CN116875045A - 一种玻璃纤维增强尼龙材料及其制备方法 - Google Patents
一种玻璃纤维增强尼龙材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种玻璃纤维增强尼龙材料及其制备方法,包括尼龙树脂、耐高温玻璃纤维、热稳定剂、氧气阻隔剂和润滑剂。本发明利用耐高温玻璃纤维作增强组分,所制备的玻璃纤维增强尼龙材料相比常规材料,在不牺牲增强尼龙材料的初始力学性能的前提下,显著提升共混材料在不同等级高温下老化后的性能保持率,具有良好的市场应用前景。
Description
技术领域
本发明属于改性塑料领域,特别涉及一种玻璃纤维增强尼龙材料及其制备方法。
背景技术
玻璃纤维增强尼龙(PA)材料,具有良好的机械性能、耐热稳定性、耐腐蚀性,在汽车、电子电器、电动工具、特种装备等领域的核心结构部件上广泛应用。在汽车制造业中,PA66和PA6是使用最多的两种尼龙材料,尤其是随着汽车轻量化的发展要求,具有优良机械性能、加工性能与耐高温性能的玻璃纤维增强PA66和PA6材料在汽车发动机周边燃油、冷却和排气系统越来越多的替代金属。另一方面,发动机周边零部件长期处于高温环境之中,材料需具备足够的长期耐高温性能,也就对玻璃纤维增强PA66和PA6材料的长期耐高温老化性能(如210℃/1000h老化后的拉伸强度和缺口冲击强度保持率≥75%)提出挑战。
现有专利中,主要通过引入长期耐热添加剂对材料进行改性,从而实现玻璃纤维增强PA66和PA6材料的长期耐高温性能。专利CN105283510A主要利用多元醇作为阻隔剂,复配铜盐类热稳定剂,制备的玻璃纤维增强尼龙材料在230℃/1000h老化后性能优异。专利CN102245706A采用聚酰亚胺、铁粉作为耐热助剂,制备的玻璃纤维增强PA66/PA6材料经210℃/1000h老化后具有良好的机械性能。专利CN103717675A同样采用含铁元素母粒制备的玻纤增强PA66/PA6材料,在230℃,2000h甚至4000h老化后,拉伸强度与初始相比,基本没有变化。
但是,这些专利由于引入生产工艺繁琐且价格较为昂贵的耐热助剂实现玻璃纤维增强聚酰胺材料长期耐高温老化性能的提升,这些特殊的耐热助剂或耐热组分一般会对聚酰胺的部分性能造成负面影响:如降低共混材料的初始机械性能、降低共混材料的加工流动性、降低共混材料的高温性能(如降低热变形温度、高温拉伸强度等)。
发明内容
本发明所要解决的技术问题是提供一种长期耐高温老化玻璃纤维增强尼龙材料及其制备方法,利用耐高温玻璃纤维作增强组分,所制备的玻璃纤维增强尼龙材料相比常规材料,在不牺牲增强尼龙材料的初始力学性能的前提下,显著提升共混材料在不同等级高温下老化后的性能保持率,具有良好的市场应用前景。
本发明提供了一种长期耐高温老化玻璃纤维增强尼龙材料,按重量份数,包括如下组分:
其中,所述耐高温玻璃纤维为带有苯环结构的玻璃纤维。
所述尼龙树脂为PA66或PA6树脂,相对粘度2.0-3.2。
所述热稳定剂为卤化铜类、受阻酚、硫代硫酸酯、胺类中的至少一种,所述热稳定剂为市售级,在玻璃纤维增强尼龙材料中具有良好的分散性。
所述氧气阻隔剂为多元醇、环氧树脂、丙烯酸酯、聚己二酸间苯二甲酰胺(MXD6)中的至少一种。
所述多元醇可以选自聚乙烯醇、双季戊四醇、甘油中的至少一种。
所述润滑剂为超支化聚酯、硬脂酸盐、乙撑双硬脂酸酰胺、聚乙烯蜡中的至少一种。
所述带有苯环结构的玻璃纤维采用偶联剂进行处理;所述偶联剂为具有苯环结构的硅烷偶联剂、铝酸酯偶联剂、钛酸酯偶联剂中的至少一种。所述偶联剂为耐高温型偶联剂,其与玻璃纤维结合后,分解温度可达350℃以上。分解温度越高,与树脂结合后在高温下的结合力更持久。通过红外与元素分析测试到处理后的玻纤带有苯环结构。
优选的,按重量份数,包括如下组分:
本发明提供了一种玻璃纤维增强尼龙材料的制备方法,包括如下步骤:
按配比,将原料预混后,由双螺杆挤出机塑化,玻璃纤维按比例由双螺杆挤出机的侧喂料口加入,经过牵引、冷却、切粒、干燥后,得到长期耐高温老化玻璃纤维增强尼龙材料;双螺杆挤出机设置温度为220-280℃,螺杆转速为200-600转/分。
本发明提供了一种玻璃纤维增强尼龙材料在汽车发动机相关的燃料系统、排气系统中的应用。
有益效果
