CN101712794A - 一种耐低温pc/pet复合材料及其制备方法 - Google Patents

一种耐低温pc/pet复合材料及其制备方法 Download PDF

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CN101712794A
CN101712794A CN200910192247A CN200910192247A CN101712794A CN 101712794 A CN101712794 A CN 101712794A CN 200910192247 A CN200910192247 A CN 200910192247A CN 200910192247 A CN200910192247 A CN 200910192247A CN 101712794 A CN101712794 A CN 101712794A
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low temperature
pet
temperature resistant
matrix material
preparation
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CN101712794B (zh
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郝建鑫
余鹏
任萍
郝源增
刘帅
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GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS CO., LTD.
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GUANGZHOU JINGYING PLASTIC CO Ltd
JUSAILONG ENGINEERING PLASTICS Co Ltd CONGHUA
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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
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
    • 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
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
    • B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
    • 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
    • B29C2948/92514—Pressure
    • 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

本发明提供一种耐低温PC/PET复合材料及其制备方法，该复合材料由PC、PET、相容剂、增韧剂、耐低温改良剂、抗氧剂干燥、搅拌、在双螺杆挤出机中熔融挤出造粒制备而成。本发明材料在相对于室温，复合材料-30℃下的悬臂梁缺口冲击强度保持90％以上，能达到近700J/m，弯曲模量2000-2300MPa，265℃，2.16kg时的熔融指数10-35g/10min，0.45MPa热变形温度＞120℃。该复合材料具有优良耐低温性能、高力学性能、耐热性及尺寸稳定性好，可广泛应用于家电、电子电器、建材、汽车等领域。

