CN102993651A - Glass-fiber-reinforced polybutylene terephthalate composite material and preparation method thereof - Google Patents

Glass-fiber-reinforced polybutylene terephthalate composite material and preparation method thereof Download PDF

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CN102993651A
CN102993651A CN 201210540088 CN201210540088A CN102993651A CN 102993651 A CN102993651 A CN 102993651A CN 201210540088 CN201210540088 CN 201210540088 CN 201210540088 A CN201210540088 A CN 201210540088A CN 102993651 A CN102993651 A CN 102993651A
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glass
polybutylene
terephthalate
material
fiber
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CN 201210540088
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潘哆吉
李旭娟
丁建萍
任英杰
姜天伟
李忠明
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新疆蓝山屯河化工股份有限公司
新疆通用塑料高性能化工程技术研究中心(有限公司)
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Abstract

The invention discloses a glass-fiber-reinforced polybutylene terephthalate composite material and a preparation method thereof. The glass-fiber-reinforced polybutylene terephthalate composite material comprises the following raw materials: polybutylene terephthalate, glass fibers, a nucleating agent, mineral fillers and a toughening agent. According to the invention, by means of carrying out coating pretreatment on the glass fibers by the nucleating agent, the surface structure of the glass fibers is changed, the interaction between the glass fibers and a polybutylene terephthalate matrix is improved, the polybutylene terephthalate is induced to crystallize, the crystallinity of the polybutylene terephthalate is improved, and the morphological structure of a blend is changed. The glass-fiber-reinforced polybutylene terephthalate composite material provided by the invention has tensile strength ranging from 98MPa to 108MPa and impact strength ranging from 6.0KJ/m<2> to 6.6KJ/m<2>, and has the characteristics of simple preparation process, high crystallization rate, high crystallinity, good mechanical property, high surface gloss, low shrinkage factor, stable dimension and low warpage, and the production cost of the material is reduced while the comprehensive performance of the material is improved.

Description

玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料及其制备方法 Glass fiber reinforced polyethylene terephthalate composite material and its preparation method

技术领域 FIELD

[0001] 本发明涉及玻纤增强塑料技术领域,是一种玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料及其制备方法。 [0001] The present invention relates to a technical field of glass fiber reinforced plastic, a glass fiber reinforced polybutylene terephthalate composite material and METHOD.

背景技术 Background technique

[0002] 聚对苯二甲酸丁二醇酯(简称PBT)作为重要的工程塑料,它以优异的物理机械和电学性能,易成型加工等特点,被广泛应用于电子电器和汽车工业等领域。 [0002] Poly (butylene terephthalate) (abbreviation PBT) as an important engineering plastics, its excellent mechanical and electrical properties, and easy molding, etc., are widely used in electronics and automotive industries.

[0003] 随着我国汽车行业的迅速发展,基础建设的大力投入,对玻纤增强工程塑料的需求也越来越大。 [0003] With the rapid development of China has invested heavily in the automotive industry, infrastructure, the demand for glass fiber reinforced plastic is also growing. 如汽车门把手、空调出风口等都需要好的综合力学性能与加工性能的工程塑料。 Such as car door handles, air conditioning vent so requires good mechanical properties of engineering plastics and processing performance. 玻纤增强的聚对苯二甲酸丁二醇酯(PBT)目前已逐渐应用于汽车行业。 Glass fiber reinforced polyethylene terephthalate, polybutylene terephthalate (PBT) has been increasingly used in the automotive industry. 近年来以上海金发发展有限公司(申请号200710046970. 5)、上海普利特复合材料有限公司(申请号200410017803. 4)、上海日之升新技术发展有限公司(申请号200710170556. 5)等为代表的国内多家公司相继对其进行研发,迄今为止申请的专利已超过50项,通过复合分别从抗光老化性、阻燃性、耐热性、光泽度和翘曲性能等角度解决了汽车用PBT材料的某一方面性能问题,但有关PBT表面、力学性能以及加工性能等综合性能的提升还有待提闻。 In recent years, with blond Shanghai Development Company Limited (Application No. 200710046970.5), Shanghai Pu Little Composites Co., Ltd. (Application No. 200410017803.4), Shanghai on the rise New Technology Development Co., Ltd. (Application No. 200710170556.5) as the domestic companies have been represented by its R & D, patent applications to date have been over 50, respectively, to solve the car from the anti-photo-aging resistance, flame resistance, heat resistance, gloss and warpage angle performance by compound performance issues with certain aspects of PBT materials, but to enhance the overall performance of the relevant surface PBT, mechanical properties and processing performance has yet to be heard mention.

发明内容 SUMMARY

[0004] 本发明提供了一种玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料及其制备方法,克服了上述现有技术之不足,制得表面、力学及加工综合性能优异的复合材料,满足汽车行业越来越高的要求。 [0004] The present invention provides a glass fiber reinforced polyethylene terephthalate composite material and its preparation method, overcomes the above deficiencies of the prior art, to prepare the surface, excellent mechanical and processing properties of the composite integrated to meet the increasing requirements of the automotive industry.

[0005] [0005]

本发明提供了一种玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料及其制备方法,克服了上述现有技术之不足,制得表面、力学及加工综合性能优异的复合材料,满足汽车行业越来越高的要求。 The present invention provides a glass fiber reinforced polyethylene terephthalate composite material and its preparation method, overcomes the above deficiencies of the prior art, to prepare the surface, mechanical and processing integrated high performance composite materials, to meet the car increasing industry requirements.

