WO2018099224A1 - 一种玻纤增强的耐冷媒pbt树脂组合物及其制备方法 - Google Patents

一种玻纤增强的耐冷媒pbt树脂组合物及其制备方法 Download PDF

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WO2018099224A1
WO2018099224A1 PCT/CN2017/108146 CN2017108146W WO2018099224A1 WO 2018099224 A1 WO2018099224 A1 WO 2018099224A1 CN 2017108146 W CN2017108146 W CN 2017108146W WO 2018099224 A1 WO2018099224 A1 WO 2018099224A1
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glass fiber
resin composition
refrigerant
pbt resin
fiber reinforced
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PCT/CN2017/108146
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English (en)
French (fr)
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王文超
陈锐
付学俊
禹权
丁超
叶南飚
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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 WO2018099224A1 publication Critical patent/WO2018099224A1/zh

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    • 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
    • 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
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • 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
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • 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
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Definitions

  • the invention belongs to the field of engineering plastics, and in particular relates to a glass fiber reinforced PBT resin composition.
  • Refrigerator compressor silencer and air conditioner compressor coil skeleton due to direct contact with the refrigerant, small molecules may be precipitated in the silencer or the skeleton material. Once the precipitation of the small molecular substance is too high, the refrigeration tube of the compressor may be clogged. The cooling effect is not good, so the material for manufacturing the muffler and the motor coil bobbin needs to have a function of resisting refrigerant precipitation.
  • the research direction of refrigerant-resistant PBT materials is mainly focused on minimizing the factors that can cause the precipitation of PBT composites.
  • patent application CN103013068A discloses a PBT composite material which is resistant to high temperature and cold resistant precipitation, and mainly uses a polyfunctional epoxy group chain extender, a magnesium aluminum hydrotalcite acid acceptor and a blocking agent of 1 to 3 epoxy groups.
  • a polyfunctional epoxy group chain extender e.g., a polyfunctional epoxy group chain extender
  • a magnesium aluminum hydrotalcite acid acceptor e.g., a magnesium aluminum hydrotalcite acid acceptor
  • a blocking agent of 1 to 3 epoxy groups e.g., a polyfunctional epoxy group chain extender, a magnesium aluminum hydrotalcite acid acceptor and a blocking agent of 1 to 3 epoxy groups.
  • the object of the present invention is to overcome the problem of low fluidity of a refrigerant-resistant glass fiber reinforced PBT resin in the prior art, and to provide a glass fiber reinforced refrigerant PBT resin composition.
  • the glass fiber reinforced refrigerant-resistant PBT resin composition has good resistance to refrigerant precipitation and maintains high fluidity.
  • Another object of the present invention is to provide a method for producing the glass fiber reinforced refrigerant-resistant PBT resin composition.
  • Another object of the present invention is to provide the use of the glass fiber reinforced refrigerant resistant PBT resin composition.
  • a glass fiber reinforced refrigerant resistant PBT resin composition having the following composition by weight:
  • Glass fiber is greater than 0 to not more than 50%
  • Inorganic porous material adsorbent 1 to 10%.
  • a glass fiber reinforced refrigerant-resistant PBT resin composition which is composed of the following components by weight:
  • Glass fiber is greater than 0 to not more than 50%
  • Inorganic porous material adsorbent 1 ⁇ 10%
  • the inventors have found that an inorganic adsorbent is used in the glass fiber reinforced PBT resin, and the inorganic adsorbent can adsorb the small molecular substance precipitated by the composition well by physical adsorption, thereby improving the refrigerant precipitation resistance of the PBT resin composition, and Additives such as chain extenders, blocking agents, etc. of the prior art are avoided, and thus the obtained PBT composition maintains better flow properties.
  • the inorganic porous material adsorbent is contained in the refrigerant-resistant PBT resin composition in an amount of from 1 to 5% by weight, more preferably from 1 to 3% by weight.
  • the polybutylene terephthalate has an intrinsic viscosity of 0.8 to 1.3 ml/g.
  • the glass fiber is an alkali-free glass fiber having a diameter of 10 to 25 ⁇ m.
  • the inorganic porous material adsorbent is any one or more of activated carbon, diatomaceous earth or porous silica.
  • the inorganic porous material adsorbent has a specific surface area of 40 to 4000 m 2 /g.
  • the inorganic porous material adsorbent has a specific surface area of 40 to 800 m 2 /g.
  • the properties are different. More preferably, when the inorganic porous material adsorbent is activated carbon, generally its specific surface area is relatively high, preferably its specific surface area is 400-4000 m 2 /g; when the inorganic porous material When the adsorbent is diatomaceous earth or porous silica, the specific surface area thereof is smaller than that of activated carbon, and when the inorganic porous material adsorbent is diatomaceous earth, the specific surface area thereof is preferably 40-100 m 2 /g; When the inorganic porous material adsorbent is porous silica, it preferably has a specific surface area of from 100 to 800 m 2 /g.
  • the inorganic porous material adsorbent is diatomaceous earth or porous silica.
