CN103937189B - 聚碳酸酯/聚对苯二甲酸乙二醇酯合金及其制备方法 - Google Patents
聚碳酸酯/聚对苯二甲酸乙二醇酯合金及其制备方法 Download PDFInfo
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Abstract
一种高分子材料技术领域的聚碳酸酯/聚对苯二甲酸乙二醇酯合金及其制备方法,其组分为:PC40‐90份,PET‐g‐EVA10‐60份,ACS‐g‐MAH5‐50份,抗氧剂0.05‐2份,热稳定剂0.05‐1份,润滑剂0.05‐1份,抗紫外剂0.05‐1份。本发明制备所得合金材料具有超高常温冲击和低温冲击韧性,由于合金含有乙烯~醋酸乙烯酯共聚物(EVA),不但起到增韧作用,还使得合金具有耐腐蚀和耐老化特性;同时由于合金含有丙烯腈‐氯化聚乙烯‐苯乙烯共聚物(ACS),使得合金材料具有阻燃和耐候特性。
Description
技术领域
本发明涉及的是一种高分子材料技术领域的方法,具体是一种耐冲击聚碳酸酯(PC)/聚对苯二甲酸乙二醇酯(PET)合金及其制备方法。
背景技术
聚碳酸酯是性能优异的工程塑料,具有良好的综合性能,机械强度高、耐冲击韧性好、尺寸稳定、耐热较好、电绝缘性好;聚对苯二甲酸乙二醇酯,具有优良的综合性能、耐油、耐溶剂、流动性好,易于加工。聚碳酸酯/聚对苯二甲酸乙二醇酯合金产品既保留聚碳酸酯树脂的韧性、耐热性、尺寸稳定性,又具有结晶材料聚对苯二甲酸乙二醇酯的耐溶剂和流动性,因此是制造汽车外装件的理想材料。
但应用于汽车如格栅、挡泥板和导流板等制件要求具有超高的冲击韧性,使制件在碰撞过程中消耗外来冲撞能量,减少碰撞破坏的产生,减少事故发生保证人身安全,而对于低温地区更注重要求低温环境下的冲击性能。同时对于用于汽车内外饰的聚碳酸酯/聚对苯二甲酸乙二醇酯合金,如格栅、导流板等制件长期暴露于大气环境中,需对材料提出更高的要求,主要体现在耐候性、耐老化性、耐腐蚀性。具有耐候、耐老化、高常温及高低温冲击的聚碳酸酯/聚对苯二甲酸乙二醇酯合应用于汽车内外饰件,使汽车产品应用地理范围更广,更易适应不同苛刻的环境条件。
经过对现有技术的检索发现,中国专利文献号CN1460116公开(公告)日2003.12.03,公开了一种再生用过的树脂并防止树脂质量劣化的方法,包括在用过的树脂中加入另一具有给定物理性能优于树脂的那些的树脂。但这些材料没有超高的常温及低温冲击韧性,没有较好的耐候特性,不足以在苛刻地理环境条件使用以扩大使用地理范围。
发明内容
本发明针对现有技术存在的上述不足,提出一种聚碳酸酯/聚对苯二甲酸乙二醇酯合金及其制备方法,制备所得合金材料具有超高常温冲击和低温冲击韧性,由于合金含有乙烯~醋酸乙烯酯共聚物(EVA),不但起到增韧作用,还使得合金具有耐腐蚀和耐老化特性;同时由于合金含有丙烯腈‐氯化聚乙烯‐苯乙烯共聚物(ACS),使得合金材料具有阻燃和耐候特性。
本发明是通过以下技术方案实现的:本发明通过分别将PET和EVA熔融共混、将丙烯腈‐氯化聚乙烯‐苯乙烯共聚物(ACS)和马来酸酐(MAH)熔融共混,各自反应挤出切粒得到PET‐g‐EVA接枝共聚物和ACS‐g‐MAH接枝共聚物,混合后与PC及助剂共混挤出得到聚碳酸酯/聚对苯二甲酸乙二醇酯合金。
所述的PET和EVA的重量比为(60~90):(40~10)。
所述的PET和EVA熔融共混中采用氧化二丁基锡(DBTO)作为催化剂,熔融共混后的挤出的温度为250~280℃,螺杆转速为200~300r/min;接枝率为10~15%。
所述的ACS和MAH的重量比为70:30。
所述的ACS和MAH熔融共混中采用过氧化二异丙苯(DCP)作为催化剂,熔融共混后的挤出温度为220~250℃,螺杆转速为150~250r/min;接枝率为5~15%。