[0006] 本发明的技术方案之一是通过以下措施来实现的:一种玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,按原料重量份数组成为聚对苯二甲酸丁二醇酯50份至85份、玻璃纤维10份至30份、成核剂O. 01份至O.1份、矿物填料5份至15份、增韧剂O.1份至5份;该玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料按下述步骤得到:第一步,将所需量的成核剂加入水中配成质量百分比浓度为1%至5%的成核剂溶液;第二步,把所需量的玻璃纤维放入成核剂溶液中进行浸泡,浸泡时间为Ih至5h,浸泡后将浸泡液和玻璃纤维放置在温度为60°C至100°C下蒸发、干燥至玻璃纤维中的含水量低于O. 01%,得到成核剂包覆后的玻璃纤维;第三步,将所需量的聚对苯二甲酸丁二醇酯在温度为100°C至140°C下干燥2h至6h ;第四步,将干燥后的聚对苯二甲酸丁二醇酯、所需量的增韧剂和矿物填料在高 [0006] One aspect of the present invention is achieved by the following measures: a fiberglass reinforced polyethylene terephthalate composite material parts by weight of the raw material composition is a poly (butylene terephthalate) 50 parts to 85 parts, 10 parts of glass fibers to 30 parts, parts of a nucleating agent to O.1 O. 01 parts, of mineral filler is 5 parts to 15 parts, toughening O.1 to 5 parts; the glass fiber reinforced polyethylene terephthalate, polybutylene terephthalate composite material obtained by the following steps: a first step, the desired amount of nucleating agent added to the mass concentration of water dubbed 1-5% solution of a nucleating agent; a second step, the desired amount of glass fibers into a solution of nucleating agent to soak, soak time to Ih 5h, after immersion soaking liquor and a glass fiber is placed in a temperature 60 ° C to 100 ° C evaporated, and dried to glass fibers containing less than O. 01%, to obtain a glass fiber coated with the nucleating agent; a third step, the desired amount of polyethylene terephthalate at a temperature of between 100 ° C 140 2h ° C to the dried 6H; a fourth step, the dried polyethylene terephthalate, polybutylene terephthalate, toughening agents and mineral filler in the desired amount of high 混机中混合后加入双螺杆挤出机中,聚对苯二甲酸丁二醇酯、增韧剂和矿物填料在双螺杆挤出机中熔融后在双螺杆挤出机中加入成核剂包覆后的玻璃纤维,共混挤出,冷却,切粒得到玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料。 Compounder mixed into the twin screw extruder, polyethylene terephthalate, polybutylene terephthalate, toughening agents, and mineral filler in a twin screw extruder added nucleating agent package in a twin screw extruder after melted after the coated glass fibers, blended extrudate was cooled, pelletized to obtain a glass fiber-reinforced poly (butylene terephthalate) composite pair.

[0007] 下面是对上述发明技术方案之一的进一步优化或/和改进: [0007] The following is a further optimization of one aspect of the invention, the above and / or improvements:

上述聚对苯二甲酸丁二醇酯的特性粘度为O. 8 dl/g至1.2 dl/g;或/和,聚对苯二甲酸丁二醇酯的熔点为220°C至230°C。 The above-mentioned polyethylene terephthalate having an intrinsic viscosity of O. 8 dl / g to 1.2 dl / g; and / or polyethylene terephthalate melting point of 220 ° C to 230 ° C.

[0008] 上述玻璃纤维为表面经硅烷偶联剂处理的玻璃纤维;或/和,玻璃纤维的直径为9μ m0 [0008] surface of the glass fiber is a glass fiber silane coupling agent-treated; and / or diameter of glass fibers 9μ m0

[0009] 上述成核剂为苯甲酸钠、1,3,2,4- 二亚苄基山梨糖醇中的一种以上混合物。 [0009] The nucleating agent is sodium benzoate, 1,3,2,4-dibenzylidene sorbitol in a mixture of one or more.

[0010] 上述增韧剂为聚乙烯-辛烯共聚物、乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯三元共聚物中的一种以上混合物。 [0010] The toughening agent is a polyethylene - octene copolymer, an ethylene - butyl acrylate - glycidyl methacrylate terpolymers of one or more mixture.

[0011] 上述矿物填料的粒径为100目至2500目。 [0011] The particle size of the mineral filler is a 100 mesh to 2500 mesh.

[0012] 上述矿物填料为滑石粉、碳酸钙、蒙脱土、膨润土、蛭石中的一种以上混合物。 [0012] The mineral filler is talc, calcium carbonate, montmorillonite, bentonite, a mixture of one or more of vermiculite.

[0013] 上述聚对苯二甲酸丁二醇酯、增韧剂和矿物填料在高混机中混合时间为2分钟至5分钟。 [0013] The polyethylene terephthalate, polybutylene terephthalate, toughening agents, and mineral filler in a high speed mixer mixing time of 2 minutes to 5 minutes.

[0014] 上述双螺杆挤出机的转速为80 r/min至200 r/min ;或/和,上述双螺杆挤出机料筒至挤出口模的温度为190°C至245°C。 Speed ​​[0014] The twin screw extruder was 80 r / min to 200 r / min; and / or the twin screw extruder barrel to the extrusion die temperature of 190 ° C to 245 ° C.