  • the antioxidant can reduce the degradation of the PBT resin during processing and has a certain effect on the improvement of its mechanical properties.
  • the antioxidant may be an antioxidant commonly used in the art, and the effect between the different antioxidants is not much different.
  • the antioxidant is a pentaerythritol ester antioxidant or a hindered amine antioxidant.
  • the preparation method of the glass fiber reinforced refrigerant-resistant PBT resin composition comprises the following steps:
  • the antioxidant is uniformly mixed with the polybutylene terephthalate or the inorganic porous material adsorbent in S2 and then enters the twin-screw extrusion. Out of the plane.
  • the process parameters of the twin-screw extruder are: one zone temperature 210-220 ° C, two zone temperature 220-230 ° C, three, four, five and six zone temperature 230-240 ° C, seven zone temperature 240 ⁇ 250 ° C, eight zones temperature 240 ⁇ 250 ° C, nine zone temperature 230 ⁇ 240 ° C, the host speed 200 ⁇ 400 rev / min.
  • the present invention has the following beneficial technical effects:
  • the glass fiber reinforced refrigerant-resistant PBT resin composition prepared by the invention adsorbs small molecular substances which may be precipitated by the inorganic porous material adsorbent, and the molecular weight reduction small molecule which is extended, blocked and the like by the prior art for PBT
  • the idea of the content of the substance is different, and the defect that the flowability of the PBT composition is lowered due to the increase in molecular weight is avoided, and the obtained PBT resin maintains good fluidity while having good resistance to precipitation of the refrigerant.
  • the raw materials used were all commercially available. In the examples, the percentages are by weight.
  • E-glass fiber was purchased from Taiwan Bicheng Co., Ltd. and has a diameter of 10 ⁇ m.
  • PBT was purchased from Taiwan Changchun Chemical Co., Ltd. under the designation PBT 1100-211M, and the intrinsic viscosity was 1.0 mL/g.
  • Diatomaceous earth was purchased from Linjiang Yirui Stone Diatomite Co., Ltd. under the designation INFILM 300, and the specific surface area was 40-65 m 2 /g.
  • Activated carbon A was purchased from Fujian Xinsen Carbon Co., Ltd., and its specific surface area was 1400-1800 m 2 /g.
  • Activated carbon B was purchased from Fujian Xinsen Carbon Co., Ltd. and had a specific surface area of 2100 m 2 /g.
  • Porous silica was purchased from Anhui Lanshitong Material Technology Co., Ltd., and its specific surface area was 200-260 m 2 /g.
  • Antioxidant A is a pentaerythritol ester antioxidant, commercially available
  • Antioxidant B is a hindered amine antioxidant, commercially available
  • the glass fiber reinforced refrigerant resistant PBT resin composition was prepared according to the formulation of the examples in Table 1 and the blank example and according to the following procedure:
  • the polybutylene terephthalate and the inorganic porous material adsorbent and the antioxidant are uniformly mixed and then enter the twin-screw extruder, the glass fiber is added in the six zones of the twin-screw extruder, and the pre-finished product is obtained by extrusion. ;
  • the process parameters of the twin-screw extruder in step S2 are: one zone temperature 210-220 ° C, two zone temperature 220-230 ° C, three, four, five and six zone temperature 230-240 ° C, seven zone temperature 240-250 ° C
  • the temperature in the eight districts is 240-250 °C
  • the temperature in the nine districts is 230-240 °C
  • the speed of the main engine is 200-400 rpm.
  • the preparation method of the composition of the comparative example was carried out in accordance with CN103013068A.
  • S2 The components of S1 are uniformly mixed to obtain a premix.
  • the premix is fed from the main feed port of the twin-screw extruder, and the glass fiber is added in the six zones of the twin-screw extruder. Finished product
  • the process parameters of the twin-screw extruder in step S2 are: one zone temperature 210-220 ° C, two zone temperature 220-230 ° C, three, four, five and six zone temperature 230-240 ° C, seven zone temperature 240-250 ° C
  • the temperature in the eight districts is 240-250 °C
  • the temperature in the nine districts is 230-240 °C
  • the speed of the main engine is 300-400 rpm.
  • the IZOD notched impact strength was tested according to the GB/T 1843-2008 standard.
  • the sample size was 80 mm ⁇ 10 mm ⁇ 4 mm, and the notch depth was 2 mm.
  • the test equipment was the Tinius Olisen impact tester from Willow Grove, USA.
  • Tensile properties were evaluated by measuring tensile rupture strength. The test was carried out according to GB/T 1040.2. The sample size was 170 mm ⁇ 20 mm ⁇ 4 mm, and the test speed was 10 mm/min. The test equipment was an electronic tensile test machine from Zwick, Germany.
  • the bending performance was evaluated by measuring the bending strength.
  • the test was carried out according to the GB/T 9341-2008 standard.
  • the sample size was 80 mm ⁇ 10 mm ⁇ 4 mm, and the test speed was 2 mm/min.
  • the test equipment was an electronic tensile test machine from Zwick, Germany.
  • the fluidity was determined by the melt index, the test condition was 250 ° C, 2.16 kg, and the test equipment was a ZMF/Roell BMF-003 type melt finger meter.
  • Resistant to refrigerant performance by extracting materials from a mixture of refrigerant and refrigerating machine oil in an autoclave The material was evaluated for its resistance to refrigerant.
  • the refrigerant used was R22 (difluorochloromethane)
  • the refrigerating machine oil was Kunlun 4GS
  • the ratio of refrigerant to refrigerating machine oil was 1:3
  • the extraction temperature was 150 ° C
  • the extraction time was 336 hours.
  • the refrigerant resistance was evaluated by the presence or absence of precipitates.

