CN103709740A - 高白度无卤阻燃导热绝缘pa6基复合材料及制备方法 - Google Patents
高白度无卤阻燃导热绝缘pa6基复合材料及制备方法 Download PDFInfo
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Abstract
本发明公开了高白度无卤阻燃导热绝缘PA6基复合材料及制备方法。按质量百分比计,其原料配方由如下组分组成:30%~40%聚酰胺6、40%~55%导热填料、5%~10%钛白粉、7%~10%二乙基次膦酸铝、0.4%~1.0%偶联剂、0.4%~1.0%流动改性剂和0.2%~0.5%抗氧剂;导热填料由具有层状结构填料和颗粒状填料组成,层状结构填料为氮化硼,长宽比为10:1~15:1;颗粒状填料粒径范围为10μm~40μm;本发明的PA6基复合材料1.6mm样条垂直燃烧均通过UL94V-0等级,法向热导率在1.1W/m.K以上,具有白度高、阻燃性能好、热导率高、绝缘、加工流动性好等特点。
Description
技术领域
本发明涉及PA6基复合材料,具体涉及一种高白度无卤阻燃导热绝缘PA6基复合材料及其制备方法;属于高分子材料改性技术领域。
发明背景
工程塑料聚酰胺6(PA6)具有质轻、强度高、绝缘且容易成型的优点,越来越多地替代金属或者陶瓷制备电子电气组件和外壳。由于大多数电子电气组件在运行时产生热量,需要所用材料有一定的导热性,另外,电子电气产品对材料的电绝缘性和阻燃性能要求较高,但没有改性的PA6热导率低,阻燃等级低,不能满足使用需要。通过在PA6基体中添加绝缘导热填料和无卤阻燃剂后导热性能可大幅增加,同时具有较高的阻燃等级和绝缘性能。不过,由于导热填料和无卤阻燃剂的填充往往又引起PA6加工性能变差,降解黄变现象严重,使PA6基复合材料白度低于80%,而产品白度高,可以给人视觉上的舒适感,有更强的生命力。白度是按GB2913-82测试标准,根据CIE色空间的Lab原理的色差仪测定的L、a、b三个值,按Stensby白度公式W=(L-3b+3a)%计算得到,一般白度值在80%以上可以称为高白度,因此高白度、无卤阻燃、导热、绝缘的聚酰胺6基复合材料制备意义重大。
发明专利CN1926192A采用次膦酸铝作为阻燃剂填充改性聚酰胺,制备了阻燃聚酰胺复合材料,在次膦酸铝为14wt%的添加量下,复合材料通过3.2mmV-0阻燃级别,而1.6mm阻燃级别为V-2。发明专利CN101157798A公开了一种高白度超分散尼龙6/纳米蒙脱土复合材料的高效连续聚合方法,该专利通过在原位聚合反应中在管式聚合反应器中添加离子分散过的蒙脱土制得不发黄、气体阻隔性好的尼龙6/纳米蒙脱土复合材料,但是上述的两种复合材料并无导热性能。
发明专利ZL200910193532.0公开了一种无机导热填料填充改性导热绝缘聚苯硫醚与聚酰胺共混合金,该专利也采用氮化物作导热填料,如果采用氮化硼,由于其为层状结构,在填充改性聚合物合金过程中,各向异性现象严重,复合材料面内热导率较高,法向热导率则较低,而聚合物基导热复合材料所制造得到的电子电气组件和外壳,其散热作用主要依赖空气对流,热量从组件高温面传递到与空气接触的低温面主要依靠复合材料法向方向的热导率,且氮化硼价格昂贵,超过一定用量后,体系流动性差,导致加工困难;发明专利CN103087389A公开了一种高导热高韧性复合材料及其制备方法,该专利采用石墨与颗粒状填料混合填充聚对苯二甲酸乙二酯制备热导率最高为1.6W/m.K的复合材料。石墨便宜,来源广泛,但是石墨颜色为黑色,少量添加即无法获得白色外观产品,且石墨导电,其改性的导热复合材料电绝缘性差,再者以上两种复合材料并不阻燃。
目前已有专利文献公开了提高PA6工程塑料阻燃性、白度或导热性的方法,但是并没有涉及到具有高白度且综合导热、绝缘和阻燃性能的PA6基复合材料,本领域迫切需要开发一种高白度无卤阻燃导热绝缘PA6基复合材料。
发明内容
本发明针对现有高分子改性领域缺乏具有良好外观且综合导热、绝缘和阻燃性能的复合材料,提供一种高白度无卤阻燃导热绝缘PA6基复合材料。
