WO2020140306A1 - 一种可抛光的与金属连接的塑料复合材料及其制备方法 - Google Patents

一种可抛光的与金属连接的塑料复合材料及其制备方法 Download PDF

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WO2020140306A1
WO2020140306A1 PCT/CN2019/072428 CN2019072428W WO2020140306A1 WO 2020140306 A1 WO2020140306 A1 WO 2020140306A1 CN 2019072428 W CN2019072428 W CN 2019072428W WO 2020140306 A1 WO2020140306 A1 WO 2020140306A1
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Prior art keywords
composite material
metal
plastic composite
polishable
titanium dioxide
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PCT/CN2019/072428
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English (en)
French (fr)
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王璐
李强
辛敏琦
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上海锦湖日丽塑料有限公司
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Priority to JP2020567514A priority Critical patent/JP7145581B2/ja
Publication of WO2020140306A1 publication Critical patent/WO2020140306A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention relates to the field of composite materials, in particular to a polishable plastic composite material connected with metals and a preparation method thereof.
  • PBT-reinforced plastics have a general surface gloss due to glass fiber reinforcement, and the surface floating fiber is more obvious.
  • the plastic parts of nano-injection were gradually used as external leakage parts.
  • Environmental protection, cost and other requirements have certain restrictions on paint spraying.
  • the trend is to require a class of nano-injection plastics that have good adhesion to metals, and can achieve a polishing effect similar to metals without spraying.
  • more patents are focused on enhancing the binding strength of nano-injection plastics that enhance PBT substrates.
  • little attention has been paid to the improvement of the polishing performance of PBT reinforced materials.
  • the purpose of the present invention is to provide a polishable plastic composite material connected to a metal and a preparation method thereof to overcome the above-mentioned defects in the prior art.
  • the invention provides a polishable plastic composite material connected with metal, including the following parts by weight of each component:
  • Short-cut glass fiber GF 10 ⁇ 50
  • Nano-TiO 2 nano-TiO 2 1 ⁇ 5
  • Dispersed fluid medium 3 ⁇ 10
  • Toughening agent 5 ⁇ 10
  • Antioxidant 0.1 ⁇ 1,
  • Lubricant 0.1 to 1.
  • the polishable metal-connected plastic composite material includes the following parts by weight of each component:
  • Short-cut glass fiber GF 10 ⁇ 30
  • Nano titanium dioxide nano-TiO 2 3 ⁇ 5
  • Dispersed fluid medium 6 ⁇ 10
  • Toughening agent 8 ⁇ 10
  • Antioxidant 0.5 ⁇ 1,
  • Lubricant 0.5 to 1.
  • the viscosity of the polybutylene terephthalate at 23°C is 0.6-1dl/g.
  • the chopped glass fiber is alkali-free chopped fiber, with a diameter of 5-17 ⁇ m and a length of 5-10 mm, and its surface is treated with a silane coupling agent, and the content of the silane coupling agent accounts for the chopped fiber 0.5-1% of glass fiber mass.
  • the nano titanium dioxide is prepared by a sol-gel method, and nickel oxide is grafted on the surface; the content of the nickel oxide is 5-10% of the mass of the nano titanium dioxide.
  • the dispersion fluid medium is an organosilicon fluid medium
  • the main component is an organosilicon liquid having a viscosity of 0.4-1.5 dl/g at 23°C, wherein PDMS accounts for 20-70% of the organosilicon fluid medium.
  • the compatibilizer is a multifunctional copolymer PS grafted with maleic anhydride and a mercapto functional group (PS-MAH-SH), which uses PS as the main chain, MAH grafting rate is 30-60%, -SH content In 5-30%.
  • PS-MAH-SH mercapto functional group
  • the toughening agent includes butyl methacrylate/acrylic polymer, acrylic toughening agent, acrylic-silicone rubber toughening agent, ethylene-methyl acrylate, ethylene-butyl acrylate, ethylene- One or two of acrylate-glycidyl methacrylate terpolymer or ethylene-vinyl acetate copolymer-functionalized maleic anhydride.
  • the antioxidant includes one or more of hindered phenol antioxidants and phosphite antioxidants.
  • hindered phenol antioxidants and phosphite antioxidants.
  • the lubricant includes one or more of silicone powder, pentaerythritol ester, ethylenebisstearamide, and butyl stearate.
  • the invention also provides a method for preparing a polishable plastic composite material connected to a metal, including the following steps:
  • step c Blending and granulating the mixture obtained in step a through a twin-screw extruder, respectively feeding chopped glass fibers and the nano-titanium dioxide processed in step b, melt extruding and granulating to obtain the composite material.