所述的PC、PET‐g‐EVA接枝共聚物、ACS‐g‐MAH接枝共聚物和助剂的重量比为(50~70):(30~50):(1~40):0.55。
所述的丙烯腈‐氯化聚乙烯‐苯乙烯共聚物(ACS)为采用本体聚合法由丙烯腈(AN)、氯化聚乙烯(CPE)与苯乙烯(St)制备得到的三元共聚物,并且氯化聚乙烯橡胶重量比例为25‐35%,CPE中氯含量为40‐70%,CPE中氯含量优选45%。
所述的乙烯‐醋酸乙烯酯共聚物(EVA)中VA含量为20‐40%,优选25%。
所述的马来酸酐(MAH)为无色针状晶体,通过红外光谱表征,酸酐特征吸收峰在1778.68cm‐1处。
所述的抗氧剂为受阻酚类抗氧剂和亚磷酸酯类抗氧剂中的一种或几种组合,优选为抗氧剂1010或抗氧剂168,即四[甲基‐β‐(3,5‐二叔丁基‐4‐羟基苯基)丙酸酯]季戊四醇或三[2,4‐二叔丁基苯基]亚磷酸酯。
所述的润滑剂为脂肪酸酯类或氧化聚乙烯蜡一种或几种,优选使用季戊四醇硬脂酸酯(PETS)。
所述的抗紫外剂为苯并三唑类、三嗪类、二苯甲酮类、受阻胺类的一种或几种光吸收剂,优选苯并三唑类光吸收剂。
所述的热稳定剂为有机锡类热稳定剂、金属皂类热稳定剂一种或几种,优选马来酸锡盐有机锡热稳定剂。
本发明涉及上述方法制备得到的聚碳酸酯/聚对苯二甲酸乙二醇酯合金,其悬臂梁缺口冲击强度在23℃环境下大于960J/m,在‐30℃环境下大于700J/m,经60℃、80RH%恒温恒湿20天老化后在23℃环境下大于945J/m。
所述的聚碳酸酯/聚对苯二甲酸乙二醇酯合金的阻燃性达到V‐2级以上。
本发明涉及上述聚碳酸酯/聚对苯二甲酸乙二醇酯合金的应用,将其用于制备汽车格栅、导流板、挡泥板等汽车内外饰件,同时可用于其它户外运动体育器材制品。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1
本实施例包括以下步骤:
1)以下实施例使用的聚碳酸酯为GE公司的双酚A型聚碳酸酯PC lexan141R,分子量为25000‐28000g/mol。聚对苯二甲酸乙二醇酯使用华源雷迪斯的PET8828AA,特性黏度为0.8dl/g。抗氧剂使用四[β‐(3,5‐二特丁基‐4‐羟基苯基)丙酸]季戊四醇酯,商品名为Irganox1010,瑞士汽巴精化公司生产,及三(2,4‐二叔丁基酚)亚磷酸酯,商品名为Irganox168,瑞士汽巴精化公司生产。本发明使用德国Berstorff公司生产的ZE‐25双螺杆挤出机。
本实施例包括以下步骤:
1)接枝PET‐g‐EVA的制备:
首先将80份PET、20份EVA、2份有机锡催化剂(DBTO)、0.1份受阻酚类抗氧剂、0.05份亚磷酸酯类抗氧剂用高速混合机均匀混合5分钟后加入到双螺杆挤出机中进行熔融共混,一区温度为200℃,二区温度为210℃,三区温度为220℃,四区温度为230℃,五区温度为240℃,六区温度为250℃,七区温度为260℃,八区温度为270℃,九区温度为265℃,螺杆转速为250转/分钟,停留时间为1‐3分钟。经挤出后冷却、干燥、切粒,得到PET‐g‐EVA共聚物;
2)接枝ACS‐g‐MAH的制备:
将70份ACS、30份MAH、0.05‐2.0份过氧化二异丙苯(DCP)和0.3‐1.0份硬脂酸用高速混合机均匀混合5分钟后加入到双螺杆挤出机中进行熔融共混,一区温度为180℃,二区温度为190℃,三区温度为200℃,四区温度为210℃,五区温度为220℃,六区温度为230℃,七区温度为240℃,八区温度为250℃,九区温度为245℃,螺杆转速为200转/分钟,停留时间为1‐3分钟,经冷却、干燥、切粒,得到马来酸酐接枝ACS共聚物。
3)聚碳酸酯/聚对苯二甲酸乙二醇酯合金的制备
