5～10份，
    聚氨酯 5～10份，
    增韧剂 1～15份，
    抗氧剂 0.01～2份，
    润滑剂 0.1～3份。
  3. 根据权利要求1所述聚碳酸酯合金组合物，其特征在于，所述聚碳酸酯的重均分子量为40000～52000，端羟基含量不大于100ppm；所述聚烯烃为聚乙烯或聚丙烯中的一种或几种。
  4. 根据权利要求1所述聚碳酸酯合金组合物，其特征在于，丙烯酸壳类硅橡胶的硅胶含量不小于10％。
  5. 根据权利要求1所述聚碳酸酯合金组合物，其特征在于，所述丙烯酸壳类硅橡胶的橡胶D50为800～1000nm。
  6. 根据权利要求1所述聚碳酸酯合金组合物，其特征在于，所述聚氨酯的Tg温度小于-30℃，折射率为1.52，且吸油值在50～150，D50为3～40μm。
  7. 根据权利要求1所述聚碳酸酯合金组合物，其特征在于，所述增韧剂为含橡胶的接枝聚合物；所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂或受阻 胺类抗氧剂中的一种或几种；所述润滑剂为PETS、GTS、GMS、硅油或白油中的一种或几种。
  8. 根据权利要求1所述聚碳酸酯合金组合物，其特征在于，所述聚碳酸酯合金组合物的注塑光泽度小于15；挤出光泽度小于20。
  9. 权利要求1～8任一所述聚碳酸酯合金组合物的制备方法，其特征在于，包括如下步骤：将聚碳酸酯、聚烯烃、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂挤出，造粒，即得所述聚碳酸酯合金组合物；或将聚碳酸酯、聚烯烃、丙烯酸壳类硅橡胶、聚氨酯、增韧剂、抗氧剂和润滑剂混合，注塑，即得所述聚碳酸酯合金组合物。
  10. 权利要求1～8任一所述聚碳酸酯合金组合物在制备通讯产品中的应用。
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