CN107418201B - 一种高效无卤阻燃增强尼龙复合材料及其制备方法 - Google Patents
一种高效无卤阻燃增强尼龙复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种高效无卤阻燃增强尼龙复合材料,按重量分数包括以下组份:尼龙树脂41.1‑71.1%;阻燃剂二乙基次磷酸盐7.5‑15%;阻燃剂三聚氰胺聚磷酸盐3‑7.5%;改性协效阻燃剂0.6‑5%;无碱短切玻璃纤维10‑40%;其它助剂1‑1.4;所述改性协效阻燃剂为硼酸锌、勃姆石、蛭石、云母中的一种或多种混合物粒子。本发明还提供一种制备上述复合材料的方法。本发明对协效阻燃剂进行表面改性,不仅大大提高了协效阻燃剂的协效阻燃作用,提高材料的加工性能,同时不影响基体材料的机械性能,扩大了材料的使用范围;本发明利用阻燃协效剂的协效阻燃作用,大大降低了主阻燃剂二乙基次磷酸盐的添加量,同时阻燃性能还得到提高,而且机械性能和加工性能得到改善,使得整体材料成本可以大大降低。
Description
技术领域
本发明涉及高分子材料技术领域,尤其涉及一种高效无卤阻燃增强尼龙复合材料及其制备方法。
背景技术
随着我国经济的高速发展,工程塑料在电子电器行业的应用获得了迅速增长,其中应用最广的是尼龙(PA)。玻纤增强尼龙具有优异的力学性能和耐热性能,然而其阻燃性能不能满足电子电器行业的要求。阻燃剂的大量添加,虽然在一定程度上改善了材料的阻燃性能,但材料的力学性能和电绝缘性能等都会受到很大的影响,直接影响了材料在电子电器行业的应用。
此外,随着环保要求的提高,传统的溴系阻燃剂已不能满足欧盟Rohs及WEEE指令的要求,无卤阻燃剂受到高度重视,常用的无卤阻燃剂有无机填料阻燃,但是因添加份数太高才能达到阻燃效果而限制使用;红磷类阻燃剂因使用过程中会析出造成安全隐患而被多国禁用;还有就是磷氮系阻燃剂,最常见的即科莱恩化工有限公司的Exolit OP1314,但其价格非常昂贵,造成下游厂商成本急剧升高。
发明内容
本发明的目的在于提供一种高效无卤阻燃增强尼龙复合材料及其制备方法,其具有优异阻燃性能且成本较低,同时也具有良好的机械性能和加工性能,可应用于制备较高要求的电子电器零部件。
为解决以上技术问题,本发明提供一种高效无卤阻燃增强尼龙复合材料,按重量分数包括以下组份:
所述改性协效阻燃剂为硼酸锌、勃姆石、蛭石、云母中的一种或多种混合物粒子;
所述改性协效阻燃剂的改性方法为:将所述阻燃协效剂与二元异氰酸酯反应制得异氰酸酯活化的粒子;以无水甲苯为分散剂,100℃下加入100份质量的阻燃协效剂粒子,搅拌下滴入12-15份的异氰酸酯,60min后利用旋转蒸发仪出去溶剂,得异氰酸酯改性的粒子;将异氰酸酯改性的粒子按重量百分数比例加入1%的钛酸酯溶液,高速搅拌制得最终的改性阻燃协效剂。
优选的,按重量分数包括以下组份:
优选的,按重量分数包括以下组份:
优选的,所述的尼龙树脂为PA6、PA66、PA1212、PA612中的一种或多种混合物。
优选的,所述的无碱短切玻璃纤维直径为9-13微米,长度为3-5mm。
本发明还提供了一种制备所述的高效无卤阻燃增强尼龙复合材料的方法,包括以下步骤:
步骤一、按上述的重量分数比例称取各种原料,并对尼龙树脂在90~110℃条件下干燥8~12h;
步骤二、将阻燃协效剂与二元异氰酸酯反应制得异氰酸酯活化的粒子:以无水甲苯为分散剂,100℃下加入100份质量的阻燃协效剂粒子,搅拌下滴入12-15份的异氰酸酯,60min后利用旋转蒸发仪出去溶剂,得异氰酸酯改性的粒子;将异氰酸酯改性的粒子按重量百分数比例加入1%的钛酸酯溶液,高速搅拌2min制得最终的改性阻燃协效剂。;
步骤三、将干燥后的尼龙树脂、主阻燃剂、改性阻燃协效剂等原料置于高速混合机中搅拌3~5min,使原料混合均匀;
步骤四、将混合均匀后的原料加入到双螺杆挤出机料斗,无碱短切玻璃纤维从挤出机中段侧喂料口加入,挤出造粒,制得无卤阻燃增强尼龙复合材料粒子,供注塑成型使用。
运用本发明的技术方案具有如下有益效果:
(1)本发明对阻燃协效剂进行表面改性,不仅能够大大提高协效阻燃剂的协效阻燃作用,而且提高了材料的加工性能,同时不影响基体材料的机械性能,扩大了材料的使用范围。
(2)本发明利用阻燃协效剂的协效阻燃作用,大大降低主阻燃剂二乙基次磷酸盐的添加量,同时阻燃性能不仅得到提高,而且机械性能和加工性能得到改善,使得整体材料成本可以大大降低。
具体实施方式
下面将结合具体实施例对本发明实施例中的技术方案进行清楚、完整地描述。
本发明还提供了一种制备所述的高效无卤阻燃增强尼龙复合材料的方法,包括以下步骤:
步骤一、按上述的重量分数比例称取各种原料,并对尼龙树脂在90~110℃条件下干燥8~12h;
