CN116284744A - 一种端六叠氮基硝酸酯聚醚粘合剂及其合成方法 - Google Patents
一种端六叠氮基硝酸酯聚醚粘合剂及其合成方法 Download PDFInfo
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Abstract
本发明公开了一种端六叠氮基硝酸酯聚醚粘合剂及其合成方法，该方法首先以三叠氮新戊醇和缩水甘油醚硝酸酯为原料，三氟化硼·乙醚络合物为催化剂，通过阳离子开环聚合反应得到三叠氮新戊基聚缩水甘油醚硝酸酯醇；再以三叠氮新戊基聚缩水甘油醚硝酸酯醇和六亚甲基二异氰酸酯为原料，二丁基锡二月桂酸酯为催化剂，通过加成反应得到端六叠氮基聚缩水甘油醚硝酸酯，即为端六叠氮基硝酸酯聚醚粘合剂。本发明主要用于固体推进剂，用于合成聚三唑弹性体提高了硬链段的含量和交联密度，促进了弹性体微相分离，从而提高了力学性能。
Description
技术领域
本发明属于固体推进剂领域，涉及一种固体推进剂用聚醚粘合剂，具体涉及一种端六叠氮基硝酸酯聚醚粘合剂及其合成方法。
背景技术
端羟基环氧乙烷-四氢呋喃共聚醚(PET)粘合剂具有与硝酸酯类增塑剂互溶性好、主链柔顺性好、粘度低、玻璃化转变温度低等特点，在硝酸酯增塑聚醚(NEPE)推进剂中已经得到了广泛的应用。PET粘合剂一般与多异氰酸酯固化剂组成异氰酸酯固化体系，通过端羟基和异氰酸酯基间的固化反应制备聚氨酯弹性体，但是异氰酸酯固化体系固化条件苛刻，对潮气敏感，异氰酸酯基团能够与水或有机酸快速反应生成CO2，在推进剂中易形成气孔，影响其力学性能、贮存性能和安全性能。
为了解决异氰酸酯固化体系存在的上述问题，科研人员开发了端叠氮基粘合剂与多炔固化剂固化制备聚三唑交联弹性体的新型固化体系。例如张晗昱等人《端叠氮基聚醚的合成及与多炔固化剂的交联反应》火炸药学报，2012，35(5)：45-48中公开了一种端六叠氮基硝酸酯聚醚粘合剂，即端叠氮基环氧乙烷-四氢呋喃共聚醚(N3PET4000)，其结构式如下：
该N3PET4000与多炔固化剂三炔丙基胺固化，加入增塑剂2,2-二硝基丙醇缩甲醛和2,2-二硝基丙醇缩乙醛混合物(A3)，在增塑比为0.5时，考察了不同叠氮基团与炔基基团的摩尔比(R值)对固化后的胶片力学性能的影响。结果表明：当R值为1.0时，固化形成的分子交联网络结构最完善，胶片的力学性能最佳，其断裂伸长率为150％，拉伸强度为0.9MPa，胶片的拉伸强度和断裂伸长率等力学性能偏低。
发明内容
针对现有技术中存在的不足，本发明的目的在于，提供一种端六叠氮基硝酸酯聚醚粘合剂及其合成方法，以克服上述弹性体胶片的力学性能偏低等问题。
为了解决上述技术问题，本发明采用如下技术方案予以实现：
一种端六叠氮基硝酸酯聚醚粘合剂，其结构式如下：
其中，n＝8～40，为整数。
一种所述的端六叠氮基硝酸酯聚醚粘合剂的合成方法，该方法首先以三叠氮新戊醇和缩水甘油醚硝酸酯为原料，三氟化硼·乙醚络合物为催化剂，通过阳离子开环聚合反应得到三叠氮新戊基聚缩水甘油醚硝酸酯醇；再以所述三叠氮新戊基聚缩水甘油醚硝酸酯醇和六亚甲基二异氰酸酯为原料，二丁基锡二月桂酸酯为催化剂，通过加成反应得到端六叠氮基聚缩水甘油醚硝酸酯，即为端六叠氮基硝酸酯聚醚粘合剂。
本发明还包括如下技术特征：
具体的，所述三叠氮新戊醇、缩水甘油醚硝酸酯和三氟化硼·乙醚络合物的摩尔比为1：8～40：0.3～0.6。。
具体的，所述三叠氮新戊基聚缩水甘油醚硝酸酯醇和六亚甲基二异氰酸酯的摩尔比为2：1，三叠氮新戊基聚缩水甘油醚硝酸酯醇和二丁基锡二月桂酸酯的质量比为1：0.0001～0.01。
具体的，包括以下步骤：
步骤1，三叠氮新戊基聚缩水甘油醚硝酸酯醇的合成：在反应瓶中加入二氯甲烷、三叠氮新戊基醇和三氟化硼·乙醚络合物，搅拌后，冰水浴降温至10℃，开始滴加缩水甘油醚硝酸酯，滴加完毕后继续反应，加入Na2CO3水溶液中和终止反应，有机相水洗至中性，浓缩后得到淡黄色粘稠液体；
