CN102424717A - 一种增强增韧聚材料的制备方法 - Google Patents

一种增强增韧聚材料的制备方法 Download PDF

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CN102424717A
CN102424717A CN2011103776735A CN201110377673A CN102424717A CN 102424717 A CN102424717 A CN 102424717A CN 2011103776735 A CN2011103776735 A CN 2011103776735A CN 201110377673 A CN201110377673 A CN 201110377673A CN 102424717 A CN102424717 A CN 102424717A
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screw extruder
twin screw
temperature
district temperature
coupling agent
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张明
支长勇
韦嘉
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NANJING HONGRUI PLASTIC PRODUCTS CO Ltd
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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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • 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
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • 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
    • 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
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing
    • 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
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone

Abstract

本发明涉及一种增强增韧聚材料的制备方法，将对苯二甲酸丁二醇酯、聚碳酸酯、增韧剂、相容剂、偶联剂和抗氧剂混合均匀，于双螺杆挤出机中熔融共混，同时加入玻璃纤维，挤出造粒；挤出机工艺条件为：双螺杆挤出机1-2区温度为190-220℃，3-4区温度为230-250℃，5-6区温度为230-250℃，7-8区温度为240-270℃，机头温度为230-250℃，螺杆转速为150-350转/分钟；上述各原料的重量用量为：聚对苯二甲酸丁二醇酯40～60％，玻璃纤维10～30％，聚碳酸酯10～20％，增韧剂5～15％，相容剂1～8％，偶联剂0.1～1％，抗氧剂0.1～0.5％。采用本发明制得的材料的强度可以与单纯玻璃纤维增强PBT材料相当，缺口冲击韧性可达40KJ/m2，接近甚至超出单纯增韧PBT材料，同时工艺简单，有着广阔的应用前景。

Description

一种增强增韧聚材料的制备方法
技术领域
本发明涉及一种一种增强增韧聚对苯二甲酸丁二醇酯材料及其制备方法，可应用于建筑工程、机械电子、汽车工程等领域，属于高分子材料技术领域。 
背景技术
聚对苯二甲酸丁二醇酯(PBT)作为一种重要的热塑性工程塑料，广泛应用在汽车、电子、电器等行业。它具有高的结晶度和结晶速率、良好的耐化学药品性及优异的加工性能，已成为五大通用工程塑料中的一个重要成员。但纯PBT缺口冲击强度低的缺点，限制了其应用范围的进一步扩大。PBT通过与弹性体共混来改善冲击性能是目前广泛采用的方法。然而，单纯采用弹性体增韧PBT在获得高冲击韧性的同时，造成材料强度的大幅度下降。如何在增韧的基础上进一步提高材料的强度，成为高分子材料研究者努力追求的目标。 
中国专利(公开号CN200310108106.5)公开了一种增韧增强聚对苯二甲酸丁二醇酯复合材料的制备方法，采用PBT与无机纳米材料、反应相容剂共混挤出，得到增韧增强聚对苯二甲酸丁二醇酯复合材料，缺点是纳米无机材料成本高，难处理，在保持了弯曲强度的前提下，其最高缺口冲击强度也仅为12.42KJ/m2；中国专利(公开号CN200710190624.4)公开了一种纳米复合增韧增强聚对苯二甲酸丁二醇酯及生产方法，由纳米碳酸钙、马来酸酐接枝POE、PBT组成，其缺口冲击可达30KJ/m2以上，但其弯曲强度只有160MPa，且纳米碳酸钙的表面活化过程繁琐，不易控制，增加了成本。 
发明内容
本发明的目的在于提供一种简单可行的增强增韧材料的制备方法，使此材料在保持刚性强度的同时，大幅提高韧性。 
本发明的具体技术方案如下： 
将对苯二甲酸丁二醇酯、聚碳酸酯、增韧剂、相容剂、偶联剂和抗氧剂混合均匀，于双螺杆挤出机中熔融共混，同时加入玻璃纤维，挤出造粒；挤出机工艺条件为：双螺杆挤出机1-2区温度为190-220℃，3-4区温度为230-250℃，5-6区温度为230-250℃，7-8区温度为240-270℃，机头温度为230-250℃，螺杆转速为150-350转/分钟；上述各原料 的重量用量如下： 
聚对苯二甲酸丁二醇酯(PBT)    40～60％、 
玻璃纤维                     10～30％、 
聚碳酸酯(PC)                 10～20％、 
增韧剂                       5～15％。 
相容剂                       1～8％ 
偶联剂                       0.1％～1％ 
抗氧剂                       0.1％～0.5％ 
上述聚对苯二甲酸丁二醇酯(PBT)为对苯二甲酸和丁二醇的缩聚物，这是本技术领域公知的，可以根据用途选用不同的牌号； 
上述玻璃纤维为无碱连续玻璃纤维，单丝直径优选在8～18μm，其原因是单丝直径如小于8μm，强度低；单丝直径如大于18μm，制得的最终材料表面粗糙，且对生产设备磨损较大。 
上述聚碳酸酯为双酚A和光气的缩聚物，这是本技术领域公知的，可以根据用途选用不同的牌号。 
上述增韧剂有多种选择，如接枝SBS、接枝POE、接枝EPDM等，本发明优选为马来酸酐接枝的SEBS(SEBS-g-MAH)，其熔融指数优选为0.5-10g/10min，接枝率优选为0.3％-1.5％，其原因是申请人经研究发现，熔融指数如果不在0.5-10g/10min范围内，会造成加工困难；而接枝率在0.3％-1.5％范围内，增韧效果最好，过低则增韧效果不明显，过高则材料会有明显的刺激性气味。 
上述相容剂为丙烯晴-苯乙烯-丙烯酸嵌段共聚物(ASA)，可以根据用途选用不同的牌号； 
上述偶联剂为γ-氨丙基三乙氧基硅烷； 
所述的抗氧剂为抗氧剂1010和抗氧剂168按重量比1∶1的混合物。 
采本发明制得的增强增韧材料材料的强度可以与单纯玻璃纤维增强PBT材料相当，缺口冲击韧性可达40KJ/m2，接近甚至超出单纯增韧PBT材料，同时其制备工艺简单，有着广阔的应用前景。 
具体实施方式
以下实施例用以进一步解释本发明，但本发明不只限于这些实施例。 
实施例1、2、3、4和对比例1、2见表1。表1中所列配方量的聚对苯二甲酸丁二醇酯、聚碳酸酯、增韧剂、相容剂、偶联剂和抗氧剂在高速混合机中混合均匀，于双螺杆挤出机中熔融共混，同时加入玻璃纤维，挤出造粒。挤出机工艺条件为：双螺杆挤出机1-2区温度为190-220℃，3-4区温度为230-250℃，5-6区温度为230-250℃，7-8区温度为240-270℃，机头温度为230-250℃，螺杆转速为150-350转/分钟。材料的性能见表2。 
表1： 
Figure DEST_PATH_GDA0000122324210000031
表2： 
Figure DEST_PATH_GDA0000122324210000041