[0015] 本发明的技术方案之二是通过以下措施来实现的:一种玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料的制备方法,按下述步骤进行:第一步,将所需量的成核剂加入水中配成质量百分比浓度为1%至5%的成核剂溶液;第二步,把所需量的玻璃纤维放入成核剂溶液中进行浸泡,浸泡时间为Ih至5h,浸泡后将浸泡液和玻璃纤维放置在温度为60°C至100°C下蒸发、干燥至玻璃纤维中的含水量低于O. 01%,得到成核剂包覆后的玻璃纤维;第三步,将所需量的聚对苯二甲酸丁二醇酯在温度为100°C至140°C下干燥2h至6h ;第四步,将干燥后的聚对苯二甲酸丁二醇酯、所需量的增韧剂和矿物填料在高混机中混合后加入双螺杆挤出机中,聚对苯二甲酸丁二醇酯、增韧剂和矿物填料在双螺杆挤出机中熔融后在双螺杆挤出机中加入成核剂包覆后的玻璃纤维,共混挤出,冷却,切 [0015] aspect of the present invention is achieved by the two following measures: A glass fiber reinforced poly (butylene terephthalate) preparing the composite material according to the following steps: the first step, The demand a nucleating agent was added to water dubbed the mass concentration of 1 to 5% solution of a nucleating agent; a second step, the desired amount of glass fibers into a solution of nucleating agent to soak, soak time Ih to 5h, and the soaking solution after soaking glass fiber is placed in a temperature 60 ° C to 100 ° C evaporated, dried to a moisture content of glass fiber is less than O. 01%, to obtain a glass fiber coated with the nucleating agent ; the third step, the required amount of the polyethylene terephthalate is dried at a temperature of 2h to 100 ° C for 6h to 140 ° C; a fourth step, the dried polybutylene terephthalate alcohol esters, and the required amount of toughener mineral filler is added in a high speed mixer after mixing twin-screw extruder, polyethylene terephthalate, polybutylene terephthalate, toughening agents, and mineral filler in a twin screw extruder glass fibers were added after the molten nucleating agent coated twin-screw extruder, the blend is extruded, cooled, cut 得到玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料;其中,该玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,按原料重量份数组成为聚对苯二甲酸丁二醇酯50份至85份、玻璃纤维10份至30份、成核剂O. 01份至O.1份、矿物填料5份至15份、增韧剂O.1份至5份。 To give a glass fiber reinforced polyethylene terephthalate composite; wherein the glass fiber reinforced polyethylene terephthalate composite material, the raw material composition by weight of polyethylene terephthalate 50 parts to 85 parts, 10 parts of glass fibers to 30 parts, parts of a nucleating agent to O.1 O. 01 parts, of mineral filler is 5 parts to 15 parts, toughening O.1 to 5 parts.

[0016] 下面是对上述发明技术方案之二的进一步优化或/和改进: [0016] The following is a further optimization of the two above-mentioned aspect of the invention and / or improvements:

上述聚对苯二甲酸丁二醇酯、增韧剂和矿物填料在高混机中混合时间为2分钟至5分钟。 The above-mentioned polyethylene terephthalate, polybutylene terephthalate, toughening agents, and mineral filler in a high speed mixer mixing time of 2 minutes to 5 minutes.

[0017] 上述双螺杆挤出机的转速为80 r/min至200 r/min。 Speed ​​[0017] The twin screw extruder was 80 r / min to 200 r / min.

[0018] 上述双螺杆挤出机料筒至挤出口模的温度为190°C至245°C。 [0018] The twin-screw extruder cylinder to the extrusion die temperature of 190 ° C to 245 ° C.

[0019] 上述聚对苯二甲酸丁二醇酯的特性粘度为O. 8 dl/g至1.2 dl/g;或/和,聚对苯二甲酸丁二醇酯的熔点为220°C至230°C。 [0019] The intrinsic viscosity of polyethylene terephthalate is O. 8 dl / g to 1.2 dl / g; and / or polyethylene terephthalate melting point of 230 to 220 ° C ° C.

[0020] 上述玻璃纤维为表面经硅烷偶联剂处理的玻璃纤维;或/和,玻璃纤维的直径为9μ m0 [0020] surface of the glass fiber is a glass fiber silane coupling agent-treated; and / or diameter of glass fibers 9μ m0

[0021] 上述成核剂为苯甲酸钠、1,3,2,4-二亚苄基山梨糖醇中的一种以上混合物。 [0021] The nucleating agent is sodium benzoate, 1,3,2,4-dibenzylidene sorbitol in a mixture of one or more.

