CN110591321A - 一种玻纤增强聚碳酸酯复合材料及其制备方法与应用 - Google Patents

一种玻纤增强聚碳酸酯复合材料及其制备方法与应用 Download PDF

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CN110591321A
CN110591321A CN201910815623.7A CN201910815623A CN110591321A CN 110591321 A CN110591321 A CN 110591321A CN 201910815623 A CN201910815623 A CN 201910815623A CN 110591321 A CN110591321 A CN 110591321A
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岑茵
李明昆
艾军伟
陈勇文
刘贤文
吴俊�
丁超
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Kingfa Science and Technology Co Ltd
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Abstract

本发明公开了一种玻纤增强聚碳酸酯复合材料及其制备方法与应用,包括以下组成:组分A:聚碳酸酯40份‑90份;组分B:聚硅氧烷嵌段共聚物1.5份‑50份;组分C:玻纤5份‑60份;组分D:含磷化合物0.1份‑30份;组分E:聚烯烃化合物0.01份‑30份。本发明选用在玻纤增强聚碳酸酯复合材料配方中添加特定含量的聚硅氧烷嵌段共聚物、含磷化合物和聚烯烃化合物,从而能够保证最终制备得到的复合材料中具有特定的硅氧烷含量和特定的磷元素和硅元素的重量比,使得制备得到的复合材料既具有优异的高模量高韧性特性,又具有优异的加工性能,与常规增强改性手段相比,该复合材料兼具刚性和韧性,特别适用于汽车、电子电气、通讯行业、建筑行业等领域。