  • the screw diameter of the twin-screw extruder is 46 mm, and the aspect ratio is 52.
  • the principle of the present invention lies in that nano-TiO 2 is dispersed through silicone fluid, and the temperature (200-260° C. melt extrusion) controls the dispersion of nano-particles, so that TiO 2 is uniformly dispersed in the PBT base material. Promote the crystallization of PBT, and effectively improve the gloss and subsequent polishing performance of PBT compound.
  • the process treatment adds the compatibilizer PS-MAH-SH, which effectively improves the dispersion of GF and nanoparticles in the composite material and the affinity with metal parts during nano-injection.
  • the nano-TiO 2 powder prepared by the Sol-gel method of the present invention is grafted with a certain component of nickel oxide on the surface as a part to improve the surface gloss of the product, which is dispersed well by an organosilicon fluid ultrasonically, and then injected into the melt sideways and screw In the seventh area, increase the distribution of functional thread elements, improve dispersion, improve the gloss of the material surface, polishing performance and crystallization performance of the substrate.
  • the use of multi-functional block copolymers improves the dispersion of the internal components of the material, and the functional groups have a strong affinity for metal groups. Effectively improve the combination of nano-injection of polishable materials and metal materials.
  • the polybutylene terephthalate used in the following examples and comparative examples is specifically MCC's 5008 with a viscosity of 0.85; GF uses Owens Corning chopped fiber 183F with a diameter of 13 ⁇ m and a length of 6 mm; nano-TIO2 Prepared for laboratory synthesis; antioxidant is antioxidant 1010 and antioxidant 168 produced by CIBA; lubricant is pentaerythritol ester PETS produced by Dongguan Xiongyue Company; silicone dispersion fluid medium is silicone liquid KH560; toughened The agent is a commercially available EMA.
  • a polishable plastic composite material connected with metal and a preparation method thereof, the method includes the following steps:
  • the screw diameter of the extruder is 46mm, and the aspect ratio is 50.
  • a polishable plastic composite material connected with metal and a preparation method thereof, the method includes the following steps:
  • the screw diameter of the extruder is 46mm, and the aspect ratio is 50.
  • Example 1 to Example 4 are formulated according to Table 1. And follow the steps below for processing:
  • the component 1 obtained in the previous step is blended and granulated by a twin-screw extruder, one side feeding port is fed with the component 2, and the other side feeding port is fed with GF. After melt extrusion, granulation is obtained
  • the product produces a polishable plastic composite material connected to the metal.
  • the melt extrusion is performed at 200-260°C, the screw extruder speed is 400 rpm, and the pressure is 2 MPa. In the screw combination, 2 distributed thread elements ZME are added in the seventh zone. After melt extrusion, the granulation is Get the product.
  • the screw diameter of the extruder is 46mm, and the aspect ratio is 50.
  • the preparation method is basically the same as the examples.
  • This comparative example is basically the same as the method in Example 2, except that the glass fiber used in this comparative example is continuous glass fiber.
  • This comparative example is basically the same as the method in Example 2, except that the surface of the chopped glass fiber used in this comparative example has not been treated with a silane coupling agent.
  • the method of this comparative example is basically the same as that of Example 2, the only difference is that the surface of the nano titanium dioxide used in this comparative example is not grafted with nickel oxide.
  • This comparative example is basically the same as the method in Example 2, except that the compatibilizer used in this comparative example is SAN-g-MAH.
  • test results of each comparative example and examples are shown in Table 2.
  • Use 10 ⁇ -3 ⁇ gauze for polishing treatment observe the surface gloss effect, and evaluate by "+, -" grade.