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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)

Abstract

本发明提供了一种玻纤增强的耐冷媒PBT树脂组合物及其制备方法。所述玻纤增强的耐冷媒PBT树脂组合物包括如下按重量百分比计算的组分：48.0～95.0％的聚对苯二甲酸丁二醇酯、大于0至不多于50％玻璃纤维、1～10％的无机多孔材料吸附剂。本发明在玻纤增强PBT树脂成分中加入了无机多孔材料吸附剂，可以吸附PBT材料可能析出的小分子物质，从而降低析出量；同时，采用无机吸附剂的方案不使用扩链剂、封端剂或偶联剂，减少了对树脂流动性能的影响，使树脂组合物保留了较好的流动性。

Description

一种玻纤增强的耐冷媒PBT树脂组合物及其制备方法 技术领域
本发明属于工程塑料领域，具体涉及一种玻纤增强的PBT树脂组合物。
背景技术
冰箱压缩机消音器及空调压缩机线圈骨架，由于直接接触冷媒，可能发生消音器或骨架材料中的小分子物质析出，一旦小分子物质的析出量过高会使压缩机的制冷管堵塞，导致制冷效果失灵，因此制造消音器和马达线圈骨架的材料需要具有耐冷媒析出的功能。目前对耐冷媒PBT材料的研究方向主要集中在尽量减少能造成PBT复合材料析出的因素。如专利申请CN103013068A公开了一种耐高温耐冷媒析出的PBT复合材料，主要采用多官能环氧基团扩链剂、镁铝水滑石吸酸剂和1～3个环氧基团的封端剂配合来降低整个树脂组合物体系存留的低分子物质的含量，但采用扩链剂、偶联剂、封端剂等添加剂，虽然可以通过化学反应，增大PBT材料的分子量，减少小分子物质，但其使用会使得树脂流动性能降低。作为冰箱压缩机消音器及空调压缩机线圈骨架材料除了要求耐冷媒析出性能外，流动性也是一个重要的因素，因此，开发一种兼具良好的流动性及耐冷媒析出性能的PBT具有实际意义。
发明内容
本发明的目的是为了克服现有技术中耐冷媒玻纤增强PBT树脂流动性不太高的问题，提供了一种玻纤增强的耐冷媒PBT树脂组合物。所述的玻纤增强的耐冷媒PBT树脂组合物具有良好的耐冷媒析出性能，并且保持较高的流动性。
本发明的另一目的在于提供所述玻纤增强的耐冷媒PBT树脂组合物的制备方法。
本发明的另一目的在于提供所述玻纤增强的耐冷媒PBT树脂组合物的应用。
本发明的上述目的通过如下技术方案予以实现：
一种玻纤增强的耐冷媒PBT树脂组合物，由如下按重量百分比计算的组分：
聚对苯二甲酸丁二醇酯 48.0～95.0％；
玻璃纤维 大于0至不多于50％；
无机多孔材料吸附剂   1～10％。
一种玻纤增强的耐冷媒PBT树脂组合物，由以下按重量百分比计算的组分：
聚对苯二甲酸丁二醇酯 48.0～95.0％；
玻璃纤维 大于0至不多于50％；
无机多孔材料吸附剂   1～10％；
抗氧剂   0.1～1％。
发明人发现，用玻纤增强PBT树脂中采用无机吸附剂，无机吸附剂可通过物理吸附作用能够很好地吸附组合物析出的小分子物质，改善PBT树脂组合物的耐冷媒析出性能，并且其避免了使用现有技术的扩链剂、封端剂等添加剂，因此获得的PBT组合物保持更好的流动性能。
优选地，所述无机多孔材料吸附剂在所述耐冷媒PBT树脂组合物的重量含量为1～5％，更优选为1～3％。