本发明利用独特的耐高温玻璃纤维作增强组分,同时进一步添加氧气阻隔剂,所制备的玻璃纤维增强尼龙材料相比常规玻璃纤维增强尼龙材料,在不牺牲增强尼龙材料的初始力学性能的前提下,共混材料在180℃、200℃及210℃温度下,1000h老化后的拉伸强度与缺口冲击强度保留率均提高到90%及以上,满足在长期高温工况下的使用条件,具有良好的市场应用前景。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
本发明所采用的试剂、方法和设备,如无特殊说明,均为本技术领域常规试剂、方法和设备。
以下实施例及对比例中采用的原料如下:
PA66树脂:购自华峰集团,相对粘度2.7±0.5,EP-158;
PA6树脂:购自海阳化纤,相对粘度2.8±0.5,HY 2800;
玻璃纤维1#:购自重庆复材,典型牌号为ECS301HP-3-H;
玻璃纤维2#:玻璃纤维1#经过煅烧处理。煅烧处理为:玻璃纤维1#经450℃煅烧2小时后,置于肥皂水中超声清洗10分钟。
玻璃纤维3#:玻璃纤维1#经过煅烧处理,KH-550(3-氨丙基三乙氧基硅烷)偶联剂浸渍。偶联剂浸渍为:质量分数为0.5%的偶联剂水溶液浸渍经高温处理的玻璃纤维,浸渍时间为2小时。
耐高温玻璃纤维1#:经过上述相同煅烧处理和浸渍,高温型偶联剂浸渍。所述高温型偶联剂为具有苯环结构的硅烷偶联剂,购自迈图,具体牌号为A-1128。
耐高温玻璃纤维2#:经过上述相同煅烧处理和浸渍,高温型偶联剂浸渍。所述高温型偶联剂为具有苯环结构的钛酸酯偶联剂,购自南京曙光化工集团有限公司,具体牌号为NDZ-201。
热稳定剂:NAUGARD 445,购自亚蒂凡特;
氧气阻隔剂1:MXD6,M30,购自上海盈固有限公司。
氧气阻隔剂2:双季戊四醇,购自广州浩宇国际贸易有限公司。
氧气阻隔剂3:纳米蒙脱土,DK-2,购自浙江丰虹新材料股份有限公司。
润滑剂:市售。
各实施例及对比例的复合材料通过如下过程制备得到:
按配比,将原料预混后,由双螺杆挤出机塑化,玻璃纤维按比例由双螺杆挤出机的侧喂料口加入,经过牵引、冷却、切粒、干燥后,得到长期耐高温老化玻璃纤维增强尼龙材料;双螺杆挤出机设置温度为220-280℃,螺杆转速为200-600转/分。
实施例和对比例经过以下测试方法或测试标准:
拉伸强度测试评价方法:依据ISO527标准,测试样条在23℃下的拉伸强度;
缺口冲击测试评价方法:依据ISO179/1eA标准,测试样条在23℃下的缺口冲击强度;
长期热老化测试方法:依据ISO 188标准,样条置于180℃,200℃,210℃温度的热老化箱内,持续老化时间为1000小时。
表1实施例和对比例配方及测试结果
续表1实施例和对比例配方及测试结果
对比例和实施例的实验结果表明:相同树脂与热稳定剂体系,采用特殊处理耐高温玻璃纤维增强PA66、PA6及PA66/PA6材料,并复配氧气阻隔剂,相比常规玻纤具有更高的初始拉伸强度,并且在180℃、200℃及210℃温度下,1000h老化后的拉伸强度与缺口冲击强度保留率均优于常规玻璃纤维增强材料。
本发明的长期耐高温老化玻璃纤维增强尼龙材料具备在保证高强度的前提下,满足180℃、200℃及210℃长期使用性能。
Claims (9)
1.一种玻璃纤维增强尼龙材料,其特征在于:按重量份数,包括如下组分:
结构的玻璃纤维。
2.根据权利要求1所述的尼龙材料,其特征在于:所述尼龙树脂为PA66或PA6树脂,相对粘度2.0-3.2。
3.根据权利要求1所述的尼龙材料,其特征在于:所述热稳定剂为卤化铜类、受阻酚、硫代硫酸酯、胺类中的至少一种。
4.根据权利要求1所述的尼龙材料,其特征在于:所述氧气阻隔剂为多元醇、环氧树脂、丙烯酸酯、聚己二酸间苯二甲酰胺中的至少一种。
5.根据权利要求1所述的尼龙材料,其特征在于:所述润滑剂为超支化聚酯、硬脂酸盐、乙撑双硬脂酸酰胺、聚乙烯蜡中的至少一种。
6.根据权利要求1所述的尼龙材料,其特征在于:所述带有苯环结构的玻璃纤维采用偶联剂进行处理;所述偶联剂为具有苯环结构的硅烷偶联剂、铝酸酯偶联剂、钛酸酯偶联剂中的至少一种。
7.根据权利要求1所述的尼龙材料,其特征在于:按重量份数,包括如下组分:
8.一种如权利要求1所述的玻璃纤维增强尼龙材料的制备方法,包括如下步骤:
按配比,将原料预混后,由双螺杆挤出机塑化,耐高温玻璃纤维按比例由双螺杆挤出机的侧喂料口加入,经过牵引、冷却、切粒、干燥后,得到长期耐高温老化玻璃纤维增强尼龙材料;双螺杆挤出机设置温度为220-280℃,螺杆转速为200-600转/分。
9.一种如权利要求1所述的玻璃纤维增强尼龙材料在汽车发动机相关的燃料系统、排气系统中的应用。
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