[0022] 上述增韧剂为聚乙烯-辛烯共聚物、乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯三元共聚物中的一种以上混合物。 [0022] The toughening agent is a polyethylene - octene copolymer, an ethylene - butyl acrylate - glycidyl methacrylate terpolymers of one or more mixture. [0023] 上述矿物填料的粒径为100目至2500目。 [0023] The particle size of the mineral filler is a 100 mesh to 2500 mesh. [0024] 上述矿物填料为滑石粉、碳酸钙、蒙脱土、膨润土、蛭石中的一种以上混合物。 [0024] The mineral filler is talc, calcium carbonate, montmorillonite, bentonite, a mixture of one or more of vermiculite. [0025] 本发明通过对玻璃纤维进行成核剂包覆预处理,改变了玻璃纤维的表面结构,提高了玻璃纤维和聚对苯二甲酸丁二醇酯基体之间的相互作用,诱导聚对苯二甲酸丁二醇酯结晶,提高了聚对苯二甲酸丁二醇酯的结晶度,改变了共混物的形态结构。 [0025] The present invention, by a glass fiber pre-coated with a nucleating agent, change the surface structure of the glass fibers, and glass fibers to improve the interaction between the polyethylene terephthalate substrate, polyethylene induction polybutylene terephthalate crystallization, increased cohesion terephthalate crystallization, alters the morphology of the blend. 本发明所得的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料的拉伸强度为98 MPa至108 MPa,冲击强度为6.0耵/1112至6.6 KJ/m2,具有制备过程简单、结晶速率快、结晶度高、力学性能好、表面光泽度高、收缩率低、尺寸稳定和低翘曲的特点,降低了生产成本,提高了综合性能。 The resulting fiber-reinforced glass of the present invention the tensile strength of polyethylene terephthalate composite material is 98 MPa to 108 MPa, impact strength Ding 6.0 / 1112 to 6.6 KJ / m2, having a simple preparation process, fast crystallization rate , high crystallinity, good mechanical properties, surface gloss, low shrinkage, low warpage and dimensional stability characteristics, reduce production costs and improve overall performance. 附图说明[0026] 附图1为原料中不加成核剂制得对比试样在超薄切片后在偏光显微镜下的晶体形态结构图。 BRIEF DESCRIPTION [0026] Figure 1 is a raw material is not obtained after addition ultrathin sections morphological chart-nucleating agent comparative sample under a polarizing microscope crystals. [0027] 附图2为至附图4为本发明试样在超薄切片后在偏光显微镜下的晶体形态结构图。 [0027] Figure 2 of the accompanying drawings to form ultrathin section 4 after crystals configuration diagram of a sample under a polarizing microscope of the present invention. 具体实施方式[0028] 本发明不受下述实施例的限制,可根据本发明的技术方案与实际情况来确定具体的实施方式。 DETAILED DESCRIPTION [0028] The present invention is not limited to the following embodiment, it may be determined in accordance with specific embodiments of the present invention, the technical solution with the actual situation. [0029] 下面结合实施例及附图对本发明作进一步描述:实施例1,该玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,按原料重量份数组成为聚对苯二甲酸丁二醇酯50份至85份、玻璃纤维10份至30份、成核剂O. 01份至O.1份、矿物填料5份至15份、增韧剂O.1份至5份。 [0029] The following embodiments and the accompanying drawings in conjunction with embodiments of the present invention is further described: Example 1, the glass fiber reinforced polyethylene terephthalate composite material, the raw material composition by weight polybutylene terephthalate 50 parts to 85 parts of an ester, 10 parts of glass fibers to 30 parts, parts of a nucleating agent to O.1 O. 01 parts, of mineral filler is 5 parts to 15 parts, toughening O.1 to 5 parts. [0030] 实施例2,该玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,按原料重量份数组成为聚对苯二甲酸丁二醇酯50 份或85份、玻璃纤维10份或30份、成核剂O. 01份或O.1份、 矿物填料5份或15份、增韧剂O.1份或5份。 [0030] Example 2, the glass fiber reinforced polyethylene terephthalate composite material, the raw material composition by weight is polyethylene 50 parts or 85 parts polybutylene terephthalate, 10 parts of glass fibers 30 or parts of a nucleating agent or parts O.1 O. 01 parts, 5 parts of mineral filler or 15 parts, 5 parts or parts O.1 toughener. [0031] 实施例3,该玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,按原料重量份数组成为聚对苯二甲酸丁二醇酯59. 99份、玻璃纤维30份、成核剂O. 01份、矿物填料5份、增韧剂5份。 [0031] Example 3, glass fiber reinforced polyethylene terephthalate composite material parts by weight of the raw material composition is a poly (butylene terephthalate) 59.99 parts, 30 parts of glass fibers, nucleating agents O. 01 parts, 5 parts of mineral filler, 5 parts of toughening agent. [0032] 实施例4,该玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,按原料重量份数组成为聚对苯二甲酸丁二醇酯59. 9份、玻璃纤维30份、成核剂O.1份、矿物填料5份、增韧剂5 份。 [0032] Example 4, the glass fiber reinforced polyethylene terephthalate composite material parts by weight of the raw material composition is a poly (butylene terephthalate) 59.9 parts, 30 parts of glass fibers, nucleating O.1 parts agent, 5 parts of mineral filler, 5 parts of toughening agent. [0033] 实施例5,作为上述实施例的优化:聚对苯二甲酸丁二醇酯的特性粘度为O. 8 dl/ 8至1.2 dl/g ;或/和,聚对苯二甲酸丁二醇酯的熔点为220°C至230°C。 [0033] Example 5, as the optimization of the above-described embodiments: an intrinsic viscosity of polyethylene terephthalate is O. 8 dl / 8 to 1.2 dl / g; and / or, polybutyleneterephthalate alcohol ester of melting point 220 ° C to 230 ° C. [0034] 实施例6,作为上述实施例的优化:实施例6的玻璃纤维为表面经硅烷偶联剂处理的玻璃纤维;或/和,玻璃纤维的直径为9 μ m。 [0034] Example 6, as the embodiment Optimization: glass fibers of Example 6 as a silane coupling agent surface treated glass fibers; and / or diameter of the glass fibers is 9 μ m. [0035] 实施例7,作为上述实施例的优化:实施例7的成核剂为苯甲酸钠;或者成核剂为1,3,2,4- 二亚苄基山梨糖醇;或者成核剂为苯甲酸钠和1,3,2,4- 二亚苄基山梨糖醇的混合物。 [0035] Example 7, as the optimization Example: Example 7 The nucleating agent is sodium benzoate embodiment; or nucleating agent is 1,3,2,4-dibenzylidene sorbitol; nucleating agents, or a mixture of benzoic acid and sodium 1,3,2,4-dibenzylidene sorbitol is. [0036] 实施例8,作为上述实施例的优化:实施例8的增韧剂为聚乙烯-辛烯共聚物;或者增韧剂为乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯三元共聚物;或者增韧剂为聚乙烯-辛烯共聚物和乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯三元共聚物的混合物。 [0036] Example 8, as the embodiment Optimization: Example 8 toughener polyethylene - octene copolymer; toughening agent or an ethylene - butyl acrylate - glycidyl methacrylate terpolymers thereof; toughener or a polyethylene - a mixture of glycidyl methacrylate terpolymer - octene copolymers and ethylene - butyl acrylate. [0037] 实施例9,作为上述实施例的优化:实施例9的矿物填料的粒径为100目至2500目。 [0037] Example 9, as the optimization Example: mineral filler particle size of Example 9 is 100 mesh to 2500 mesh. [0038] 实施例10,作为上述实施例的优化:实施例10的矿物填料为滑石粉、碳酸钙、蒙脱土、膨润土、蛭石中的一种以上混合物。 [0038] Example 10, as the optimization Example: Example 10 mineral filler is talc, calcium carbonate, montmorillonite, bentonite, vermiculite mixture of more than one embodiment. [0039] 实施例11,上述实施例1至实施例10的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料的制备方法,按下述步骤进行:第一步,将所需量的成核剂加入水中配成质量百分比浓度为1%至5%的成核剂溶液;第二步,把所需量的玻璃纤维放入成核剂溶液中进行浸泡,浸泡时间为Ih至5h,浸泡后将浸泡液和玻璃纤维放置在温度为60°C至100°C下蒸发、干燥至玻璃纤维中的含水量低于O. 01%,得到成核剂包覆后的玻璃纤维;第三步,将所需量的聚对苯二甲酸丁二醇酯在温度为100°C至140°C下干燥2h至6h ;第四步,将干燥后的聚对苯二甲酸丁二醇酯、所需量的增韧剂和矿物填料在高混机中混合后加入双螺杆挤出机中,聚对苯二甲酸丁二醇酯、增韧剂和矿物填料在双螺杆挤出机中熔融后在双螺杆挤出机中加入成核剂包覆后的玻璃纤维,共混挤出,冷却,切粒得到玻璃纤维增强 [0039] Example 11, the above-described Example 1 for preparing poly (butylene terephthalate) composite material, according to the following steps to the glass fiber reinforced Example 10: The first step, into the desired amount of dubbed nucleating agent was added to water percentage concentration of 1% by mass to 5% solution of a nucleating agent; a second step, the desired amount of glass fibers into a solution of nucleating agent to soak, soak time to Ih 5h, soaking after soaking solution and placed in a glass fiber evaporation temperature to 60 ° C under 100 ° C, dried to a moisture content of glass fiber is less than O. 01%, to obtain a glass fiber coated with the nucleating agent; step , the desired amount of polyethylene terephthalate is dried at a temperature of 2h to 100 ° C for 6h to 140 ° C; a fourth step, the dried polyethylene terephthalate, the demand tougheners and mineral filler after the addition of a twin screw compounder high mixing extruder, polyethylene terephthalate, polybutylene terephthalate, toughening agents, and mineral filler in a twin screw extruder in the melt glass fibers in the twin screw extruder after addition of the nucleating agent is coated with the blend is extruded, cooled, pelletized to obtain a glass fiber-reinforced 聚对苯二甲酸丁二醇酯复合材料。 Composite polyester terephthalate. [0040] 实施例12,上述实施例1至实施例10的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料的制备方法,按下述步骤进行:第一步,将所需量的成核剂加入水中配成质量百分比浓度为1%或5%的成核剂溶液;第二步,把所需量的玻璃纤维放入成核剂溶液中进行浸泡,浸泡时间为Ih或5h,浸泡后将浸泡液和玻璃纤维放置在温度为60°C或100°C下蒸发、干燥至玻璃纤维中的含水量低于O. 01%,得到成核剂包覆后的玻璃纤维;第三步,将所需量的聚对苯二甲酸丁二醇酯在温度为100°C或140°C下干燥2h或6h ;第四步,将干燥后的聚对苯二甲酸丁二醇酯、所需量的增韧剂和矿物填料在高混机中混合后加入双螺杆挤出机中,聚对苯二甲酸丁二醇酯、增韧剂和矿物填料在双螺杆挤出机中熔融后在双螺杆挤出机中加入成核剂包覆后的玻璃纤维,共混挤出,冷却,切粒得到玻璃纤维增强 [0040] Example 12, the above-described Example 1 for preparing poly (butylene terephthalate) composite material, according to the following steps to the glass fiber reinforced Example 10: The first step, into the desired amount of nucleating agent was added to water dubbed the mass concentration of 1% or 5% solution of a nucleating agent; a second step, the desired amount of glass fibers into a solution of nucleating agent to soak, soak time or Ih 5h, soaking after soaking solution and a glass fiber is placed in a 60 ° C temperature of 100 ° C or evaporated, dried to a moisture content of glass fiber is less than O. 01%, to obtain a glass fiber coated with the nucleating agent; step , the desired amount of polyethylene terephthalate at a temperature of 100 ° C for 2h or 140 ° C or dried 6H; a fourth step of drying the poly (butylene terephthalate), the demand tougheners and mineral filler after the addition of a twin screw compounder high mixing extruder, polyethylene terephthalate, polybutylene terephthalate, toughening agents, and mineral filler in a twin screw extruder in the melt glass fibers in the twin screw extruder after addition of the nucleating agent is coated with the blend is extruded, cooled, pelletized to obtain a glass fiber-reinforced 对苯二甲酸丁二醇酯复合材料。 Composite terephthalate esters. [0041] 实施例13,作为上述实施例的优化:实施例13的聚对苯二甲酸丁二醇酯、增韧剂和矿物填料在高混机中混合时间为2分钟至5分钟。 [0041] Example 13, as the above-described embodiment the optimization: polyethylene terephthalate, polybutylene terephthalate, toughening agents and fillers mineral Example 13 in a high speed mixer mixing time of 2 minutes to 5 minutes. [0042] 实施例14,作为上述实施例的优化:实施例14的双螺杆挤出机的转速为80 r/min 至200 r/min。 [0042] Example 14, as the above-described embodiment the optimization: speed twin-screw extruder Example 14 embodiment is 80 r / min to 200 r / min. [0043] 实施例15,作为上述实施例的优化:实施例15的双螺杆挤出机料筒及挤出口模的温度为190°C至245°C。 [0043] Example 15, as the above-described embodiment the optimization: an extruder barrel and extrusion die temperature Example 15 twin-screw embodiment is 190 ° C to 245 ° C. [0044] 上述实施例所得的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料置于鼓风烘箱中干燥后,采用注塑成型机注塑制得本发明试样;原料中不加成核剂制得对比试样;本发明试样和对比试样的平均性能参数如表I所示:表I [0044] Examples of the above-described embodiment the resultant glass fiber reinforced polyethylene terephthalate composite material is placed in a forced air oven and dried, using the samples of the invention prepared by injection molding an injection molding machine; feedstock without addition of the nucleating agent comparative sample was prepared; average performance parameters and Comparative sample sample of the present invention shown in table I: tABLE I