本发明以层状结构填料与颗粒状填料按照一定比例复合填充改性PA6,所得复合材料中颗粒状填料分布在层状结构填料间,这样在面内、法向均有较高的热导率,且流动加工性得到改善,同时材料成本较低;另外,以二乙基次膦酸铝为阻燃剂,其受热时分解释放出的二乙基次膦酸不仅在气相中发挥自由基捕捉作用,同时在凝聚相促进PA6基体成炭,并与层状结构填料共同构成致密的玻璃状保护炭层,隔热隔氧作用明显增加,二乙基次膦酸铝与层状结构填料的协效阻燃作用使复合材料1.6mm样条垂直燃烧通过UL94V-0等级;采用颜色遮盖力比蒙脱土更强的钛白粉,提高材料对蓝色光的反射作用,提高白度至83%以上;所用各类填料绝缘性均好,复合材料表面电阻率达1×1014Ω·cm。
为了实现本发明目的,本发明采用如下技术方案:
高白度无卤阻燃导热绝缘PA6基复合材料,其特征在于,按质量百分比计,其原料配方由如下组分组成:30%~40%聚酰胺6、40%~55%导热填料、5%~10%钛白粉、7%~10%二乙基次膦酸铝、0.4%~1.0%偶联剂、0.4%~1.0%流动改性剂和0.2%~0.5%抗氧剂;
所述导热填料由具有层状结构填料和颗粒状填料组成,其中层状结构填料所占导热填料的质量百分数为50%~80%;所述层状结构填料为白度90%以上的氮化硼,长宽比为10:1~15:1,长度为35μm~75μm;所述颗粒状填料为白度95%以上的氧化镁、氧化铝和氧化锌中的一种或多种,颗粒粒径范围为10μm~40μm;
所述偶联剂为γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷和γ-巯丙基三甲氧基硅烷中的一种或者多种;
所述抗氧剂为四[甲基-β-(3,5-二叔丁基-4-羟基苯基)丙酸酯]季戊四醇酯、β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯、N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺和三[2.4-二叔丁基苯基]亚磷酸酯中的一种或者多种;
所述流动改性剂为硬脂酸钙与硬脂酸锌按1:2~2:1质量比混合的组合物。
本发明与现有技术相比,具有以下效果:
1.本发明高白度无卤阻燃导热绝缘PA6基复合材料白度在83%以上,1.6mm样条垂直燃烧均通过UL94V-0等级,法向热导率在1.1W/m.K以上,面内热导率在3.5W/m.K以上,表面电阻率达1×1014Ω·cm,同时具有白度高、阻燃性能好、热导率高、绝缘、加工流动性好等特点。
2.本发明高白度无卤阻燃导热绝缘PA6基复合材料法向和面内热导率均较高,在导热填料填充量都为55wt%的条件下,本发明所得复合材料跟单一层状结构填料填充所得复合材料相比,法向热导率提高了54.5%,熔体流动速率提高了314.3%,材料导热性和加工流动性大幅度提高。
具体实施方式
以下结合具体实施例来对本发明作进一步说明,但本发明所要求保护的范围并不局限于实施例所表述的范围。
本发明所用PA6为广东新会美达锦纶股份有限公司产品,牌号M22403;二乙基次膦酸铝为天津市振兴化工有限责任公司产品,牌号ZX-ADP900;钛白粉为杜邦中国集团有限公司产品,牌号Ti-Pure R-104,白度为98%,中位径0.2μm。氮化硼B1长宽比为10:1,长度为35μm,白度为92%;氮化硼B2长宽比为10:1,长度为50μm,白度为92%;氮化硼B3长宽比为15:1,长度为75μm,白度为90%。氧化镁(MgO),中位径10μm,白度95%;氧化铝(Al2O3)中位径为40μm,白度为96%;氧化锌(ZnO),中位径15μm,白度98%。
偶联剂均用国产牌号表示:KH560为γ-缩水甘油醚氧丙基三甲氧基硅烷;KH550为γ-氨丙基三乙氧基硅烷;KH590为γ-巯丙基三甲氧基硅烷。
抗氧剂均用牌号表示:抗氧剂1010为四(β-(3,5-二叔丁基-4-羟基苯基)丙酸)季戊四醇酯、抗氧剂1076为β-(4-羟基苯基-3,5-二叔丁基)丙酸正十八碳醇酯;抗氧剂1098为N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺;抗氧剂168为亚磷酸酯类抗氧剂有亚磷酸三(2,4-二叔丁基苯基)酯;抗氧剂B215为抗氧剂1010与抗氧剂168以1:2的质量比复合配制、抗氧剂B225这抗氧剂1010与抗氧剂168以1:1的质量比复合配制。
流动改性剂为硬脂酸钙、硬脂酸锌混合的组合物。流动改性剂S1为硬脂酸钙与硬脂酸锌以1:2质量比混合配制、S2为硬脂酸钙与硬脂酸锌以1:1质量比混合配制、S3为硬脂酸钙与硬脂酸锌以2:1的质量比混合配制。
实施例1:
