CN110511372B - 一种含能端异氰酸酯基固化剂及其合成方法 - Google Patents

一种含能端异氰酸酯基固化剂及其合成方法 Download PDF

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CN110511372B
CN110511372B CN201910801643.9A CN201910801643A CN110511372B CN 110511372 B CN110511372 B CN 110511372B CN 201910801643 A CN201910801643 A CN 201910801643A CN 110511372 B CN110511372 B CN 110511372B
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李娜
赵凤起
杨燕京
安亭
张建侃
李辉
张明
蒋周峰
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Abstract

本发明属于固体推进剂领域，具体涉及一种含能端异氰酸酯基固化剂及其合成方法，其结构式如下：

Description

一种含能端异氰酸酯基固化剂及其合成方法
技术领域
本发明属于固体推进剂领域，具体涉及一种含能端异氰酸酯基固化剂及其合成方法。
背景技术
近几年来，人们对固体推进剂不仅要求其能量高，同是还要求微烟、少烟和低易损性，并认为发展新型含能粘合剂系统是同时兼顾解决这些矛盾的有效途径之一。叠氮粘合剂具有正的生成热、燃烧快、能量高、燃气清洁、热稳定性好和机械感度低等优点，因而是世界各国竞相研究的重要目标。自从1972年Vandenberg合成出GAP后不久，叠氮粘合剂剂在枪炮发射药、火箭推进剂、气体发生器和高能炸药中得到广泛应用，由于含能，故被用来代替传统惰性粘合剂(如HTPB或HTPE)。叠氮粘合剂是含端羟基的高分子聚合物，在使用时一般与多官能度异氰酸酯固化剂(如IPDI、N-100等)组成异氰酸酯固化体系，通过端羟基和异氰酸酯基反应固化，为了使叠氮推进剂具有良好的力学性能和结构完整性，必须选择或合成合适结构的叠氮粘合剂和固化剂，二者对推进剂的力学性能均有重要影响。
从提高力学性能和能量角度出发，理想的固化剂应具备以下几个条件：1)粘性液体；2)均为伯异氰酸酯基团；3)官能度≥3；4)带有能量基团；5)与粘合剂、硝酸酯增塑剂相溶性好。
欧洲专利EP 0 296 310公开了以叠氮缩水甘油醚(GAP)为基础的两种大分子液体叠氮固化剂的制备方法，但没有报道具体的力学性能数据，其结构如下所示：
Figure BDA0002182482570000011
《Synthesis and properties ofpoly-isocyanate energetic curing agent》Polymer Bulletin,2006,56(6):563～569，公开了一种以季戊四醇为起始剂，官能度为4的叠氮聚醚型含能固化剂Ec01～Ec03，其结构为：
Figure BDA0002182482570000021
上述大分子含能固化剂均是用低相对分子质量的GAP与六次甲基二异氰酸酯(HDI)经加成反应制得的。由于相应的GAP均是以1,4-丁二醇、三羟甲基丙烷、季戊四醇等链状脂肪醇为起始剂，因此这些GAP分子链中不含强极性基团，这也导致最终所得的叠氮固化剂存在分子链中所含强极性基团较少，分子链间的作用力较小等缺陷，所以上述固化剂并没有使叠氮粘合剂体系的力学性能有较为明显的改善。
发明内容
本发明所要解决的技术问题是克服背景技术的不足，提供一种力学性能较高的含能端异氰酸酯基固化剂及其制备方法。
本发明的构思是：1)在端异氰酸酯基固化剂分子中引入强极性基团氮杂环结构单元，通过增强分子间的作用力来提高弹性体的力学性能；2)在端异氰酸酯基固化剂中引入柔性的聚醚链，提高弹性体的延伸率；3)在端异氰酸酯基固化剂中引入叠氮基和硝酸酯基团来提高弹性体的能量。
为了解决上述技术问题，本发明提供的含能端异氰酸酯基固化剂，其结构式如下所示：
Figure BDA0002182482570000031
其中，x，y，z均为2～6的正整数。
本发明的合成路线如下所示：
Figure BDA0002182482570000032
其中，x，y，z均为2～6的正整数。
具体包括以下步骤：
1)以1,3,5-三羟乙基异氰尿酸酯为引发剂，三氟化硼乙醚络合物为催化剂，二氯乙烷为溶剂，3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷为单体，按阳离子开环聚合机理，合成端羟基3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷聚醚；所述1,3,5-三羟乙基异氰尿酸酯和3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷的摩尔比为1:6～18，1,3,5-三羟乙基异氰尿酸酯和三氟化硼乙醚络合物的摩尔比为2:1，反应温度为12℃～15℃。
2)在乙酸乙酯介质中，三苯基铋为催化剂，端羟基3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷聚醚与异佛尔酮二异氰酸酯反应形成含能端异氰酸酯基固化剂；所述端羟基3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷聚醚和异佛尔酮二异氰酸酯的摩尔比为1:3.1，反应温度为82℃～85℃。
本发明的有益效果：
