CN114075425A - 一种用于粘接聚醚醚酮的聚酰亚胺胶黏剂 - Google Patents
一种用于粘接聚醚醚酮的聚酰亚胺胶黏剂 Download PDFInfo
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Abstract
本发明的一种用于粘接聚醚醚酮的聚酰亚胺配方及其制备工艺属于高分子聚合物的技术领域。该胶黏剂的配方是将双马来酰亚胺树脂,热塑性聚酰亚胺和芳香族二元胺按照一定比例在有机溶剂中进行共混,得到混合均匀的树脂。其制备工艺是将胶黏剂树脂涂于清洗干净的聚醚醚酮粘接件表面,将粘接件搭接在一起,于温度为160℃‑240℃,压力为1MPa‑5MPa的条件下完成胶黏剂的固化。本发明的胶黏剂树脂粘度适中,固化温度低,具有良好的工艺性;同时固化后的胶黏剂具有优异的耐热性,粘结件在250℃保持较高的剪切强度,是一种适用于粘结聚醚醚酮的耐高温胶黏剂。
Description
技术领域
本发明属于高分子聚合物技术领域,具体涉及一种用于粘接聚醚醚酮的聚酰亚胺胶粘剂。
背景技术
聚醚醚酮(Poly ether ether ketone,PEEK)是一种新型特种工程塑料,具有优异的综合性能,包括耐高温特性,优良的机械性能,自润滑性,耐化学药品性,阻燃性和耐疲劳性。由于PEEK具有优异的物理化学性能,以及可以采用传统的热塑性塑料成型加工方法进行加工,其已经在航空航天、核能、信息通讯、电子电器、石油化工和机械制造等高技术领域得到应用,从而使许多行业的传统产品实现了更新换代。
胶粘剂是能把两种相同或不同的材料通过粘接作用将其连接起来,并能具备一定力学性能、物理性能和化学性能的一类物质。胶粘剂的应用随着现代技术的发展而越发广泛,胶接技术已经成为包括胶接、焊接和机械连接在内的当代三大连接技术之一。尤其是在胶粘剂应用最早最多最主要的航空工业,胶粘剂主要用于金属结构、金属与塑料、金属与橡胶、蜂窝夹层结构与壁板等的粘接,会逐渐代替部分铆钉和焊接。这主要是由于采用粘接技术可以明显减轻结构的重量,提高疲劳寿命,简化工艺过程。
随着PEEK在高技术领域应用范围的加大,对适用于粘接PEEK的胶粘剂的开发也成为必然。但是PEEK制品具有材料表面致密度和光滑度高,表面能低的特性,因此一般的胶粘剂粘接效果较差;另外,PEEK制品的使用温度较高,一些基于PEEK的复合材料的使用温度高达300℃,因此,需要开发出适用于粘接PEEK的耐高温胶粘剂。
发明内容
本发明的目的是提供一种适用于粘接聚醚醚酮的聚酰亚胺胶黏剂。
一种用于粘接聚醚醚酮的耐高温胶黏剂,按质量和100%计算,由30%~85%的双马来酰亚胺树脂、10%~30%的芳香族二元胺和5%~40%的热塑性聚酰亚胺组成。
其中,双马来酰亚胺树脂的结构通式为:
热塑性聚酰亚胺的数均分子量在5000~60000(优选为25000~30000),结构单元的分子式如下:
本发明所述的用于粘接聚醚醚酮的耐高温胶黏剂的应用,其步骤如下:
1)使用注塑得到的长方形PEEK薄片作为粘接件,尺寸为50mm*15mm*3mm,对粘结件先用丙酮超声处理15min以脱脂,用清水冲洗,再用蒸馏水清洗烘干待用;
2)胶粘剂的制备:将上述比例的双马来酰亚胺树脂、芳香族二元胺和热塑性聚酰亚胺溶解于有机溶剂中,固含量为10%~30%,40℃加热蒸出部分溶剂,得到均一的树脂粘稠液;
3)粘结接头的制备:按照GB7124-2008,将制得的胶粘剂涂于经处理后的粘结件上,然后搭接在一起,将热压机的温度设定为160℃~240℃,施加1MPa~5MPa的压强,加热进行固化,得到可以测试剪切强度的粘结接头。