步骤2，端六叠氮基聚缩水甘油醚硝酸酯的合成：室温下，在反应瓶中加入三叠氮新戊基聚缩水甘油醚硝酸酯醇、二丁基锡二月桂酸酯和六亚甲基二异氰酸酯，加热后反应，得到黄色粘稠液体，即为端六叠氮基硝酸酯聚醚粘合剂。
具体的，所述步骤1中，搅拌时间为30min～1h。
具体的，所述步骤1中，滴加缩水甘油醚硝酸酯的滴加时间为6h～15h，滴加完毕后继续反应12h～18h。
具体的，所述步骤2中，加热至60℃～70℃反应8h～12h。
本发明与现有技术相比，具有如下技术效果：
本发明的端六叠氮基硝酸酯聚醚粘合剂一方面在分子链两端引入了六个活性反应叠氮基团，具有较高的官能度，另一方面在主链中间引入了基团间具有较强的氢键作用的氨基甲酸酯基，用于合成聚三唑弹性体提高了硬链段的含量和交联密度，促进了弹性体微相分离，从而提高了力学性能。
本发明的端六叠氮基硝酸酯聚醚粘合剂基弹性体胶片20℃时拉伸强度为1.6MPa，断裂伸长率为185％；而现有技术中的N3PET4000基弹性体胶片20℃时拉伸强度为0.9MPa，断裂伸长率为150％。
具体实施方式
本发明的构思是：N3PET4000基弹性体胶片的力学性能偏低是由于N3PET4000粘合剂平均官能度为2左右，偏低，且硬链段聚三唑基团含量偏低，难于聚集促使弹性体微相分离。为了提高弹性体胶片的力学性能，本发明设想：选用分子链间作用力较强的聚缩水甘油醚硝酸酯为主链，一方面在分子链两端引入多个活性反应叠氮基团，提高官能度，另一方面在主链中间引入基团间具有较强的氢键作用的氨基甲酸酯基，起到物理交联作用的效果，促进弹性体的微相分离，从而提高弹性体的力学性能。
本发明的端六叠氮基硝酸酯聚醚粘合剂，其结构式如下：
其中，n＝8～40，为整数。
本发明的端六叠氮基硝酸酯聚醚粘合剂合成路线如下：
其中，n＝8～40，为整数。
本发明的端六叠氮基硝酸酯聚醚粘合剂合成方法包括以下步骤：
(1)以三叠氮新戊醇和缩水甘油醚硝酸酯为原料，三氟化硼·乙醚络合物为催化剂，通过阳离子开环聚合反应得到三叠氮新戊基聚缩水甘油醚硝酸酯醇。
(2)以三叠氮新戊基聚缩水甘油醚硝酸酯醇和六亚甲基二异氰酸酯为原料，二丁基锡二月桂酸酯为催化剂，通过加成反应得到端六叠氮基聚缩水甘油醚硝酸酯，即为本发明的端六叠氮基硝酸酯聚醚粘合剂。
以下给出本发明的具体实施例，需要说明的是本发明并不局限于以下具体实施例，凡在本申请技术方案基础上做的等同变换均落入本发明的保护范围。
测试仪器：
(1)红外光谱采用美国Nicolet公司的Nexus 870型傅里叶变换红外光谱仪测试；
(2)羟值采用邻苯二甲酸酐-吡啶酰化法测试。
(3)数均分子量
设备：英国PL公司GPC-50型凝胶渗透色谱仪；
GPC测试条件：色谱柱为PLgel MIXED-E串联；流动相为THF；柱温为40℃；检测器为示差折光检测器。
(4)力学性能
设备：美国Instron公司Instron 4505型万能材料试验机；
测试方法：按照GB/T528-1998方法。
实施例1：
本实施例提供一种端六叠氮基硝酸酯聚醚粘合剂及其合成方法，合成方法包括以下步骤：
步骤1，三叠氮新戊基聚缩水甘油醚硝酸酯醇的合成
在反应瓶中加入20mL二氯甲烷、2.11g三叠氮新戊基醇和0.71g三氟化硼·乙醚络合物，搅拌30min后，冰水浴降温至10℃，开始滴加17.85g缩水甘油醚硝酸酯，滴加时间为12h，滴加完毕后继续反应16h，加入Na2CO3水溶液中和终止反应，有机相水洗至中性，浓缩后得到淡黄色粘稠液体。
结构鉴定：
IR(KBr，cm-1)：3447(-OH)，2102(-N3)，1630、1281、870(-ONO2)，1123(C-O-C)。
分子量及分布：Mn＝1985，Mw＝2958，Mw/Mn＝1.49。