1)含有与黑索金(RDX)、奥克托今(HMX)结构相类似的强极性基团氮杂环结构单元，能提高叠氮粘合剂体系网络分子链间的作用力，最终可提高叠氮聚氨酯弹性体的力学性能；2)含有能量基团，能允许叠氮粘合剂和固化剂的分子量有较大幅度的变化，使得推进剂配方调节有相对大的自由度；3)具有和叠氮粘合剂及硝酸酯粘合剂类似的主链结构，同时具有和硝酸酯增塑剂相同的硝酸酯基团，因此本发明固化剂和叠氮粘合剂、硝酸酯粘合剂和硝酸酯增塑剂都有着良好的相溶性，具备了调节力学性能的必要条件。
具体实施方式
下面结合实施例对本发明做进一步的说明。
数均分子量测试
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。
胶片力学性能测试
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。
实施例1
1含能端异氰酸酯基固化剂的合成
1.1端羟基3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷聚醚的合成
在一个配有机械搅拌、回流冷凝管、温度计、滴液漏斗的500ml四口圆底烧瓶中依次加入150ml二氯乙烷、22.47g(0.086mol)1,3,5-三羟乙基异氰尿酸酯(THEIC)和5.45ml(0.043mol)催化剂三氟化硼·乙醚络合物，室温搅拌30min后，开始滴加97.01g(0.516mol)的3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷(AMNMO)，滴加期间控制聚合温度在12～15℃，保温反应8h。用Na2CO3水溶液终止反应，有机相水洗至中性，浓缩，用石油醚萃取除去冠醚副产物，浓缩后得到淡黄色粘稠液体112.43g，产率94.1％。
结构表征：红外(KBr,cm-1)：3370(O-H),1470、769(氮杂环),1639、1285、878(－ONO2)，2109、1271(－N3)，1121(C-O-C)。
1.2含能端异氰酸酯基固化剂的合成
在一个配有机械搅拌、回流冷凝管、温度计、滴液漏斗的500ml四口圆底烧瓶中依次加入150ml乙酸乙酯、61.12g(0.044mol)端羟基3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷聚醚和0.46g(0.0011mol)三苯基铋，搅拌均匀，加热至60℃，然后向上述反应体系中滴加30.32g(0.136mol)异佛尔酮二异氰酸酯，滴加完毕后82℃～85℃反应10h。冷却至室温，将反应液倒入水中，用正己烷萃取，用水洗涤油相至中性，蒸除正己烷，真空干燥后，得到淡黄色透明液体84.95g，产率92.9％。
结构表征：红外(KBr,cm-1)：2771(－NCO)，2108、1271(－N3)，1720(－NHCO－)，1632、1285、876(－ONO2)，1320、935(氮杂环)，1129(C-O-C)。
理论数均分子量为2055，实测数均分子量为～2013。
上述数据证实所合成的化合物就是含有叠氮基和硝酸酯基聚醚链的端异氰酸酯基固化剂。
2本发明的应用性能
(1)与叠氮粘合剂和硝酸酯粘合剂的混溶性
选聚叠氮缩水甘油醚(GAP)和端羟基3-甲基-3-硝酸酯甲基氧杂环丁烷聚醚(PNIMMO)为粘合剂，考察了含能端异氰酸酯基固化剂与粘合剂的混溶性以及反应性。
本发明的含能端异氰酸酯基固化剂与GAP和PNIMMO粘合剂都具有很好的混溶性，混合物清澈透明，所形成的混合液在50～60℃下都能够平稳的进行固化反应。
(2)聚氨酯弹性体的力学性能
将GAP粘合剂分别与固化剂N100、IPDI、Ec01、Ec03和本发明固化剂反应生成聚氨酯弹性体，其中－NCO/－OH摩尔比为1.2/1，其相应的力学性能见表1：
表1固化剂对聚氨酯弹性体的力学性能(25℃)
Figure BDA0002182482570000061
由表1可见，与制式固化剂N100、IPDI相比，本发明的固化剂能提供较高的拉伸强度和延伸率，与理论官能度为4的固化剂EC01-EC03相比，本发明的固化剂能提供较高的拉伸强度。

Claims (1)

1.一种含能端异氰酸酯基固化剂的合成方法，其特征在于，固化剂的结构式如下：
Figure FDA0003509421390000011
其中，x，y，z均为2～6的正整数；
具体包括如下步骤：
1)以1,3,5-三羟乙基异氰尿酸酯为引发剂，三氟化硼乙醚络合物为催化剂，二氯乙烷为溶剂，3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷为单体，按阳离子开环聚合机理，合成端羟基3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷聚醚；
2)在乙酸乙酯介质中，三苯基铋为催化剂，端羟基3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷聚醚与异佛尔酮二异氰酸酯反应形成含能端异氰酸酯基固化剂；
所述步骤1)中引发剂1,3,5-三羟乙基异氰尿酸酯和3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷的摩尔比为1:6～18，引发剂1,3,5-三羟乙基异氰尿酸酯和三氟化硼乙醚络合物的摩尔比为2:1，反应温度为12℃～15℃；
所述步骤2)中端羟基3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷聚醚和异佛尔酮二异氰酸酯的摩尔比为1:3.1，三苯基铋和端羟基3-叠氮甲基-3-硝酸酯甲基氧杂环丁烷聚醚的摩尔比为1:40，反应温度为82℃～85℃。
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