第2)步中的有机溶剂可以是二氯甲烷,三氯甲烷或二甲基甲酰胺。
本发明提供的胶粘剂具有以下优点:可以有效的粘结PEEK,室温下粘结件的剪切强度达到16MPa;具有优异的耐高温特性,在250℃下仍保持很高的粘结力,剪切强度为12.8MPa。同时胶粘剂的制备方法比较简单,固化温度较低,易于成型。
附图说明
图1:a曲线为实施例1采用的双马来酰亚胺树脂的DSC扫描曲线,b曲线为实施例1制备得到的胶粘剂树脂的DSC扫描曲线。双马来酰亚胺树脂具有较低的熔点,为76℃,在220℃出现交联峰;改性后的胶黏剂树脂由于芳香族二胺起到固化剂的作用,因此在180℃出现交联峰;
图2:实施例1制备得到的粘结接头的室温下剪切强度曲线。按照该配方制得的胶黏剂在室温下具有较高的剪切强度,达到16MPa;
图3:实施例1制备得到的粘结接头在250℃下的剪切强度曲线。按照该配方制得的胶黏剂在250℃仍然保持较高的剪切强度,达到12.8MPa。
具体实施方式
实施例1
向40mL二氯甲烷溶剂中添加5.4g N,N’-间苯氧基二苯甲酮型双马来酰亚胺树脂,1.8g1,4-(对氨基苯氧基)-2-苯基苯和0.8g分子量为25000的热塑性聚酰亚胺树脂A,待物料溶解均匀后,加热至40℃蒸出一半量的溶剂,得到均一的树脂粘稠液。将制得的树脂粘稠液涂于经处理后的PEEK薄片粘结件上,然后搭接在一起。将粘接件置于80℃的烘箱中保持10min以烘净溶剂,再转移至温度设定为200℃的热压机中,施加2MPa的压强保持3h,得到可以测试剪切强度的粘结接头。
在室温和250℃下对该粘接件测试剪切强度,室温下剪切强度为16MPa,250℃下为12.8MPa。
实施例2
向40mL二氯甲烷溶剂中添加6.8g N,N’-间苯氧基二苯甲酮型双马来酰亚胺树脂,0.8g 1,4-(对氨基苯氧基)-2-苯基苯和0.4g分子量为25000的热塑性聚酰亚胺树脂A,待物料溶解均匀后,加热至40℃蒸出一半量的溶剂,得到均一的树脂粘稠液。将制得的树脂粘稠液涂于经处理后的PEEK薄片粘结件上,然后搭接在一起。将粘接件置于80℃的烘箱中保持10min以烘净溶剂,再转移至温度设定为200℃的热压机中,施加2MPa的压强保持3h,得到可以测试剪切强度的粘结接头。
在室温和250℃下对该粘接件测试剪切强度,室温下剪切强度为13.1MPa,250℃下为11.5MPa。
实施例3
向40mL二氯甲烷溶剂中添加5.4g N,N’-间苯氧基二苯甲酮型双马来酰亚胺树脂,1.8g1,4-(对氨基苯氧基)-2-苯基苯和1.6g分子量为25000的热塑性聚酰亚胺树脂A,待物料溶解均匀后,加热至40℃蒸出一半量的溶剂,得到均一的树脂粘稠液。将制得的树脂粘稠液涂于经处理后的PEEK薄片粘结件上,然后搭接在一起。将粘接件置于80℃的烘箱中保持10min以烘净溶剂,再转移至温度设定为200℃的热压机中,施加2MPa的压强保持3h,得到可以测试剪切强度的粘结接头。
在室温和250℃下对该粘接件测试剪切强度,室温下剪切强度为14.3MPa,250℃下为9.8MPa。
实施例4
向40mL二氯甲烷溶剂中添加2.4g N,N’-间苯氧基二苯甲酮型双马来酰亚胺树脂,2.4g1,4-(对氨基苯氧基)-2-苯基苯和3.2g分子量为25000的热塑性聚酰亚胺树脂A,待物料溶解均匀后,加热至40℃蒸出一半量的溶剂,得到均一的树脂粘稠液。将制得的树脂粘稠液涂于经处理后的PEEK薄片粘结件上,然后搭接在一起。将粘接件置于80℃的烘箱中保持10min以烘净溶剂,再转移至温度设定为200℃的热压机中,施加2MPa的压强保持3h,得到可以测试剪切强度的粘结接头。
