CN108530596B - 一种***键交联的聚叠氮缩水甘油醚及其制备方法 - Google Patents
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Abstract
本发明涉及一种***键交联的聚叠氮缩水甘油醚及其制备方法,以优化传统聚叠氮缩水甘油醚基粘合剂合成路线,简化其合成步骤。所涉及的***键交联的聚叠氮缩水甘油醚分子结构式如下:
Description
技术领域
本发明涉及涉及一种聚叠氮缩水甘油醚基粘合剂,更具体地说,涉及一种***键交联的聚叠氮缩水甘油醚,属于含能材料领域。
背景技术
自从2001年Shrapless提出“点击化学”(Click Chemistry)的概念以来,其作为一种简单、高效、可控和快捷的合成方法被广泛应用于粘合剂制备。炔基和叠氮基的Huisgen环加成反应是点击化学中应用最为成功的反应,这类反应条件温和,生成的***环具有高的生成焓,燃烧释放清洁的氮气,同时可以避免异氰酸酯体系容易因异氰酸酯的过量而产生气泡的问题,因此在新型固化体系中大量研究使用。例如Hagen等人在《Curing ofGlycidylAzide Polymer(GAP)Diol Using Isocyanate,Isocyanate-Free,SynchronousDual,and Sequential Dual Curing Systems》Propellants Explosives Pyrotechnics,2015,40(2):275-284中利用聚叠氮缩水甘油醚、异氰酸酯和小分子二炔化合物制备***键交联的聚叠氮缩水甘油醚胶片,其拉伸强度不高于1.2MPa,延伸率为48~285%,整体力学性能较差。
发明内容
本发明所要解决的技术问题是克服现有技术的不足,提供一种拉伸强度高、力学性能好的***键交联的聚叠氮缩水甘油醚及其制备方法。
本发明的构思是:基于点击化学制备的聚叠氮缩水甘油醚基粘合剂力学性能较差的原因是炔基和叠氮基反应活性不高,而亚铜盐类催化剂的加入又会影响粘合剂整体力学性能。为了提高聚叠氮缩水甘油醚基粘合剂的应用性能,本发明设想:一方面将反应活性较高的异佛尔酮二异氰酸酯用于主链扩链反应,提高主链分子量;另一方面而利用扩链剂小分子炔二醇上的炔基和聚叠氮缩水甘油醚上的叠氮基进行适度交联反应;这样可使异氰酸酯与羟基的摩尔比不过量,避免产生气泡,同时提高粘合剂整体力学性能。
为了解决上述技术问题,本发明的***键交联的聚叠氮缩水甘油醚,其分子结构式如下所示:
其中n,x,y,z为整数,x/y为0.2~5。
本发明的***键交联的聚叠氮缩水甘油醚合成路线如下:
其中n,x,y,z为整数,x/y为0.2~5。
本发明的***键交联的聚叠氮缩水甘油醚的制备方法,包括以下步骤:
将聚叠氮缩水甘油醚和小分子炔二醇以0.2~5:1的摩尔比加入至反应器中,利用机械搅拌混匀,然后称量加入异佛尔酮二异氰酸酯和有机锡类催化剂,其中聚叠氮缩水甘油醚和小分子炔二醇摩尔数之和、异佛尔酮二异氰酸酯与有机锡类催化剂的摩尔比为1:0.8~1.05:0.0001~0.01,经充分混合后转移到模具中。将模具置于氮气气氛,于60~100℃反应7~28d,反应结束后将模具中得到的胶片取出,经干燥后得到***键交联的聚叠氮缩水甘油醚。
所述的聚叠氮缩水甘油醚的相对分子质量范围为500~4000;
所述的小分子炔二醇为1,4-丁炔二醇,2-戊炔-1,4-二醇或3-己炔-2,5-二醇;
所述的有机锡类催化剂为二丁基氧化锡、二丁基二月桂酸锡或辛酸亚锡。
本发明的优点:
本发明的***键交联的聚叠氮缩水甘油醚利用一锅法制备,制备方法简单易行;利用小分子炔基二元醇作为扩链剂和固化剂,可以避免异氰酸酯含量过多而产生气泡的问题。本发明的***键交联的聚叠氮缩水甘油醚表现出良好的力学性能,其拉伸强度为2.3MPa,断裂伸长率为310%;而对比文件中***交联的聚叠氮缩水甘油醚的拉伸强度为1.2MPa,延伸率为48~285%。
具体实施方式
下面结合实施例进一步对发明作详细说明。
(1)测试仪器:
红外光谱利用德国Bruker公司Tensor 27型红外光谱仪测试,测试条件:扫描分辨率为4cm-1,扫描次数为20次。
热分解利用美国TA公司DSC-2910型差热分析扫描仪测试,测试条件:升温速度为10℃/min。
力学性能利用美国Instron5940型万能材料试验机测试,测试条件:25℃,拉伸速率为500mm/min。
(2)原材料准备:
聚叠氮缩水甘油醚是通过文献方法(Glycidylazidepolymer(GAP).I.Synthesesand characterization.Polimeros-Ciencia E Tecnologia,2012,22(5):407-413)合成。
下面通过实施例对本发明作进一步描述,但本发明并不限于此。
实施例1
在带有机械搅拌、温度计及回流装置的250mL三口瓶中,加入相对分子质量为1000的聚叠氮缩水甘油醚60g(60mmol),1,4-丁炔二醇10.33g(120mmol)和异佛尔酮二异氰酸酯38.01g,加热至50℃,搅拌20min直至均匀。然后加入100μL二月桂酸二丁基锡,继续搅拌20min,将体系转移至模具中。将模具置放于真空烘箱内,利用循环抽真空的方法除去体系中的气泡,通氮气保护后将反应体系于70℃反应14d。反应结束后将模具中得到的胶片取出,即得到***键交联的聚叠氮缩水甘油醚。
结构鉴定:
红外(KBr,cm-1):3365,2917,2845,2102,1740,1600,1532,1276,1220,1136,1070,769。
上述分析数据证实按该合成方法得到的物质确实是***键交联的聚叠氮缩水甘油醚。
实施例2
在带有机械搅拌、温度计及回流装置的250mL三口瓶中,加入相对分子质量为1500的聚叠氮缩水甘油醚60g(40mmol),2-戊炔-1,4-二醇2.0g(20mmol)和异佛尔酮二异氰酸酯14.0g,加热至50℃,搅拌20min直至均匀。然后加入50μL二丁基氧化锡,继续搅拌20min,将体系转移至模具中。将模具置放于真空烘箱内,利用循环抽真空的方法除去体系中的气泡,通氮气保护后将反应体系于80℃反应7d。反应结束后将模具中得到的胶片取出,即得到***键交联的聚叠氮缩水甘油醚。
实施例3
在带有机械搅拌、温度计及回流装置的250mL三口瓶中,加入相对分子质量为2000的聚叠氮缩水甘油醚60g(30mmol),3-己炔-2,5-二醇13.69g(120mmol)和异佛尔酮二异氰酸酯31.68g,加热至50℃,搅拌20min直至均匀。然后加入80μL辛酸亚锡,继续搅拌20min,将体系转移至模具中。将模具置放于真空烘箱内,利用循环抽真空的方法除去体系中的气泡,通氮气保护后将反应体系于85℃反应7d。反应结束后将模具中得到的胶片取出,即得到***键交联的聚叠氮缩水甘油醚。
性能测试:本发明通过实施例1得到的***键交联的聚叠氮缩水甘油醚胶片,其热分解峰值温度为252.6℃,起始失重温度为214.1℃,拉伸强度为2.3MPa,断裂伸长率为310%。
Claims (3)
1.一种***键交联的聚叠氮缩水甘油醚的制备方法,其特征在于,包括以下步骤:
将聚叠氮缩水甘油醚和小分子炔二醇以0.2~5:1的摩尔比加入至反应器中,然后加入异佛尔酮二异氰酸酯和有机锡类催化剂,其中聚叠氮缩水甘油醚和小分子炔二醇摩尔数之和、异佛尔酮二异氰酸酯与有机锡类催化剂的摩尔比为1:0.8~1.05:0.0001~0.01,经充分混合后转移到模具中,将模具置于氮气气氛,于60~100℃反应7~28d,反应结束后将模具中得到的胶片取出,经干燥后即为***键交联的聚叠氮缩水甘油醚;所述的小分子炔二醇为1,4-丁炔二醇,2-戊炔-1,4-二醇或3-己炔-2,5-二醇。
2.根据权利要求1所述的***键交联的聚叠氮缩水甘油醚的制备方法,其特征在于:所述的聚叠氮缩水甘油醚的相对分子质量范围为500~4000。
3.根据权利要求1所述的***键交联的聚叠氮缩水甘油醚的制备方法,其特征在于:所述的有机锡类催化剂为二丁基氧化锡、二丁基二月桂酸锡或辛酸亚锡。
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