羟值：27.98mgKOH/g。
以上分析数据证实所合成的化合物为三叠氮新戊基聚缩水甘油醚硝酸酯醇。
步骤2，端六叠氮基聚缩水甘油醚硝酸酯的合成
室温下，在反应瓶中加入19.85g三叠氮新戊基聚缩水甘油醚硝酸酯醇、0.02g二丁基锡二月桂酸酯和0.84g六亚甲基二异氰酸酯，加热至65℃反应8h，得到黄色粘稠液体。
结构鉴定：
IR(KBr，cm-1)：3309(-NH-)，2102(-N3)，1740(C＝O)，1630、1281、870
(-ONO2)，1123(C-O-C)。
分子量及分布：Mn＝4120，Mw＝6922，Mw/Mn＝1.68。
以上分析数据证实所合成的化合物为端六叠氮基聚缩水甘油醚硝酸酯。
本发明的端六叠氮基硝酸酯聚醚粘合剂应用性能：
(1)与固化剂的混溶性评价
选用三炔丙基胺为固化剂，考察了端六叠氮基硝酸酯聚醚粘合剂与固化剂的混溶性以及反应性。
本发明的端六叠氮基硝酸酯聚醚粘合剂与三炔丙基胺固化剂具有很好的混溶性，混合物清澈透明，所形成的混合液在50～70℃下能够平稳的进行固化反应。
(2)弹性体的力学性能
将本发明的端六叠氮基硝酸酯聚醚粘合剂与三炔丙基胺固化剂固化，并且加入增塑剂A3，在增塑比为0.5时，制成A3增塑的聚三唑弹性体胶片，其力学性能结果见表1。
表1弹性体胶片的力学性能
可见，本发明的端六叠氮基硝酸酯聚醚粘合剂固化后的弹性体胶片力学性能明显优于N3PET4000固化后的弹性体胶片力学性能。
Claims (8)
1.一种端六叠氮基硝酸酯聚醚粘合剂，其特征在于，其结构式如下：
其中，n＝8～40，为整数。
2.一种权利要求1所述的端六叠氮基硝酸酯聚醚粘合剂的合成方法，其特征在于，该方法首先以三叠氮新戊醇和缩水甘油醚硝酸酯为原料，三氟化硼·乙醚络合物为催化剂，通过阳离子开环聚合反应得到三叠氮新戊基聚缩水甘油醚硝酸酯醇；再以所述三叠氮新戊基聚缩水甘油醚硝酸酯醇和六亚甲基二异氰酸酯为原料，二丁基锡二月桂酸酯为催化剂，通过加成反应得到端六叠氮基聚缩水甘油醚硝酸酯，即为端六叠氮基硝酸酯聚醚粘合剂。
3.如权利要求2所述的端六叠氮基硝酸酯聚醚粘合剂的合成方法，其特征在于，所述三叠氮新戊醇、缩水甘油醚硝酸酯和三氟化硼·乙醚络合物的摩尔比为1：8～40：0.3～0.6。
4.如权利要求3所述的端六叠氮基硝酸酯聚醚粘合剂的合成方法，其特征在于，所述三叠氮新戊基聚缩水甘油醚硝酸酯醇和六亚甲基二异氰酸酯的摩尔比为2：1，三叠氮新戊基聚缩水甘油醚硝酸酯醇和二丁基锡二月桂酸酯的质量比为1：0.0001～0.01。
5.如权利要求4所述的端六叠氮基硝酸酯聚醚粘合剂的合成方法，其特征在于，包括以下步骤：
步骤1，三叠氮新戊基聚缩水甘油醚硝酸酯醇的合成：在反应瓶中加入二氯甲烷、三叠氮新戊基醇和三氟化硼·乙醚络合物，搅拌后，冰水浴降温至10℃，开始滴加缩水甘油醚硝酸酯，滴加完毕后继续反应，加入Na2CO3水溶液中和终止反应，有机相水洗至中性，浓缩后得到淡黄色粘稠液体；
步骤2，端六叠氮基聚缩水甘油醚硝酸酯的合成：室温下，在反应瓶中加入三叠氮新戊基聚缩水甘油醚硝酸酯醇、二丁基锡二月桂酸酯和六亚甲基二异氰酸酯，加热后反应，得到黄色粘稠液体，即为端六叠氮基硝酸酯聚醚粘合剂。
6.如权利要求5所述的端六叠氮基硝酸酯聚醚粘合剂的合成方法，其特征在于，所述步骤1中，搅拌时间为30min～1h。
7.如权利要求5所述的端六叠氮基硝酸酯聚醚粘合剂的合成方法，其特征在于，所述步骤1中，滴加缩水甘油醚硝酸酯的滴加时间为6h～15h，滴加完毕后继续反应12h～18h。
8.如权利要求5所述的端六叠氮基硝酸酯聚醚粘合剂的合成方法，其特征在于，所述步骤2中，加热至60℃～70℃反应8h～12h。
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