Description

一种耐低温PC/PET复合材料及其制备方法
技术领域
本发明涉及高分子材料技术领域，具体涉及一种耐低温PC/PET复合材料的制备方法。
背景技术
PC(聚碳酸酯)具有优异的力学强度、热稳定性，是五大通用工程塑料之一。然而PC存在熔体粘度高、成型加工难、不耐油和溶剂、低温冲击差等缺点。PET(聚对苯二甲酸乙二醇酯)是结晶性材料，耐油性和耐溶剂性优异，然而PET单独使用时，存在耐热性差、力学强度不高等缺点。
目前国内对PC/PET复合材料研究不多，尤其关于耐低温PC/PET复合材料几乎没有。如，中国专利《一种PC/PET合金及其制备方法》，专利申请号：200710074569.2，报道了一种PC/PET复合材料的制备方法；中国专利《一种PC/PET合金及其制备方法》，专利申请号：200710019829.6，报道一种PC/PET合金片材的制备方法。以上发明均没有涉及到PC/PET复合材料的耐低温性能研究。因此，如何通过配方设计制备出具有优良低温性能的PC/PET复合材料，以替代PC或PC/ABS用于对耐低温性、耐油耐溶剂性、耐热性较高的领域，将具有重要的实际应用价值，相关途径还未见报道。
发明内容
本发明的目的是针对现有技术的不足而提供一种制备容易、低成本、耐低温性好、耐油耐溶剂好、耐热性佳、力学性能优异的耐低温PC/PET复合材料及其制备方法。
本发明的上述目的可以通过以下技术方案实现：
一种耐低温PC/PET复合材料及其制备方法，其特征在于：包括如下步骤，
(1)将PC、PET树脂于110℃-120℃鼓风干燥3-6小时；
(2)将干燥好的PC和PET树脂、相容剂、增韧剂、低温改良剂、抗氧剂依次加入搅拌机中，在300-500转/分的转速下搅拌混合3-5分钟；
(3)将上述混合物加入双螺杆挤出机中，经熔融挤出造粒即得成品。加工工艺如下：双螺杆挤出机一区温度200-215℃，二区温度220-235℃，三区温度220-235℃，四区温度220-235℃，五区温度200-215℃，六区温度220-240℃，机头温度225-240℃，压力为11-17MPa，螺杆转速为250-400rpm；水槽温度20-40℃；切粒机转速为600-1000rpm；
上述组分按重量百分比为：
(1)PC                    60-85％；
(2)PET                   9-30％；
(3)相容剂                0-5％；
(4)增韧剂                0-6％；
(5)低温改良剂            0.5-2％；
(6)抗氧剂                0-0.5％；
上述各组分配方比例总和为100％。
所述的PC分子量为20000-30000g/mol。
所述PET的特性粘度为0.6-1.0dl/g。
所述相容剂为乙烯-马来酸酐-缩水甘油酯共聚物、丙烯酸酯-缩水甘油酯-乙烯共聚物、苯乙烯-马来酸酐共聚物、丙烯酸酯类聚合物中的至少一种，如丙烯酸酯-缩水甘油酯-乙烯类相容剂KT-22。
所述的增韧剂为甲基丙烯酸-丁二烯-苯乙烯共聚物、乙烯-丙烯酸酯共聚物、丙烯腈-丙烯酸-苯乙烯共聚物、丙烯腈-丁二烯-苯乙烯共聚物、丙烯腈-乙烯-苯乙烯共聚物中的至少一种，如甲基丙烯酸-丁二烯-苯乙烯类增韧剂罗门哈斯2678。
所述的低温改良剂为聚硅氧烷共聚物、有机硅氧烷、苯甲基硅酮、硅酮的至少一种，如有机硅氧烷类低温改良剂道康宁MB50-007。
所述的抗氧剂为为酚类抗氧剂、亚磷酸酯类抗氧剂、金属钝化剂中的任一种或两种以上的混合物，如酚类抗氧化剂1010。
本发明所述配方及工艺制得的无卤阻燃PC/PET复合材料采用ASTM标准检测，性能如下：
密度：                     1.20-1.23g/cm3
断裂伸长率：               200-300％
拉伸强度：                 50-65MPa
弯曲模量：                 2000-2300MPa
23℃悬臂梁缺口冲击强度：   500-730J/m
-30℃悬臂梁缺口冲击强度：  450-685J/m
熔融指数：                 15-35g/10min(265℃，2.16Kg)
热变形温度(0.45MPa)        120-131℃
耐油性(花生油48h浸泡)      不变色，不开裂
其有益效果是：常规PC/PET复合材料具有流动性好、耐溶剂性、耐热性好的特点，然而其低温下力学强度较差，限制了该材料的应用范围。本发明通过硅橡胶的低温改良，提供一种耐低温PC/PET复合材料，可替代PC或PC/ABS用于对耐低温、耐油、耐溶剂、耐热等要求较高的领域。
具体实施方式
实施例1：
下述组分按重量百分比为：
(1)PC                         78％；
(2)PET                        13％；
(3)相容剂：KT-22              3％；
(4)增韧剂：罗门哈斯2678       4％；
(5)低温改良剂：
有机硅氧烷道康宁MB50-007      1.5％；
(6)抗氧化剂：1010             0.5％；
先将PC、PET树脂于110℃鼓风干燥4小时，将干燥好的PC和PET树脂、相容剂、增韧剂、低温改良剂、抗氧剂依次加入搅拌机中，在500转/分的转速下搅拌混合3分钟。然后将上述混合物加入双螺杆挤出机中，经熔融挤出造粒即得成品。加工工艺如下：双螺杆挤出机一区温度210℃，二区温度230℃，三区温度230℃，四区温度230℃，五区温度200℃，六区温度230℃，机头温度235℃，压力为15MPa，螺杆转速为300rpm；水槽温度40℃；切粒机转速为800rpm；
所得耐低温PC/PET复合材料经检测性能如下：
密度：                     1.20g/cm3
断裂伸长率：               225％
拉伸强度：                 61MPa
弯曲模量：                 2180MPa
23℃悬臂梁缺口冲击强度：   720J/m
-30℃悬臂梁缺口冲击强度：  675J/m
熔融指数：                 19g/10min(265℃，2.16Kg)
热变形温度(0.45MPa)        130℃
耐油性(花生油48h浸泡)      不变色，不开裂。
实施例2：
下述组分按重量百分比为：
(1)PC                      66％；
(2)PET                     24％；
(3)相容剂：KT-22           4.5％；
(4)增韧剂：罗门哈斯2678    4％；
(5)低温改良剂：
有机硅氧烷道康宁MB50-007   1％；
(6)抗氧化剂：1010        0.5％；
先将PC、PET树脂于110℃鼓风干燥4小时，将干燥好的PC和PET树脂、相容剂、增韧剂、低温改良剂、抗氧剂依次加入搅拌机中，在500转/分的转速下搅拌混合3分钟。然后将上述混合物加入双螺杆挤出机中，经熔融挤出造粒即得成品。加工工艺如下：双螺杆挤出机一区温度210℃，二区温度230℃，三区温度230℃，四区温度230℃，五区温度200℃，六区温度230℃，机头温度235℃，压力为15MPa，螺杆转速为300rpm；水槽温度40℃；切粒机转速为800rpm；
所得耐低温PC/PET复合材料经检测性能如下：
密度：                     1.22g/cm3
断裂伸长率：               275％
拉伸强度：                 55MPa
弯曲模量：                 2080MPa
23℃悬臂梁缺口冲击强度：   700J/m
-30℃悬臂梁缺口冲击强度：  665J/m
熔融指数：                 28g/10min(265℃，2.16Kg)
热变形温度(0.45MPa)        127℃
耐油性(花生油48h浸泡)      不变色，不开裂。