步骤二、将阻燃协效剂与二元异氰酸酯反应制得异氰酸酯活化的粒子:以无水甲苯为分散剂,100℃下加入100份质量的阻燃协效剂粒子,搅拌下滴入12-15份的异氰酸酯,60min后利用旋转蒸发仪出去溶剂,得异氰酸酯改性的粒子;将异氰酸酯改性的粒子按重量百分数比例加入1%的钛酸酯溶液,高速搅拌2min制得最终的改性阻燃协效剂;异氰酸酯能够在阻燃协效剂表面形成一层异氰酸酯活性分子膜,使阻燃协效剂表面带有活性基团,再在其表面接着钛酸酯,一方面可以提高阻燃协效剂与基体树脂的相容性,同时一定的钛酸酯溶剂对阻燃起到促进作用,提升阻燃性能。
步骤三、将干燥后的尼龙树脂、主阻燃剂、改性阻燃协效剂等原料置于高速混合机中搅拌3~5min,使原料混合均匀;
步骤四、将混合均匀后的原料加入到双螺杆挤出机料斗,无碱短切玻璃纤维从挤出机中段侧喂料口加入,挤出造粒,制得无卤阻燃增强尼龙复合材料粒子,供注塑成型使用。
具体的,在本实施例中,首先使用前将尼龙66树脂在100℃条件干燥8h。将干燥后的尼龙树脂、主阻燃剂、改性阻燃协效剂等原料置于高速混合机中搅拌3~5min,使原料混合均匀;加入双螺杆挤出机,在侧向喂料口处添加短切玻璃纤维。加工工艺如下:一区温度250~260℃,二区温度265~280℃,三区温度265~280℃,四区温度265~280℃,五区温度260~275℃,六区温度250~265℃,七区温度240~260℃,八区温度240~260℃,九区温度240~265℃,主机转速240~400转/分钟。挤出后冷却、干燥、切粒即得增强尼龙复合材料。
按照上述制备方法,重量百分比配方如表1:
表1 实施例1~6及对比例的组份含量
性能检测方法:
拉伸强度按ASTM-D638标准来进行拉伸强度的检测,试样类型为I型,样条尺寸(mm):(165±2)×(12.70±0.2)×(3.20±0.2),拉伸速度为50mm/min。
弯曲强度和弯曲模量按ASTM-D790标准进行检验,试样尺寸(mm):(127±2)×(12.7±0.2)×(3.20±0.2),弯曲速度为13mm/min。
缺口冲击强度按按ASTM-D256标准进行检验,试样类型为V缺口型,试样尺寸(mm):63.5×(12.7±0.2)×(3.2±0.2);缺口类型为V口类,缺口剩余厚度10.16mm。
阻燃性能按美国UL标准注塑成标准燃烧试样条。
表2 高效无卤阻燃增强尼龙复合材料
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本发明的保护范围。
Claims (4)
1.一种高效无卤阻燃增强尼龙复合材料,其特征在于,按重量分数包括以下组分:
尼龙树脂 41.1%
阻燃剂二乙基次磷酸盐 7.5%
阻燃剂三聚氰胺聚磷酸盐 5%
改性协效阻燃剂 5%
无碱短切玻璃纤维 40%
抗氧剂 0.3%
润滑剂 0.8%
KH-550 0.3%;
协效阻燃剂为勃姆石、云母中的一种或两种混合物粒子;
所述改性协效阻燃剂的改性方法为:将所述协效阻燃剂与二元异氰酸酯反应制得异氰酸酯活化的粒子;以无水甲苯为分散剂,100℃下加入100质量份的协效阻燃剂粒子,搅拌下滴入12-15份的异氰酸酯,60min后利用旋转蒸发仪除去溶剂,得到异氰酸酯改性的粒子;将异氰酸酯改性的粒子按重量百分数比例加入1%的钛酸酯溶液,高速搅拌制得最终的改性协效阻燃剂。
2.根据权利要求1所述的一种高效无卤阻燃增强尼龙复合材料,其特征在于:所述的尼龙树脂为PA6、PA66、PA1212、PA612中的一种或多种混合物。
3.根据权利要求1~2任一项所述的一种高效无卤阻燃增强尼龙复合材料,其特征在于:所述的无碱短切玻璃纤维直径为9-13微米,长度为3-5mm。
4.一种制备权利要求1~3任一项所述的高效无卤阻燃增强尼龙复合材料的方法,其特征在于,包括以下步骤:
步骤一、按上述的重量分数比例称取各种原料,并对尼龙树脂在90~110℃条件下干燥8~12h;
步骤二、将协效阻燃剂与二元异氰酸酯反应制得异氰酸酯活化的粒子:以无水甲苯为分散剂,100℃下加入100质量份的阻燃协效剂粒子,搅拌下滴入12-15份的异氰酸酯,60min后利用旋转蒸发仪除去溶剂,得异氰酸酯改性的粒子;将异氰酸酯改性的粒子按重量百分数比例加入1%的钛酸酯溶液,高速搅拌2min制得最终的改性协效阻燃剂;
步骤三、将干燥后的尼龙树脂,阻燃剂二乙基次磷酸盐、阻燃剂三聚氰胺聚磷酸盐、改性协效阻燃剂、抗氧剂、润滑剂、KH-550原料置于高速混合机中搅拌3~5min,使原料混合均匀;
步骤四、将混合均匀后的原料加入到双螺杆挤出机料斗,无碱短切玻璃纤维从挤出机中段侧喂料口加入,挤出造粒,制得无卤阻燃增强尼龙复合材料粒子,供注塑成型使用。
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