Description

一种玻纤增强聚碳酸酯复合材料及其制备方法与应用
技术领域
本发明涉及工程塑料技术领域,特别涉及一种玻纤增强聚碳酸酯复合材料及其制备方法与应用。
背景技术
聚碳酸酯树脂PC是一种综合性能优良的热塑性工程塑料。近年来,其较高的透明度,良好的阻燃性、耐热性、电绝缘性和尺寸稳定性,较低的吸水率等特点而被广泛应用于汽车、电子电气、通讯行业、建筑行业等领域。随着其应用领域的扩展,聚碳酸酯的冲击强度、弯曲模量、拉伸强度、流动性、介电损耗等性能都有了较高的要求,单纯的聚碳酸酯或普通的聚碳酸酯材料仍无法满足要求,因此,需要对聚碳酸酯材料进行改性处理。为了提升材料性能和档次,满足最终部件和客户的需求,一般通过玻璃纤维增强来改进其加工性和改性。
但是,现有玻纤增强聚碳酸酯复合材料存在高刚性但是低韧性的矛盾,而常规的增韧方法是直接添加增韧剂,这同样会大幅度降低复合材料的流动性,且复合材料的刚性和韧性的提高也非常有限,从而严重限制了其在汽车、电子电气、通讯行业、建筑行业等领域中的应用。
发明内容
为了克服现有技术的缺点与不足,本发明的目的在于提供一种兼具刚性和韧性,且具有高流动性的玻纤增强聚碳酸酯复合材料。
本发明的另一目的是提供上述玻纤增强聚碳酸酯复合材料的制备方法。
本发明的再一目的是提供上述玻纤增强聚碳酸酯复合材料的用途。
本发明是通过以下技术方案实现的:
一种玻纤增强聚碳酸酯复合材料,按重量份计,包括以下组成:
组分A:聚碳酸酯 40份- 90份;
组分B:聚硅氧烷嵌段共聚物 1.5份-50份;
组分C:玻纤 5份-60份;
组分D:含磷化合物 0.1份-30份;
组分E:聚烯烃化合物 0.01份-30份。
优选地,玻纤增强聚碳酸酯复合材料,按重量份计,包括以下组成:
组分A:聚碳酸酯 40份- 90份;
组分B:聚硅氧烷嵌段共聚物 3.5份-45份;
组分C:玻纤 5份-60份;
组分D:含磷化合物 8份-12份;
组分E:聚烯烃化合物 6份-10份。
其中,所述玻纤增强聚碳酸酯复合材料中硅氧烷含量占组合物总重量的百分比为0.6wt%-17wt%,优选为2.8wt%-12wt%。
其中,所述玻纤增强聚碳酸酯复合材料中磷元素和硅元素的重量比为1:(0.1-3.2),优选为1:(0.6-2.5)。
其中,所述聚碳酸酯选自芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯中的一种或几种;优选为芳香族聚碳酸酯;
优选地,所述芳香族聚碳酸酯为粘均分子量13000-40000的芳香族聚碳酸酯,优选为粘均分子量18000-28000的芳香族聚碳酸酯。当粘均分子量在上述范围内,机械强度良好并且能保持优异的成型性。其中,粘均分子量是通过使用二氯甲烷作为溶剂在测试温度为25℃的溶液粘度计算出来的。
上述聚碳酸酯的制备方法可以通过界面聚合法和酯交换法制得,并且可以在过程中控制端羟基的含量。
其中,所述聚硅氧烷嵌段共聚物包括聚二甲基硅氧烷嵌段和双酚A的聚碳酸酯嵌段,具有基于组分B重量0.6wt%-36wt%的硅氧烷含量。加入硅氧烷嵌段共聚物后,可以通过近红外分析法对玻纤增强聚碳酸酯复合材料的硅氧烷含量进行测试,测试方法是称量固定重量的玻纤增强聚碳酸酯复合材料粒料用甲烷均匀溶解成片状后进行检测。
其中,所述含磷化合物选自含氧磷酸、磷酸盐类及其衍生物;所述含氧磷酸选自磷酸和/或次磷酸;所述磷酸盐类及其衍生物选自磷酸钠和/或次磷酸锌。
其中,所述聚烯烃化合物选自饱和性直链型的聚烯烃、含有不饱和键的聚烯烃、含有部分支链的聚烯烃、改性聚烯烃中的一种或几种;所述饱和性直链型的聚烯烃选自聚乙烯、聚丙烯、聚丁烯中的一种或几种;所述含有不饱和键的聚烯烃选自聚丁二烯及其衍生物;所述含有部分支链的聚烯烃选自聚X-烯烃;所述改性聚烯烃选自环氧改性聚烯烃、马来酸苷改性聚烯烃中的一种或几种。
本发明所述的玻纤增强聚碳酸酯复合材料,基于玻纤增强聚碳酸酯复合材料重量,还可以包括组分F:其它助剂0-10份;所述其它助剂选自稳定剂、阻燃剂、抗滴落剂、润滑剂、脱模剂、增塑剂、填料、抗静电剂、抗菌剂、着色剂中的一种或几种。