Claims (8)

1.一种耐低温PC/PET复合材料及其制备方法，其特征在于：包括如下步骤，
(1)将PC、PET树脂于110℃-120℃鼓风干燥3-6小时；
(2)将干燥好的PC和PET树脂、相容剂、增韧剂、耐低温改良剂、抗氧剂依次加入搅拌机中，在300-500转/分的转速下搅拌混合3-5分钟；
(3)将上述混合物加入双螺杆挤出机中，经熔融挤出造粒即得成品；加工工艺如下：双螺杆挤出机一区温度200-215℃，二区温度220-235℃，三区温度220-235℃，四区温度220-235℃，五区温度200-215℃，六区温度220-240℃，机头温度225-240℃，压力为11-17MPa，螺杆转速为250-400rpm，水槽温度20-40℃，切粒机转速为600-1000rpm；
上述组分按重量百分比为：
(1)PC              60-85％；
(2)PET             9-30％；
(3)相容剂          0-5％；
(4)增韧剂          0-6％；
(5)低温改良剂      0.5-2％；
(6)抗氧剂          0-0.5％；
上述各组分配方比例总和为100％。
2.根据权利要求1所述的一种耐低温PC/PET复合材料及其制备方法，其特征在于：所述的PC分子量为20000-30000g/mol。
3.根据权利要求1所述的一种耐低温PC/PET复合材料及其制备方法，其特征在于：所述PET的特性粘度为0.6-1.0dl/g。
4.根据权利要求1所述的一种耐低温PC/PET复合材料及其制备方法，其特征在于：所述相容剂为乙烯-马来酸酐-缩水甘油酯共聚物、丙烯酸酯-缩水甘油酯-乙烯共聚物、苯乙烯-马来酸酐共聚物、丙烯酸酯类聚合物中的至少一种。
5.根据权利要求1所述的一种耐低温PC/PET复合材料及其制备方法，其特征在于：所述的增韧剂为甲基丙烯酸-丁二烯-苯乙烯共聚物、乙烯-丙烯酸酯共聚物、丙烯腈-丙烯酸-苯乙烯共聚物、丙烯腈-丁二烯-苯乙烯共聚物、丙烯腈-乙烯-苯乙烯共聚物中的至少一种。
6.根据权利要求1所述的一种耐低温PC/PET复合材料及其制备方法，其特征在于：所述的低温改良剂为聚硅氧烷共聚物、有机硅氧烷、苯甲基硅酮、硅酮中的至少一种。
7.根据权利要求1所述的一种耐低温PC/PET复合材料及其制备方法，其特征在于：所述的抗氧剂为酚类抗氧剂、亚磷酸酯类抗氧剂、金属钝化剂中的任一种或两种以上的混合物。
8.根据权利要求1所述的一种耐低温PC/PET复合材料及其制备方法，其特征在于：所述相容剂为丙烯酸酯-缩水甘油酯-乙烯类相容剂KT-22；增韧剂为甲基丙烯酸-丁二烯-苯乙烯类增韧剂罗门哈斯2678；低温改良剂为有机硅氧烷类低温改良剂道康宁MB50-007；抗氧剂为酚类抗氧化剂1010。
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CN102134369A (zh) * 2011-02-24 2011-07-27 金发科技股份有限公司 一种abs/pet/共聚酯三元合金及其制备方法
CN103113725A (zh) * 2013-03-22 2013-05-22 上海顶新箱包有限公司 Pet树脂组合物及其制备方法和应用
CN103333482A (zh) * 2013-07-19 2013-10-02 上海锦湖日丽塑料有限公司 一种高高温弯曲模量的pc/pet合金及其制备方法
CN103360741A (zh) * 2013-07-14 2013-10-23 上海秋橙新材料科技有限公司 抗老化pc-pet塑料合金
CN103540105A (zh) * 2012-07-10 2014-01-29 晋德塑料科技(东莞)有限公司 一种聚碳酸酯、聚对苯二甲酸乙二酯与丙烯腈-丁二烯-苯乙烯的组合物及其制备方法
CN106589785A (zh) * 2016-12-31 2017-04-26 滁州晨润工贸有限公司 适用于模内覆膜工艺的耐寒片材
CN111363338A (zh) * 2020-05-07 2020-07-03 吉林庭然景观材料科技有限公司 一种含pet、pc的合金型材及其制备方法