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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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

本发明涉及一种可抛光的与金属连接的塑料复合材料及其制备方法，该复合材料包括以下重量份的各组分：PBT：50～80，GF：10～50，纳米二氧化钛：1～5，分散流体介质：3～10，相容剂：1～8份，增韧剂：5～10，抗氧剂：0.1～1，润滑剂：0.1～1其制备方法包括：(a)将PBT树脂、纳米二氧化钛、增韧剂、相容剂、抗氧剂和润滑剂加入混合搅拌机中进行混合；(b)将步骤a所得混合物通过双螺杆挤出机共混造粒，侧喂入GF，经过熔融挤出，造粒即得。与现有技术相比，本发明所提供的该种塑料复合物，通过特有工艺添加相容性组份，达到对金属强的亲和力和优异的后加工抛光性能。

Description

一种可抛光的与金属连接的塑料复合材料及其制备方法 技术领域
本发明涉及复合材料材料领域，尤其是涉及一种可抛光的与金属连接的塑料复合材料及其制备方法。
背景技术
塑料件同金属的连接形式多种多样，因为金属与塑料的亲和力不足，分子状态差距较大，所以会出现较高的连接不良率。日本大成普拉斯首次开发的纳米注塑(NMT)技术，将塑料和金属件能通过更加紧密的结合力，以加强金属与塑料件之间的结合。通常塑料选择结晶性的PA，PPS，PBT的增强材料。因为PPS增强材料配色存在一定难度，PA增强材料的纳米注塑结合力及尺寸稳定性有差，所以目前趋势是采用PBT增强塑料为纳米注塑的材料。
PBT增强的塑料因为玻纤增强，表面光泽度一般，表面浮纤比较明显。但是后续手机的发展，渐渐将纳米注塑的塑料部分也做外漏件。环保、成本等需求对喷漆有一定限制，趋势需要一类与金属结合力好的纳米注塑塑料，且可以免喷涂达到和金属相近的抛光效果。目前，较多专利关注于，提升增强PBT基材的纳米注塑塑料的结合力。而鲜少关注到PBT增强材料的抛光性能改善。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种可抛光的与金属连接的塑料复合材料及其制备方法。
本发明的目的是通过以下技术方案实现的：
本发明提供了一种可抛光的与金属连接的塑料复合材料，包括以下重量份的各组分：
聚对苯二甲酸丁二醇酯PBT：50～80，
短切玻璃纤维GF：10～50，
纳米二氧化钛nano-TiO 2：1～5，
分散流体介质：3～10，
相容剂：1～8份，
增韧剂：5～10，
抗氧剂：0.1～1，
润滑剂：0.1～1。
更优选地，所述可抛光的与金属连接的塑料复合材料包括以下重量份的各组分：
聚对苯二甲酸丁二醇酯PBT：60～80，
短切玻璃纤维GF：10～30，
纳米二氧化钛nano-TiO 2：3～5，
分散流体介质：6～10，
相容剂：5～8份，
增韧剂：8～10，
抗氧剂：0.5～1，
润滑剂：0.5～1。
优选地，所述的聚对苯二甲酸丁二醇酯在23℃下的粘度在0.6-1dl/g。
优选地，所述的短切玻璃纤维为无碱短切纤维，直径在5-17μm，长度为5-10mm，其表面采用硅烷偶联剂处理过，所述硅烷偶联剂的含量占短切玻璃纤维质量的0.5-1％。
优选地，所述的纳米二氧化钛采用溶胶-凝胶法制备，并且其表面接枝氧化镍；所述氧化镍的含量为纳米二氧化钛质量的5-10％。
优选地，所述的分散流体介质为有机硅流体介质，主要成分为23℃下的粘度在0.4～1.5dl/g的有机硅液体，其中PDMS占有机硅流体介质的比例为20-70％。
优选地，所述相容剂为多官能团共聚物PS接枝马来酸酐和巯基官能团(PS-MAH-SH)，其以PS为主链，MAH接枝率在30-60％，-SH含量在5-30％。
优选地，所述的增韧剂包括甲基丙烯酸丁酯/丙烯酸类聚合物、丙烯酸类增韧剂、丙烯酸-硅橡胶类增韧剂、乙烯-丙烯酸甲酯、乙烯-丙烯酸丁酯、乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物或者乙烯-醋酸乙烯共聚物-功能化马来酸酐中一种或两种。
优选地，所述的抗氧剂包括受阻酚类抗氧剂及亚磷酸酯类抗氧剂中的一种或几种。如市售抗氧剂245、抗氧剂1076、抗氧剂168、抗氧剂264。
优选地，所述的润滑剂包括硅酮粉、季戊四醇酯、乙撑双硬酯酰胺、硬脂酸丁酯中 的一种或几种。