控制总量为3Kg,将30wt%PA6、27.5wt%BN、27.5wt%MgO、6wt%钛白粉、7wt%二乙基次膦酸铝、0.4wt%抗氧剂168、0.6wt%偶联剂KH550,1wt%流动改性剂S1加入到高速搅拌机中,常温搅拌混合均匀后,所得预混料通过双螺杆挤出机在220℃~240℃温度下熔融、混炼、挤出、冷却、切粒和干燥,得到高白度无卤阻燃导热绝缘PA6基复合材料。改变各原料的配比,按照实施例1的方法制备本发明的其他7个实施例以及2个对比例。
将制备好的复合材料在110℃烘烤3小时后,注塑成Φ80×1mm、Φ12.7×1.0mm圆片用于测试电阻率和热导率,注塑成100.0×50.0×2.5mm方片和125.0×13.0×1.6mm样条用于测试Lab值和阻燃性能。
根据ASTM E1461标准测量材料热导率,根据GB/T1410标准测量材料电阻率,根据UL94标准测量材料阻燃级别,根据GB3682-2000标准测量材料熔体流动速率,根据GB/T1040-2006标准测量材料拉伸强度,根据GB/T1843-1996标准测量材料冲击强度,根据GB/T9341-2000标准测量材料弯曲强度;白度(W)以GB2913-82测试标准,根据CIE色空间的Lab原理的色差仪测定L、a、b三个值,按W=(L-3b+3a)%计算得到,所得结果列于表1、表2中。
表1:实施例1-2和对比例1-2的原料配方和复合材料性能
表2:实施例3-8的原料配方和复合材料性能
从以上两表可知,本发明PA6基复合材料白度在83%以上,1.6mm样条垂直燃烧均通过UL94V-0等级,法向热导率在1.1W/m.K以上,面内热导率在3.5W/m.K以上,表面电阻率达1×1014Ω·cm,同时具有白度高、阻燃性能好、热导率高、绝缘、加工流动性好等特点,可以很好地满足电子电气散热组件制造需要。另外,本发明PA6基复合材料法向和面内热导率均较高,在导热填料填充量都为55wt%条件下,层状结构填料氮化硼与颗粒状填料复合填充所得复合材料(实施例2),跟单一层状结构填料填充所得复合材料(对比例1)相比,法向热导率提高了54.5%,复合材料熔体流动速率提高了314.3%,复合材料导热性和加工流动性大幅度提高。
Claims (5)
1.高白度无卤阻燃导热绝缘PA6基复合材料,其特征在于,按质量百分比计,其原料配方由如下组分组成:30%~40%聚酰胺6、40%~55%导热填料、5%~10%钛白粉、7%~10%二乙基次膦酸铝、0.4%~1.0%偶联剂、0.4%~1.0%流动改性剂和0.2%~0.5%抗氧剂;
所述导热填料由具有层状结构填料和颗粒状填料组成,其中层状结构填料所占导热填料的质量百分数为50%~80%;所述层状结构填料为白度90%以上的氮化硼,长宽比为10:1~15:1,长度为35μm~75μm;所述颗粒状填料为白度95%以上的氧化镁、氧化铝和氧化锌中的一种或多种,颗粒粒径范围为10μm~40μm;
所述偶联剂为γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷和γ-巯丙基三甲氧基硅烷中的一种或者多种;
所述抗氧剂为四[甲基-β-(3,5-二叔丁基-4-羟基苯基)丙酸酯]季戊四醇酯、β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯、N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺和三[2.4-二叔丁基苯基]亚磷酸酯中的一种或者多种;
所述流动改性剂为硬脂酸钙与硬脂酸锌按1:2~2:1质量比混合的组合物。
2.根据权利要求1所述的高白度无卤阻燃导热绝缘PA6基复合材料,其特征在于:所述钛白粉具有95%以上的白度,颗粒粒径范围为0.2μm~0.5μm。
3.根据权利要求1所述的高白度无卤阻燃导热绝缘PA6基复合材料,其特征在于:所述层状结构填料所占导热填料的质量百分数为60%~70%。
4.根据权利要求1所述的高白度无卤阻燃导热绝缘PA6基复合材料,其特征在于:按质量百分比计,所述导热填料的用量为45%~50%.
5.根据权利要求1-4任一项所述的高白度无卤阻燃导热绝缘PA6基复合材料的制备方法,其特征在于:按原料配方质量百分比,将聚酰胺6、导热填料、二乙基次膦酸铝、偶联剂、流动改性剂和抗氧剂分散混合,通过双螺杆挤出机在220℃~240℃下熔融、混炼、挤出、冷却、切粒和干燥,得高白度无卤阻燃导热绝缘PA6基复合材料。
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