Figure CN102993651AD00081

注塑试样的拉伸性能测试按照GB/T1040. 1-2006标准测试,拉伸速率为10 mm/min ;弯曲性能测试按照GB/T 9341-2008标准测试,弯曲速率为2 mm/min ;缺口冲击强度测试按照GB/T 1843-2008标准测试,V型缺口,摆锤能量为5. 5 J0注塑试样的结晶度和结晶速率采用差示扫描量热仪进行测试,升温速率为10 °C/min,降温速率为20 °C/min ;偏光显微镜观察PBT的晶体形态。 Injection molding of tensile test specimens according to GB / T1040 1-2006 standard test, a tensile rate of 10 mm / min; bending performance tested in accordance with GB / T 9341-2008 standard test, the bending rate of 2 mm / min; gap impact strength test according to GB / T 1843-2008 standard test, V-notch Charpy energy of crystallinity and crystallization rate of 5. 5 J0 injection molded specimens using a differential scanning calorimeter for testing, heating rate in 10 ° C / min, cooling rate of 20 ° C / min; a polarizing microscope observation of the crystal morphology of PBT. 注塑样品的表面质量(表面光泽度、翘曲程度)观察采用的试样尺寸为: 直径为50 mm,厚度为2 mm,其主要分为:“良好、一般、较差”三个等级。 Sample size of the surface quality of injection molded samples (surface gloss, warpage) was used to observe: a diameter of 50 mm, a thickness of 2 mm, which is divided into: "good, fair, poor." Three levels. [0045] 从表I可以看出,本发明试样的拉伸强度、弯曲模量、冲击强度、结晶度、结晶速率-半结晶时间和表面质量分别为98 MPa至108 MPa,6431 MPa至6859 MPa、6. O KJ/m2至6.6 KJ/m2、42. 7%至48.3%、4. 14 s至5. 05 S、良好;对比试样的拉伸强度、弯曲模量、冲击强度、结晶度、结晶速率(半结晶时间)和表面质量分别为69 MPa至95 MPa,3560 MPa至7100 MPa,2. 8 KJ/m2 至5. 6 KJ/m2、35. 4% 至36. 8%、8· 13 s 至8. 94 S、一般;本发明试样较对比试样的拉伸强度、弯曲模量、冲击强度、结晶度和表面质量都有提高且结晶速率快。 [0045] I can be seen from the table, the tensile strength of the sample of the present invention, the flexural modulus, impact strength, crystallinity, crystallization rate - half-crystallization time and surface quality are 98 MPa to 108 MPa, 6431 MPa to 6859 ... MPa, 6 O KJ / m2 to 6.6 KJ / m2,42 7% to 48.3%, 4 14 s to 5. 05 S, good; Comparative tensile strength, flexural modulus, impact strength, crystallization degree, rate of crystallinity (crystallization half time) and the surface quality are 69 MPa to 95 MPa, 3560 MPa to 7100 MPa, 2. 8 KJ / m2 to 5. 6 KJ / m2,35. 4% to 36. A 8% to 8 · 13 s 8. 94 S, generally; samples of the invention than the comparative tensile strength, flexural modulus, impact strength, crystallinity and surface quality are improved and faster crystallization rate. 所以玻璃纤维能有效地提高聚对苯二甲酸丁二醇酯(PBT)的力学性能,但过多的玻璃纤维会影响聚对苯二甲酸丁二醇酯(PBT)复合材料表面质量;而适量的矿物填料能获得一定力学性能的基础上得到生产成本的降低;而成核剂的引入,有效地提高体系的结晶度和结晶速率,从而获得了力学性能的有效改善。 Therefore, the glass fibers can improve the mechanical properties of polyethylene terephthalate, polybutylene terephthalate (PBT), but too much can affect the surface quality of the glass fiber composite polyethylene terephthalate, polybutylene terephthalate (PBT); the amount mineral filler can be obtained based on certain mechanical properties to give the reduction in production costs; obtained by introducing a nucleating agent, crystallinity and effectively improve the crystallization rate of the system, thereby obtaining improved mechanical properties effectively. [0046] 从附图1至附图4中可进一步得知:本发明的晶体颗粒更小,表明成核剂起到了成核作用,提高了结晶速率。 [0046] From Figures 1 to 4 may further that: the crystal particles of the present invention is smaller, indicating that the nucleating agent serves the nucleation, the crystallization rate improved. [0047] 以上技术特征构成了本发明的实施例,其具有较强的适应性和实施效果,可根据实际需要增减非必要的技术特征,来满足不同情况的需求。 Technical characteristics [0047] The above embodiments of the present invention is constituted, which has strong adaptability embodiments and effects can increase or decrease the actual needs of non-essential technical features to meet the needs of different situations according to.