Claims (1)

1.一种增强增韧聚材料的制备方法，其特征在于将对苯二甲酸丁二醇酯、聚碳酸酯、增韧剂、相容剂、偶联剂和抗氧剂混合均匀，于双螺杆挤出机中熔融共混，同时加入玻璃纤维，挤出造粒；挤出机工艺条件为：双螺杆挤出机1-2区温度为190-220℃，3-4区温度为230-250℃，5-6区温度为230-250℃，7-8区温度为240-270℃，机头温度为230-250℃，螺杆转速为150-350转/分钟；上述各原料的重量用量如下：
Figure FDA0000111732420000011
上述玻璃纤维为无碱连续玻璃纤维，单丝直径在8～18μm；增韧剂为马来酸酐接枝的SEBS(SEBS-g-MAH)，其熔融指数为0.5-10g/10min，接枝率为0.3％-1.5％；相容剂为丙烯晴-苯乙烯-丙烯酸嵌段共聚物(ASA)；偶联剂为γ-氨丙基三乙氧基硅烷；抗氧剂为1010和抗氧剂168按重量比1∶1的混合物。
CN2011103776735A 2011-11-24 2011-11-24 一种增强增韧聚材料的制备方法 Pending CN102424717A (zh)

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN103214801A (zh) * 2013-04-16 2013-07-24 上海瀚氏模具成型有限公司 一种抗老化塑料汽车保险杠及其制备方法
CN104558692A (zh) * 2014-12-10 2015-04-29 常州诺瑞格纳米科技有限公司 一种能够循环使用的一次性塑料杯
CN107759984A (zh) * 2017-10-23 2018-03-06 安徽江淮汽车集团股份有限公司 一种pbt‑pc复合材料及其制备方法
CN108047659A (zh) * 2017-11-21 2018-05-18 横店集团得邦工程塑料有限公司 一种pbt/pc/asa复合材料及其制备方法
CN110903616A (zh) * 2019-12-06 2020-03-24 江苏垶恒复合材料有限公司 一种高韧性再生pet材料及其制备方法
CN113462141A (zh) * 2021-06-15 2021-10-01 上海电力大学 一种高韧低浮纤增强pc/pbt合金材料及制备方法

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CN101787183A (zh) * 2009-10-15 2010-07-28 上海锦湖日丽塑料有限公司 一种低翘曲高表面光泽玻纤增强聚酯复合材料及制备方法
CN101851401A (zh) * 2010-03-09 2010-10-06 上海锦湖日丽塑料有限公司 一种高流动聚酯组合物及制备方法

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CN101787183A (zh) * 2009-10-15 2010-07-28 上海锦湖日丽塑料有限公司 一种低翘曲高表面光泽玻纤增强聚酯复合材料及制备方法
CN101851401A (zh) * 2010-03-09 2010-10-06 上海锦湖日丽塑料有限公司 一种高流动聚酯组合物及制备方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103214801A (zh) * 2013-04-16 2013-07-24 上海瀚氏模具成型有限公司 一种抗老化塑料汽车保险杠及其制备方法
CN103214801B (zh) * 2013-04-16 2016-01-20 上海瀚氏模具成型有限公司 一种抗老化塑料汽车保险杠及其制备方法
CN104558692A (zh) * 2014-12-10 2015-04-29 常州诺瑞格纳米科技有限公司 一种能够循环使用的一次性塑料杯
CN107759984A (zh) * 2017-10-23 2018-03-06 安徽江淮汽车集团股份有限公司 一种pbt‑pc复合材料及其制备方法
CN108047659A (zh) * 2017-11-21 2018-05-18 横店集团得邦工程塑料有限公司 一种pbt/pc/asa复合材料及其制备方法
CN110903616A (zh) * 2019-12-06 2020-03-24 江苏垶恒复合材料有限公司 一种高韧性再生pet材料及其制备方法
CN113462141A (zh) * 2021-06-15 2021-10-01 上海电力大学 一种高韧低浮纤增强pc/pbt合金材料及制备方法

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Application publication date: 20120425