优选地，所述聚对苯二甲酸丁二醇酯的特性粘数为0.8～1.3ml/g。
优选地，所述玻璃纤维为直径为10～25μm的无碱玻璃纤维。
优选地，所述无机多孔材料吸附剂为活性炭、硅藻土或多孔二氧化硅中的任意一种或几种。
优选地，所述无机多孔材料吸附剂的比表面积为40～4000m2/g。
更优选地，所述无机多孔材料吸附剂的比表面积为40～800m2/g。
根据不同的材料，性质有差别，更优选地，当所述无机多孔材料吸附剂为活性炭时，一般其比表面积比较高，优选其比表面积为400～4000m2/g；当所述无机多孔材料吸附剂为硅藻土或多孔二氧化硅时，其比表面积较活性炭要小，当所述无机多孔材料吸附剂为硅藻土时，优选其比表面积为40～100m2/g；当所述无机多孔材料吸附剂为多孔二氧化硅时，优选其比表面积为100～800m2/g。但如活性炭这类材料，其颜色较深，在使用过程中可能会影响组合物的颜色，使用会受到限制。优选所述无机多孔材料吸附剂为硅藻土或多孔二氧化硅。在本发明中，抗氧剂可以减少加工过程中PBT树脂的降解从而对其力学性能提升有一定的效果。抗氧剂可以是本领域常用的抗氧剂，不同抗氧剂之间效果差异不大。
更优选地，所述抗氧剂为季戊四醇酯类抗氧剂或受阻胺类抗氧剂。
所述玻纤增强的耐冷媒PBT树脂组合物的制备方法，包括以下步骤：
S1.称取聚对苯二甲酸丁二醇酯、玻璃纤维、无机多孔材料吸附剂；
S2.将聚对苯二甲酸丁二醇酯、无机多孔材料吸附剂均匀混合后进入双螺杆挤出机，在双螺杆挤出机的六区加入玻璃纤维，挤出得到预成品；
S3.将S2中所得预成品冷却、干燥、切粒即得玻纤增强的耐冷媒PBT树脂组合物。
当所述玻纤增强的耐冷媒PBT树脂组合物中含有抗氧剂时，抗氧剂在S2中，与聚对苯二甲酸丁二醇酯、无机多孔材料吸附剂均匀混合后进入双螺杆挤出机。
优选地，步骤S2中，双螺杆挤出机的工艺参数为：一区温度210～220℃，二区温度220～230℃，三、四、五和六区温度230～240℃，七区温度240～250℃，八区温度240～250℃，九区温度230～240℃，主机转速200～400转/分钟。
所述玻纤增强的耐冷媒PBT树脂组合物在制备压缩机耐冷媒材料中的应用。
与现有技术相比，本发明具有以下有益技术效果：
本发明制备的玻纤增强的耐冷媒PBT树脂组合物，通过无机多孔材料吸附剂来吸附可能会析出的小分子物质，与现有技术的对PBT进行扩链、封端等提升分子量减少小分子物质的含量的思路不同，避免了因为分子量提高导致PBT组合物流动性能下降的缺陷，所得的PBT树脂在具有良好的耐冷媒析出性能的同时，保持了良好的流动性。
具体实施方式
下面结合具体实施例和对比例对本发明做进一步的详细说明，但本发明并不限于下述实施例。
实施例中，所用的原料均为市售商品。实施例中，所述的百分含量为重量百分含量。
无碱玻璃纤维购自，台湾必成股份有限公司，直径为10μm。PBT购自台湾长春化工有限公司，牌号PBT 1100-211M，特性粘数为1.0mL/g。
硅藻土购自临江益瑞石硅藻土有限公司，牌号INFILM 300，比表面积为 40～65m2/g。
活性炭A购自福建省鑫森炭业股份有限公司，比表面积为1400～1800m2/g。
活性炭B购自福建省鑫森炭业股份有限公司，比表面积为2100m2/g。
多孔二氧化硅购自安徽壹石通材料科技股份有限公司，比表面积为200～260m2/g。
抗氧剂A为季戊四醇酯类抗氧剂，市售