合适的稳定剂,可以包括有机亚磷酸酯,如亚磷酸三苯酯,亚磷酸三-(2,6-二甲基苯基)酯,亚磷酸三-壬基苯基酯,二甲基苯膦酸酯,磷酸三甲酯等,有机亚磷酸酯,烷基化的一元酚或者多元酚,多元酚和二烯的烷基化反应产物,对甲酚或者二环戊二烯的丁基化反应产物,烷基化的氢醌类,羟基化的硫代二苯基醚类,亚烷基-双酚,苄基化合物,多元醇酯类,苯并三唑类,二苯甲酮类的一种或者多种组合。
合适的阻燃剂,可以包括基于磷酸酯的阻燃剂或者磺酸盐阻燃剂。较好的磷酸酯阻燃剂包括双酚A二磷酸四苯酯,磷酸三苯酯、磷酸三甲苯酯、磷酸甲苯基二苯酯、双酚A二磷酸四甲苯酯、间苯二酚四(2,6-二甲基苯酯)和四甲苄基哌啶酰胺;也可以阻燃剂选择磺酸盐,如Rimar盐全氟丁基磺酸钾、KSS二苯砜磺酸钾、苯磺酸钠等均为合适。
上述玻纤增强聚碳酸酯复合材料的制备方法,包括如下步骤:
1)按照配比称取聚碳酸酯、聚硅氧烷嵌段共聚物、含磷化合物、聚烯烃化合物、其它助剂在高混机中搅拌共混1-3min,得到预混料;
2)将得到的预混料置于双螺杆挤出机的主喂料口中,在侧喂料口加入玻纤进行熔融挤出,造粒干燥,即得。
其中,所述双螺杆挤出机长径比为46:1-50:1;所述双螺杆挤出机的温度从喂料段到机头依次为:一区温度120℃-160℃,二区温度200℃-230℃,三区温度200℃-230℃,四区温度200℃-220℃,五区温度200℃-220℃,六区温度200℃-220℃,七区温度200℃-220℃,八区温度200℃-220℃,九区温度200℃-220℃,十区温度200℃-220℃,十一区温度200℃-220℃,机头温度220℃-240℃,主机转速350转/分钟-500转/分钟。
上述制备方法得到的玻纤增强聚碳酸酯复合材料在汽车、电子电气、通讯行业、建筑行业中的应用。
本发明与现有技术相比,具有如下有益效果:
本发明选用在玻纤增强聚碳酸酯复合材料配方中添加特定含量的聚硅氧烷嵌段共聚物、含磷化合物和聚烯烃化合物,从而能够保证制备得到的复合材料中具有特定含量的硅氧烷含量和特定的磷元素和硅元素的重量比,制备得到的复合材料既具有优异的高模量高韧性特性,又具有优异的流动性和加工性能,与常规增强改性手段相比,该复合材料兼具刚性和韧性,适用于汽车、电子电气、通讯行业、建筑行业等领域。
具体实施方式
下面通过具体实施方式来进一步说明本发明,以下实施例为本发明较佳的实施方式,但本发明的实施方式并不受下述实施例的限制。
各性能的测试标准或方法:
Izod无缺口冲击强度的测试方式:根据ASTM D256-2010标准;
拉伸强度的测试方式:根据ASTM D638-2014标准,拉伸速度为10mm/min;
弯曲模量的测试方式根据ASTM D790-2010标准,弯曲速度为2mm/min;
流动性的测试方式:根据ASTM D1238-2013标准,熔融温度为300℃。
本发明中使用的聚碳酸酯:
组分A-1:粘均分子量为18000的芳香族聚碳酸酯,日本出光;
组分A-2:粘均分子量为27000的芳香族聚碳酸酯,日本出光;
本发明中使用的聚硅氧烷嵌段共聚物:
组分B-1:硅氧烷含量为8wt%的聚硅氧烷嵌段共聚物,日本出光;
组分B-2:硅氧烷含量为34wt%的聚硅氧烷嵌段共聚物,日本出光;
本发明中使用的玻纤:
组分C-1:日本东洋纺;
本发明中使用的含磷化合物:
组分D-1:次磷酸,阿拉丁;
组分D-2:磷酸钠,博德化工;
本发明中使用的聚烯烃化合物:
组分E-1:聚乙烯,厂家为中石化;
组分E-2:聚X-烯烃,厂家为创新化工;
本发明中使用的其它助剂:
组分F-1:稳定剂:2112,艾迪科;
组分F-2:润滑剂:PETS,龙沙。
实施例1-8及对比例1-6:玻纤增强聚碳酸酯复合材料的制备
按照配比称取聚碳酸酯、聚硅氧烷嵌段共聚物、含磷化合物、聚烯烃化合物、其它助剂在高混机中搅拌共混1-3min,得到预混料;将得到的预混料置于双螺杆挤出机的主喂料口中,在侧喂料口加入玻纤进行熔融挤出,造粒干燥,即得玻纤增强聚碳酸酯复合材料。对上述玻纤增强聚碳酸酯复合材料的Izod缺口冲击强度、Izod无缺口冲击强度、拉伸强度、弯曲模量、流动性进行测试,测试得到的数据如表1所示。
表1 实施例1-8及对比例1-6的具体配比(重量份)及其测试性能结果
续表1