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CN100545211C (zh) * 2006-09-07 2009-09-30 浙江俊尔新材料有限公司 耐低温pc/pbt塑料合金
CN101220199B (zh) * 2007-12-28 2011-09-28 深圳市科聚新材料有限公司 一种环保阻燃玻纤增强聚酯合金材料及其制备方法

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CN102134369A (zh) * 2011-02-24 2011-07-27 金发科技股份有限公司 一种abs/pet/共聚酯三元合金及其制备方法
CN103540105A (zh) * 2012-07-10 2014-01-29 晋德塑料科技(东莞)有限公司 一种聚碳酸酯、聚对苯二甲酸乙二酯与丙烯腈-丁二烯-苯乙烯的组合物及其制备方法
CN103113725A (zh) * 2013-03-22 2013-05-22 上海顶新箱包有限公司 Pet树脂组合物及其制备方法和应用
CN103360741A (zh) * 2013-07-14 2013-10-23 上海秋橙新材料科技有限公司 抗老化pc-pet塑料合金
CN103360741B (zh) * 2013-07-14 2015-09-16 上海秋橙新材料科技有限公司 抗老化pc-pet塑料合金
CN103333482A (zh) * 2013-07-19 2013-10-02 上海锦湖日丽塑料有限公司 一种高高温弯曲模量的pc/pet合金及其制备方法
CN103333482B (zh) * 2013-07-19 2015-08-26 上海锦湖日丽塑料有限公司 一种高高温弯曲模量的pc/pet合金及其制备方法
CN106589785A (zh) * 2016-12-31 2017-04-26 滁州晨润工贸有限公司 适用于模内覆膜工艺的耐寒片材
CN111363338A (zh) * 2020-05-07 2020-07-03 吉林庭然景观材料科技有限公司 一种含pet、pc的合金型材及其制备方法

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