抗氧剂B为受阻胺类抗氧剂，市售
按表1中实施例及空白例的配方并按照下述步骤制备玻纤增强的耐冷媒PBT树脂组合物：
S1.称取聚对苯二甲酸丁二醇酯、无碱玻璃纤维、无机多孔材料吸附剂；
S2.将聚对苯二甲酸丁二醇酯和无机多孔材料吸附剂、抗氧剂均匀混合后进入双螺杆挤出机，在双螺杆挤出机的六区加入玻璃纤维，挤出得到预成品；
S3.将S2中所得预成品冷却、干燥、切粒即得玻纤增强的耐冷媒PBT树脂组合物。
步骤S2中双螺杆挤出机的工艺参数为：一区温度210～220℃，二区温度220～230℃，三、四、五和六区温度230～240℃，七区温度240～250℃，八区温度240～250℃，九区温度230～240℃，主机转速200～400转/分钟。
对比例的组合物的制备方法参照CN103013068A进行。
S1.称取聚对苯二甲酸丁二醇酯、含多官能环氧基团扩链剂ADR-4370、镁铝水滑石吸酸剂、含1～3个环氧基团的封端剂SAG-005，成核剂NAV101，氨基硅烷类偶联剂KH550，季戊四醇酯抗氧剂；
S2.将S1的组分均匀混合后得到预混料，预混料从双螺杆挤出机一区主进料口进料，在双螺杆挤出机的六区加入玻璃纤维，挤出得到预成品；
S3.将S2中所得预成品冷却、干燥、切粒即得玻纤增强的耐冷媒PBT树脂组合物。
步骤S2中双螺杆挤出机的工艺参数为：一区温度210～220℃，二区温度220～230℃，三、四、五和六区温度230～240℃，七区温度240～250℃，八区温度240～250℃，九区温度230～240℃，主机转速300～400转/分钟。
表1 本发明实施例1～7及空白例的组分及用量(％)
Figure PCTCN2017108146-appb-000001
将按照上述表中配方制备所得的各树脂组合物，按照下述方法进行相应的性能测试，所得结果如表2所示。
IZOD缺口冲击强度按GB/T 1843-2008标准进行测试，试样尺寸80mm×10mm×4mm，缺口深度2mm，测试设备为美国Willow Grove公司的TiniusOlisen冲击试验机。
拉伸性能通过测定拉伸断裂强度评价，测试按GB/T 1040.2标准进行，试样尺寸为170mm×20mm×4mm，测试速度10mm/min，测试设备为德国Zwick公司电子拉力实验机。
弯曲性能通过测定弯曲强度评价，测试按GB/T 9341-2008标准进行，试样尺寸为80mm×10mm×4mm，测试速度为2mm/min，测试设备为德国Zwick公司的电子拉力实验机。
流动性通过熔指来测定，测试条件为250℃，2.16kg，测试设备为美国Zwick/Roell公司BMF-003型熔指仪。
耐冷媒性能通过在高压釜内采用冷媒和冷冻机油混合液体对材料进行萃 取来评价材料的耐冷媒性。冷媒采用R22(二氟一氯甲烷)，冷冻机油采用昆仑4GS，冷媒和冷冻机油比例为1:3，萃取温度为150℃，萃取时间为336小时，通过是否有析出物来评价耐冷媒性。
表2 实施例1～7、空白例和对比例1～4所得树脂组合物的性能
Figure PCTCN2017108146-appb-000002
从表2可知，无机多孔材料吸附剂的加入可以显著提高PBT树脂组合物的耐冷媒析出性能，同时会稍微降低其力学性能，但对其流动性几乎无影响；而对比例中由于加入了扩链剂、封端剂、偶联剂等，熔指较空白例出现明显的下降，对树脂的流动性有较大影响。