本发明还提供了一种可抛光的与金属连接的塑料复合材料的其制备方法，包括以下步骤：
(a)将PBT树脂、增韧剂、相容剂、抗氧剂和润滑剂加入混合搅拌机中进行混合；
(b)将纳米二氧化钛混入有机硅流体中，超声分散得处理的纳米二氧化钛；
(c)将步骤a所得混合物通过双螺杆挤出机共混造粒，分别侧喂入短切玻璃纤维和步骤b所得处理的纳米二氧化钛，经过熔融挤出，造粒即得所述复合材料。
优选地，步骤(c)中，所述双螺杆挤出机的螺杆直径为46mm，长径比为52。
本发明的原理在于：通过有机硅流体分散纳米TiO 2，温度(200～260℃下熔融挤出)控制纳米粒子的分散，使得TiO 2均匀分散在PBT基材中。促进PBT的结晶完善，并有效改善增强PBT复合料的光泽性和后续抛光性能。同时通过螺杆组合变换，工艺处理添加相容剂PS-MAH-SH，有效提高复合材料内部GF，纳米粒子的分散和纳米注塑时与金属制件的亲和力。
与现有技术相比，本发明具有的有益效果为：
本发明的Sol-gel方法制备的nano-TiO 2粉末，表面接枝一定组份的氧化镍，作为提高制件表面光泽的部分，通过有机硅流体超声分散好，然后侧喂注入熔体，螺杆在第七区增加分配功能螺纹元件，改善分散，提高材料表面的光泽，抛光性能及基材结晶性能。运用多官能团的嵌段共聚物，使得材料内部组份分散得到改善，同时官能团对金属基有较强的亲和力。有效提升可抛光的材料与金属材料的纳米注塑结合力。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变化和改进。这些都属于本发明的保护范围。
以下实施例及对比例中选用的聚对苯二甲酸丁二醇酯具体是用MCC公司的5008，粘度为0.85；GF选用欧文斯康宁短切纤维183F，直径为13μm，长度为6mm；纳米TIO2为实验室合成制备；抗氧剂为CIBA公司生产的抗氧剂1010、抗氧剂168；润滑剂为东莞雄越公司生产的季戊四醇酯PETS；有机硅分散流体介质为有机硅液体KH560；增韧剂为市售EMA。
对比例1
一种可抛光的与金属连接的塑料复合材料及其制备方法，该方法包括以下步骤：
(1)将PBT树脂、增韧剂、抗氧剂和润滑剂加入高速搅拌机中进行混合，混炼机转速在1000r，得到混合均匀混合物；
(2)将上一步骤所得混合物1通过双螺杆挤出机共混造粒，侧喂口喂入GF，经过熔融挤出，造粒即得到产品制得一种可抛光的与金属连接的塑料复合材料。在200～260℃下熔融挤出，螺杆挤出机转速为400rpm，压力为2MPa，选用螺杆组合中，在第七区增加分布螺纹元件ZME 2块，经过熔融挤出，造粒即得到产品。
(3)挤出机螺杆直径为46mm，长径比为50。
对比例2
一种可抛光的与金属连接的塑料复合材料及其制备方法，该方法包括以下步骤：
(1)将PBT树脂、增韧剂、多官能团共聚物、抗氧剂和润滑剂加入高速搅拌机中进行混合，混炼机转速在1000r，得到混合均匀组份1；同时，将表面氧化镍修饰的，溶胶凝胶法制备的纳米二氧化钛，单独作为一组份。
(2)将上一步骤所得混合物1通过双螺杆挤出机共混造粒，侧喂入纳米二氧化钛，另一个侧喂口喂入GF，经过熔融挤出，造粒即得到产品制得一种可抛光的与金属连接的塑料复合材料。在200～260℃下熔融挤出，螺杆挤出机转速为400rpm，压力为2MPa，选用螺杆组合中，在第七区增加分布螺纹元件ZME 2块，经过熔融挤出，造粒即得到产品。
(3)挤出机螺杆直径为46mm，长径比为50。
实施例1-4
实施例1～实例4按照表1组份配料。并按照下述步骤进行加工：
(1)将PBT树脂、增韧剂、多官能团共聚物、抗氧剂和润滑剂加入高速搅拌机中进行混合，混炼机转速在1000r，得到混合均匀组份1；同时，将表面氧化镍修饰的、溶胶凝胶法制备的纳米二氧化钛，混入有机硅流体中，在超声波环境下进行超声分散。得到组份2。GF作为单独的一个组份，按分量称好。
(2)将上一步骤所得组份1通过双螺杆挤出机共混造粒，一个侧喂口喂入组份2，另一个侧喂口喂入GF，经过熔融挤出，造粒即得到产品制得一种可抛光的与金属连接的塑料复合材料。所述熔融挤出在200～260℃下进行，螺杆挤出机转速为400rpm，压力为2MPa，选用螺杆组合中，在第七区增加分布螺纹元件ZME 2块，经过熔融挤出， 造粒即得到产品。
(3)挤出机螺杆直径为46mm，长径比为50。
对比例3-6
对比例3-6按照表1组份配料。制备方法与实施例基本相同。