Claims (10)

  1. 1. 一种玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,其特征在于按原料重量份数组成为聚对苯二甲酸丁二醇酯50份至85份、玻璃纤维10份至30份、成核剂0. 01份至0.1份、矿物填料5份至15份、增韧剂0.1份至5份;该玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料按下述步骤得到:第一步,将所需量的成核剂加入水中配成质量百分比浓度为1%至5%的成核剂溶液;第二步,把所需量的玻璃纤维放入成核剂溶液中进行浸泡,浸泡时间为Ih至5h,浸泡后将浸泡液和玻璃纤维放置在温度为60°C至100°C下蒸发、干燥至玻璃纤维中的含水量低于0. 01%,得到成核剂包覆后的玻璃纤维;第三步,将所需量的聚对苯二甲酸丁二醇酯在温度为100°C至140°C下干燥2h至6h ;第四步,将干燥后的聚对苯二甲酸丁二醇酯、所需量的增韧剂和矿物填料在高混机中混合后加入双螺杆挤出机中,聚对 1. A glass fiber reinforced polyethylene terephthalate composite material, wherein the raw material composition by weight is polyethylene 50 parts to 85 parts polybutylene terephthalate, 10 parts glass fibers to 30 parts , nucleating agent 0.01 parts to 0.1 parts, of mineral filler is 5 parts to 15 parts, 0.1 parts to 5 parts of toughening agent; glass fiber reinforced polyethylene terephthalate composite material obtained by the following steps: the first step, the desired amount of nucleating agent added to the mass concentration of water dubbed 1-5% solution of a nucleating agent; a second step, the desired amount of glass fibers into the solution for nucleating agent soak, soak time to Ih 5h, after soaking the glass fibers and placed in a soaking liquor temperature of 60 ° C for evaporated to 100 ° C, dried to a moisture content of glass fiber is less than 0.01% a nucleating agent after the coated glass fibers; a third step, the required amount of the polyethylene terephthalate is dried at a temperature of 2h to 100 ° C for 6h to 140 ° C; a fourth step, the dried poly terephthalate, polybutylene terephthalate, toughening agents and mineral filler in the desired amount of the addition of a twin-screw mixing machine in a high compounding extruder, poly 二甲酸丁二醇酯、增韧剂和矿物填料在双螺杆挤出机中熔融后在双螺杆挤出机中加入成核剂包覆后的玻璃纤维,共混挤出,冷却,切粒得到玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料。 Butylene naphthalate, toughening agents, and mineral filler is added in a twin screw extruder into a glass fiber coated with the nucleating agent in the melt in the twin screw extruder, blender extruded, cooled and pelletized to give glass fiber reinforced polybutylene terephthalate composite pair.
  2. 2.根据权利要求1所述的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,其特征在于聚对苯二甲酸丁二醇酯的特性粘度为0. 8 dl/g至1. 2d dl/g ;或/和,聚对苯二甲酸丁二醇酯的熔点为220°C至230°C。 The glass fiber according to claim 1, polyethylene terephthalate, polybutylene terephthalate reinforced composite material, characterized in that a polyethylene terephthalate having an intrinsic viscosity of 0. 8 dl / g to 1. 2d dl / g; and / or polyethylene terephthalate melting point of 220 ° C to 230 ° C.
  3. 3.根据权利要求1或2所述的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,其特征在于玻璃纤维为表面经硅烷偶联剂处理的玻璃纤维;或/和,玻璃纤维的直径为9 um。 The glass fiber of claim 12 or claim reinforced polyethylene terephthalate composite material, characterized in that the surface of the glass fiber is a glass fiber silane coupling agent-treated; and / or glass fibers having a diameter of 9 um.
  4. 4.根据权利要求1或2或3所述的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,其特征在于成核剂为苯甲酸钠、1,3,2,4- 二亚苄基山梨糖醇中的一种以上混合物。 The glass fiber of claim 1 or 2 or 3 reinforced polyethylene terephthalate composite material, wherein the nucleating agent is sodium benzoate, 1,3,2,4-dibenzylidene claim mixture of one or more of sorbitol.
  5. 5.根据权利要求1或2或3或4所述的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,其特征在于增韧剂为聚乙烯-辛烯共聚物、乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯三元共聚物中的一种以上混合物。 The glass fiber 1 or 2 or 3 or 4, wherein the polyethylene terephthalate reinforced composite material as claimed in claim wherein the toughener is a polyethylene - octene copolymer, an ethylene - butyl acrylate - one or more glycidyl methacrylate terpolymer mixture glycerides.
  6. 6.根据权利要求1或2或3或4或5所述的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,其特征在于矿物填料的粒径为100目至2500目。 The glass fiber 1 or 2 or 3 or 4 or 5, wherein the polyethylene terephthalate reinforced composite material, characterized in that the mineral filler particle size of 100 mesh to 2500 mesh claims.
  7. 7.根据权利要求1或2或3或4或5或6所述的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料,其特征在于矿物填料为滑石粉、碳酸钙、蒙脱土、膨润土、蛭石中的一种以上混合物。 The glass fiber 1 or 2 or 3 or 4 or 5 or claim 6 reinforced polyethylene terephthalate composite material, characterized in that the mineral filler is talc, calcium carbonate, montmorillonite, bentonite, a mixture of one or more of vermiculite.
  8. 8. 一种根据权利要求17所述的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料的制备方法,其特征在于按下述步骤进行:第一步,将所需量的成核剂加入水中配成质量百分比浓度为1%至5%的成核剂溶液;第二步,把所需量的玻璃纤维放入成核剂溶液中进行浸泡,浸泡时间为Ih至5h,浸泡后将浸泡液和玻璃纤维放置在温度为60°C至100°C下蒸发、干燥至玻璃纤维中的含水量低于0. 01%,得到成核剂包覆后的玻璃纤维;第三步,将所需量的聚对苯二甲酸丁二醇酯在温度为100°C至140°C下干燥2h至6h ;第四步,将干燥后的聚对苯二甲酸丁二醇酯、所需量的增韧剂和矿物填料在高混机中混合后加入双螺杆挤出机中,聚对苯二甲酸丁二醇酯、增韧剂和矿物填料在双螺杆挤出机中熔融后在双螺杆挤出机中加入成核剂包覆后的玻璃纤维,共混挤出,冷却,切粒得到玻璃纤维增强 8. A glass fiber according to claim 17 Preparation reinforced polyethylene terephthalate composite material, characterized by the following steps performed: a first step, the required amount of a nucleating agent was added to water dubbed the mass concentration of 1 to 5% solution of a nucleating agent; a second step, the desired amount of glass fibers into a solution of nucleating agent to soak, soak time to Ih 5h, after soaking glass fibers and placed in a soaking solution evaporation temperature to 60 ° C under 100 ° C, dried to a moisture content of glass fiber is less than 0.01%, to obtain a glass fiber coated with the nucleating agent; the third step, desired amount of polyethylene terephthalate is dried at a temperature of 2h to 100 ° C for 6h to 140 ° C; a fourth step, the dried polyethylene terephthalate, the desired amount of tougheners and mineral filler in a high speed mixer was added after the twin screw mixing extruder, polyethylene terephthalate, polybutylene terephthalate, toughening agents, and mineral filler in a twin screw extruder after melted in a twin-screw glass fiber extruder nucleating agent is added after the coating blend is extruded, cooled, pelletized to obtain a glass fiber-reinforced 对苯二甲酸丁二醇酯复合材料。 Composite terephthalate esters.
  9. 9.根据权利要求8所述的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料的制备方法,其特征在于聚对苯二甲酸丁二醇酯、增韧剂和矿物填料在高混机中混合时间为2分钟至5分钟。 9. The glass fiber of claim 8 Preparation reinforced polyethylene terephthalate composite material, characterized in that polyethylene terephthalate, polybutylene terephthalate, toughening agents and mineral filler in a high speed mixer the mixing time is 2-5 minutes.
  10. 10.根据权利要求8或9所述的玻璃纤维增强聚对苯二甲酸丁二醇酯复合材料的制备方法,其特征在于双螺杆挤出机的转速为80 r/min至200 r/min ;或/和,双螺杆挤出机料筒至挤出口模的温度为190°C至245°C。 10. The glass fiber of claim 8 or claim 9 Preparation reinforced polyethylene terephthalate composite material, characterized in that the rotational speed of the twin screw extruder of 80 r / min to 200 r / min; and / or, to a twin screw extruder barrel temperature of the extrusion die is 190 ° C to 245 ° C.
CN 201210540088 2012-12-14 2012-12-14 Glass-fiber-reinforced polybutylene terephthalate composite material and preparation method thereof CN102993651A (en)