在室温和250℃下对该粘接件测试剪切强度,室温下剪切强度为8.6MPa,250℃下为6.1MPa。
实施例5
向40mL二氯甲烷溶剂中添加4.5g N,N’-间苯氧基二苯甲酮型双马来酰亚胺树脂,2.5g1,4-(对氨基苯氧基)-2-苯基苯和0.8g分子量为27000的热塑性聚酰亚胺树脂A,待物料溶解均匀后,加热至40℃蒸出一半量的溶剂,得到均一的树脂粘稠液。将制得的树脂粘稠液涂于经处理后的PEEK薄片粘结件上,然后搭接在一起。将粘接件置于80℃的烘箱中保持10min以烘净溶剂,再转移至温度设定为200℃的热压机中,施加2MPa的压强保持3h,得到可以测试剪切强度的粘结接头。
在室温和250℃下对该粘接件测试剪切强度,室温下剪切强度为12.1MPa,250℃下为9.2MPa。
实施例6
向40mL二氯甲烷溶剂中添加5.4g N,N’-间苯氧基二苯二酮间苯型双马来酰亚胺树脂,1.8g 4,4’-二氨基二苯甲烷和0.8g分子量为25000的热塑性聚酰亚胺树脂C,待物料溶解均匀后,加热至40℃蒸出一半量的溶剂,得到均一的树脂粘稠液。将制得的树脂粘稠液涂于经处理后的PEEK薄片粘结件上,然后搭接在一起。将粘接件置于80℃的烘箱中保持10min以烘净溶剂,再转移至温度设定为200℃的热压机中,施加2MPa的压强保持3h,得到可以测试剪切强度的粘结接头。
在室温和250℃下对该粘接件测试剪切强度,室温下剪切强度为12.5MPa,250℃下为8.2MPa。
实施例7
向40mL二氯甲烷溶剂中添加5.4g N,N’-间苯氧基二苯二酮间苯型双马来酰亚胺树脂,1.8g 4,4’-二氨基二苯甲烷和0.8g分子量为27000的热塑性聚酰亚胺树脂C,待物料溶解均匀后,加热至40℃蒸出一半量的溶剂,得到均一的树脂粘稠液。将制得的树脂粘稠液涂于经处理后的PEEK薄片粘结件上,然后搭接在一起。将粘接件置于80℃的烘箱中保持10min以烘净溶剂,再转移至温度设定为200℃的热压机中,施加4MPa的压强保持3h,得到可以测试剪切强度的粘结接头。
在室温和250℃下对该粘接件测试剪切强度,室温下剪切强度为11.2MPa,250℃下为7.9MPa。
实施例8
向40mL二氯甲烷溶剂中添加4.6g N,N’-间苯氧基二苯二酮间苯型双马来酰亚胺树脂,2.4g 4,4’-二氨基二苯甲烷和0.8g分子量为25000的热塑性聚酰亚胺树脂C,待物料溶解均匀后,加热至40℃蒸出一半量的溶剂,得到均一的树脂粘稠液。将制得的树脂粘稠液涂于经处理后的PEEK薄片粘结件上,然后搭接在一起。将粘接件置于80℃的烘箱中保持10min以烘净溶剂,再转移至温度设定为200℃的热压机中,施加2MPa的压强保持3h,得到可以测试剪切强度的粘结接头。
在室温和250℃下对该粘接件测试剪切强度,室温下剪切强度为11.5MPa,250℃下为9.2MPa。
Claims (5)
1.一种用于粘接聚醚醚酮的聚酰亚胺胶黏剂,其特征在于:按质量和100%计算,由30%~85%的双马来酰亚胺树脂、10%~30%的芳香族二元胺和5%~40%的热塑性聚酰亚胺组成。
5.如权利要求4所述的一种用于粘接聚醚醚酮的聚酰亚胺胶黏剂,其特征在于:热塑性聚酰亚胺的数均分子量为25000~30000。
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