表1各实施例和对比例中的组份添加量
Figure PCTCN2019072428-appb-000001
对比例7
本对比例与实施例2的方法基本相同，不同之处仅在于：本对比例采用的玻璃纤维为连续玻璃纤维。
对比例8
本对比例与实施例2的方法基本相同，不同之处仅在于：本对比例采用的短切玻璃纤维表面未经过硅烷偶联剂处理。
对比例9
本对比例与实施例2的方法基本相同，不同之处仅在于：本对比例采用的纳米二氧化钛表面未接枝氧化镍。
对比例10
本对比例与实施例2的方法基本相同，不同之处仅在于：本对比例采用的相容剂为 SAN-g-MAH。
效果验证：
各对比例及实施例的测试结果如表2所示。采用10μ-3μ的纱布进行抛光处理，观测表面光泽效果，通过“+，-”的等级进行评定。“+”数目越多表示表面抛光效果越好。“-”数目越多表示效果越差。通过粒子纳米注塑工艺，与金属件结合，并用拉伸仪器测试纳米注塑结合力，记录如下表。
表2
Figure PCTCN2019072428-appb-000002
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变化或修改，这并不影响本发明的实质内容。在不冲突的情况下，本申请的实施例和实施例中的特征可以任意相互组合。

Claims (11)

  1. 一种可抛光的与金属连接的塑料复合材料，其特征在于，包括以下重量份的各组分：
    聚对苯二甲酸丁二醇酯：50～80，
    短切玻璃纤维：10～50，
    纳米二氧化钛：1～5，
    分散流体介质：3～10，
    相容剂：1～8份，
    增韧剂：5～10，
    抗氧剂：0.1～1，
    润滑剂：0.1～1。
  2. 根据权利要求1所述的可抛光的与金属连接的塑料复合材料，其特征在于，所述的聚对苯二甲酸丁二醇酯在23℃下的粘度在0.6-1dl/g。
  3. 根据权利要求1所述的可抛光的与金属连接的塑料复合材料，其特征在于，所述的短切玻璃纤维为无碱短切纤维，直径在5-17μm，长度为5-10mm，其表面采用硅烷偶联剂处理过，所述硅烷偶联剂的含量占短切玻璃纤维质量的0.5-1％。
  4. 根据权利要求1所述的可抛光的与金属连接的塑料复合材料，其特征在于，所述的纳米二氧化钛采用溶胶-凝胶法制备，并且其表面接枝氧化镍；所述氧化镍的含量为纳米二氧化钛质量的5-10％。
  5. 根据权利要求1所述的可抛光的与金属连接的塑料复合材料，其特征在于，所述的分散流体介质为有机硅流体介质，主要成分为23℃下的粘度在0.4～1.5dl/g的有机硅液体，其中PDMS占有机硅流体介质的比例为20-70％。
  6. 根据权利要求1所述的可抛光的与金属连接的塑料复合材料，其特征在于，所述相容剂为多官能团共聚物PS接枝马来酸酐和巯基官能团，其以PS为主链，MAH接枝率在30-60％，-SH含量在5-30％。
  7. 根据权利要求1所述的可抛光的与金属连接的塑料复合材料，其特征在于，所述的增韧剂包括甲基丙烯酸丁酯/丙烯酸类聚合物、丙烯酸类增韧剂、丙烯酸-硅橡胶类增韧剂、乙烯-丙烯酸甲酯、乙烯-丙烯酸丁酯、乙烯-丙烯酸酯-甲基丙烯酸缩水甘油酯三元共聚物或者乙烯-醋酸乙烯共聚物-功能化马来酸酐中一种或两种。
  8. 根据权利要求1所述的可抛光的与金属连接的塑料复合材料，其特征在于，所述的抗氧剂包括受阻酚类抗氧剂及亚磷酸酯类抗氧剂中的一种或几种。
  9. 根据权利要求1所述的可抛光的与金属连接的塑料复合材料，其特征在于，所述的润滑剂包括硅酮粉、季戊四醇酯、乙撑双硬酯酰胺、硬脂酸丁酯中的一种或几种。
  10. 一种根据权利要求1所述的可抛光的与金属连接的塑料复合材料的其制备方法，其特征在于，包括以下步骤：
    (a)将PBT树脂、增韧剂、相容剂、抗氧剂和润滑剂加入混合搅拌机中进行混合；
    (b)将纳米二氧化钛混入有机硅流体中，超声分散得处理的纳米二氧化钛；
    (c)将步骤a所得混合物通过双螺杆挤出机共混造粒，分别侧喂入短切玻璃纤维和步骤b所得处理的纳米二氧化钛，经过熔融挤出，造粒即得所述复合材料。
  11. 根据权利要求10所述的可抛光的与金属连接的塑料复合材料的其制备方法，其特征在于，步骤(c)中，所述双螺杆挤出机的螺杆直径为40-50mm，长径比为50-55。
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