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CN104151789A (en) * 2014-07-16 2014-11-19 厦门金越电器有限公司 Low-warping high voltage resistance PBT modified material and preparation method thereof
CN106009539A (en) * 2016-06-22 2016-10-12 西华大学 Polymer material containing flame retardant adopting gradient concentration distribution

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US3812077A (en) * 1971-12-27 1974-05-21 Gen Electric Fiber reinforced composite materials
CN102464868A (en) * 2010-11-05 2012-05-23 合肥杰事杰新材料股份有限公司 Scratch-resistant polybutylene terephthalate composition and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US3812077A (en) * 1971-12-27 1974-05-21 Gen Electric Fiber reinforced composite materials
CN102464868A (en) * 2010-11-05 2012-05-23 合肥杰事杰新材料股份有限公司 Scratch-resistant polybutylene terephthalate composition and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104151789A (en) * 2014-07-16 2014-11-19 厦门金越电器有限公司 Low-warping high voltage resistance PBT modified material and preparation method thereof
CN104151789B (en) * 2014-07-16 2016-10-05 厦门金越电器有限公司 A low-warpage, high voltage pbt modified based material and method
CN106009539A (en) * 2016-06-22 2016-10-12 西华大学 Polymer material containing flame retardant adopting gradient concentration distribution
CN106009539B (en) * 2016-06-22 2018-04-20 西华大学 A method for preparing a polymer material and a flame retardant concentration gradient distribution

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