Claims (12)

1.一种玻纤增强聚碳酸酯复合材料,按重量份计,包括以下组成:
组分A:聚碳酸酯 40份- 90份;
组分B:聚硅氧烷嵌段共聚物 1.5份-50份;
组分C:玻纤 5份-60份;
组分D:含磷化合物 0.1份-30份;
组分E:聚烯烃化合物 0.01份-30份。
2.根据权利要求1所述的玻纤增强聚碳酸酯复合材料,按重量份计,包括以下组成:
组分A:聚碳酸酯 40份- 90份;
组分B:聚硅氧烷嵌段共聚物 3.5份-45份;
组分C:玻纤 5份-60份;
组分D:含磷化合物 8份-12份;
组分E:聚烯烃化合物 6份-10份。
3.根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料,其特征在于,所述玻纤增强聚碳酸酯复合材料中硅氧烷含量占组合物总重量的百分比为0.6wt%-17wt%,优选为2.8wt%-12wt%。
4.根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料,其特征在于,所述玻纤增强聚碳酸酯复合材料中磷元素和硅元素的重量比为1:(0.1-3.2),优选为1:(0.6-2.5)。
5.根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料,其特征在于,所述聚碳酸酯选自芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯中的一种或几种;优选为芳香族聚碳酸酯;所述芳香族聚碳酸酯为粘均分子量13000-40000的芳香族聚碳酸酯,优选为粘均分子量18000-28000的芳香族聚碳酸酯。
6.根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料,其特征在于,所述聚硅氧烷嵌段共聚物包括聚二甲基硅氧烷嵌段和双酚A的聚碳酸酯嵌段,具有基于组分B重量0.6wt%-36wt%的硅氧烷含量。
7.根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料,其特征在于,所述含磷化合物选自含氧磷酸、磷酸盐类及其衍生物;所述含氧磷酸选自磷酸和/或次磷酸;所述磷酸盐类及其衍生物选自磷酸钠和/或次磷酸锌。
8.根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料,其特征在于,所述聚烯烃化合物选自饱和性直链型的聚烯烃、含有不饱和键的聚烯烃、含有部分支链的聚烯烃、改性聚烯烃中的一种或几种;所述饱和性直链型的聚烯烃选自聚乙烯、聚丙烯、聚丁烯中的一种或几种;所述含有不饱和键的聚烯烃选自聚丁二烯及其衍生物;所述含有部分支链的聚烯烃选自聚X-烯烃;所述改性聚烯烃选自环氧改性聚烯烃、马来酸苷改性聚烯烃中的一种或几种。
9.根据权利要求1或2所述的玻纤增强聚碳酸酯复合材料,其特征在于,基于玻纤增强聚碳酸酯复合材料重量,还包括组分F:其它助剂0-10份;所述其它助剂选自稳定剂、阻燃剂、抗滴落剂、润滑剂、脱模剂、增塑剂、填料、抗静电剂、抗菌剂、着色剂中的一种或几种。
10.一种如权利要求1-9任一项所述的玻纤增强聚碳酸酯复合材料的制备方法,其特征在于,包括如下步骤:
1)按照配比称取聚碳酸酯、聚硅氧烷嵌段共聚物、含磷化合物、聚烯烃化合物、其它助剂在高混机中搅拌共混1-3min,得到预混料;
2)将得到的预混料置于双螺杆挤出机的主喂料口中,在侧喂料口加入玻纤进行熔融挤出,造粒干燥,即得。
11.根据权利要求10所述的玻纤增强聚碳酸酯复合材料的制备方法,其特征在于,所述双螺杆挤出机长径比为46:1-50:1;所述双螺杆挤出机的温度从喂料段到机头依次为:一区温度120℃-160℃,二区温度200℃-230℃,三区温度200℃-230℃,四区温度200℃-220℃,五区温度200℃-220℃,六区温度200℃-220℃,七区温度200℃-220℃,八区温度200℃-220℃,九区温度200℃-220℃,十区温度200℃-220℃,十一区温度200℃-220℃,机头温度220℃-240℃,主机转速350转/分钟-500转/分钟。
12.如权利要求10所述的制备方法得到的玻纤增强聚碳酸酯复合材料在汽车、电子电气、通讯行业、建筑行业中的应用。
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