将PC、PET‐g‐EVA、ACS‐g‐MAH、受阻酚类抗氧剂、亚磷酸酯类抗氧剂、热稳定剂、润滑剂和抗紫外剂按照实施例的重量配比用高速混合机均匀混合10分钟后加入到双螺杆挤出机中进行熔融共混,一区温度为200℃,二区温度为220℃,三区温度为230℃,四区温度为240℃,五区温度为250℃,六区温度为260℃,七区温度为270℃,八区温度为280℃,九区温度为275℃,螺杆转速为250‐350转/分钟,停留时间为2分钟。经挤出后冷却、干燥、切粒,得到PC/PET合金。
缺口冲击强度按ASTM D256进行测试,试样尺寸为64mm*12.7mm*3.2mm,缺口深度为2.2mm,测试设备为英国Ray‐Ran公司的冲击试验机。
阻燃等级测试按UL‐94,测试设备为美国ATLAS HVUL‐2垂直燃烧仪。
各重量百分比和测试物性结果如下表:
表1
实施例中,添加自制聚对苯二甲酸乙二醇酯‐g‐EVA之后,使聚碳酸酯/聚对苯二甲酸乙二醇酯合金材料冲击韧性增加,具有超高常温冲击韧性及超高低温冲击韧性,并随添加含量的增加而增加;
实施例中,添加自制聚对苯二甲酸乙二醇酯‐g‐EVA和自制ACS‐g‐MAH之后,使聚碳酸酯/聚对苯二甲酸乙二醇酯合金材料具有耐候性、耐老化特性,60℃~80%湿度恒温恒湿20天之后的冲击韧性未出现下降趋势;
实施例中,添加ACS‐g‐MAH之后,使聚碳酸酯/聚对苯二甲酸乙二醇酯合金材料阻燃性增加,甚至达到V‐1级。
Claims (6)
1.一种聚碳酸酯/聚对苯二甲酸乙二醇酯合金的制备方法,其特征在于,通过分别将PET和EVA熔融共混、将丙烯腈-氯化聚乙烯-苯乙烯共聚物和马来酸酐熔融共混,各自反应挤出切粒得到PET-g-EVA接枝共聚物和ACS-g-MAH接枝共聚物,混合后与PC及助剂共混挤出得到聚碳酸酯/聚对苯二甲酸乙二醇酯合金;
所述的PET和EVA的重量比为(60~90):(40~10);
所述的PET和EVA熔融共混中采用氧化二丁基锡作为催化剂,熔融共混后的挤出的温度为250~280℃,螺杆转速为200~300r/min;接枝率为10~15%;
所述的ACS和MAH的重量比为70:30;
所述的ACS和MAH熔融共混中采用过氧化二异丙苯(DCP)作为催化剂,熔融共混后的挤出温度为220~250℃,螺杆转速为150~250r/min;接枝率为5~15%。
2.根据权利要求1所述的方法,其特征是,所述的PC、PET-g-EVA接枝共聚物、ACS-g-MAH接枝共聚物和助剂的重量比为(50~70):(30~50):(1~40):0.55。
3.根据权利要求1所述的方法,其特征是,所述的乙烯-醋酸乙烯酯共聚物中VA含量为20-40%;所述的丙烯腈-氯化聚乙烯-苯乙烯共聚物为采用本体聚合法由丙烯腈、氯化聚乙烯与苯乙烯制备得到的三元共聚物,并且氯化聚乙烯橡胶重量比例为25-35%,CPE中氯含量为40-70%。
4.一种根据权利要求1或3所述方法制备得到的聚碳酸酯/聚对苯二甲酸乙二醇酯合金,其特征在于,其组分为:PC 40-90份、 PET-g-EVA 10-60份、ACS-g-MAH 5-50份、抗氧剂 0.05-2份、热稳定剂 0.05-1份、润滑剂 0.05-1份、抗紫外剂 0.05-1份;该材料的悬臂梁缺口冲击强度在23℃环境下大于960 J/m,在-30℃环境下大于700 J/m,经60℃、80RH%恒温恒湿20天老化后在23℃环境下大于945 J/m。
5.根据权利要求4所述的聚碳酸酯/聚对苯二甲酸乙二醇酯合金,其特征是,其组分为:PC 50-70份、PET-g-EVA 30-50份、ACS-g-MAH 10-40份、抗氧剂 0.15份、热稳定剂 0.1份、润滑剂 0.1份、抗紫外剂 0.2份。
6.一种根据上述任一权利要求中所述的聚碳酸酯/聚对苯二甲酸乙二醇酯合金的应用,其特征在于,将其用于制备汽车内外饰件或户外运动体育器材制品。
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