Claims (10)

  1. 一种玻纤增强的耐冷媒PBT树脂组合物，其特征在于，由以下按重量百分比计算的组分：
    聚对苯二甲酸丁二醇酯  48.0～95.0％；
    玻璃纤维  大于0至不多于50％；
    无机多孔材料吸附剂                  1～10％。
  2. 一种玻纤增强的耐冷媒PBT树脂组合物，其特征在于，由以下按重量百分比计算的组分：
    Figure PCTCN2017108146-appb-100001
  3. 根据权利要求1或2所述玻纤增强的耐冷媒PBT树脂组合物，其特征在于，所述聚对苯二甲酸丁二醇酯的特性粘数为0.8～1.3mL/g。
  4. 根据权利要求1或2所述玻纤增强的耐冷媒PBT树脂组合物，其特征在于，所述玻璃纤维为直径为10～25μm的无碱玻璃纤维。
  5. 根据权利要求1或2所述玻纤增强的耐冷媒PBT树脂组合物，其特征在于，所述无机多孔材料吸附剂为活性炭、硅藻土或多孔二氧化硅中的任意一种或几种。
  6. 根据权利要求1或2所述玻纤增强的耐冷媒PBT树脂组合物，其特征在于，所述无机多孔材料吸附剂的比表面积为40～4000m2/g，优选比表面积为40～800m2/g。
  7. 根据权利要求2所述玻纤增强的耐冷媒PBT树脂组合物，其特征在于，所述抗氧剂为季戊四醇酯类抗氧剂或受阻胺类抗氧剂。
  8. 权利要求1至7任一项所述玻纤增强的耐冷媒PBT树脂组合物的制备方法，包括以下步骤：
    S1.称取聚对苯二甲酸丁二醇酯、玻璃纤维、无机多孔材料吸附剂；
    S2.将聚对苯二甲酸丁二醇酯、无机多孔材料吸附剂均匀混合后进入双螺杆挤出机，在双螺杆挤出机的六区加入玻璃纤维，挤出得到预成品；
    S3.将S2中所得预成品冷却、干燥、切粒即得玻纤增强的耐冷媒PBT树脂 组合物；
    如需要，抗氧剂在S2.中与聚对苯二甲酸丁二醇酯、无机多孔材料吸附剂一同加入双螺杆挤出机。
  9. 根据权利要求8所述的一种玻纤增强的耐冷媒PBT树脂组合物的合成方法，其特征在于，所述步骤S2中，双螺杆挤出机的工艺参数为：一区温度210～220℃，二区温度220～230℃，三、四、五和六区温度230～240℃，七区温度240～250℃，八区温度240～250℃，九区温度230～240℃，主机转速200～400转/分钟。
  10. 权利要求1至7任一项所述玻纤增强的耐冷媒PBT树脂组合物在制备压缩机耐冷媒材料中的应用。
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