CN113861699B - 一种抗小分子迁移、低发烟阻燃型耐烧蚀绝热材料及其制备方法 - Google Patents
一种抗小分子迁移、低发烟阻燃型耐烧蚀绝热材料及其制备方法 Download PDFInfo
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Abstract
一种抗小分子迁移、低发烟阻燃型耐烧蚀绝热材料及其制备方法，属于耐烧蚀材料技术领域。针对目前传统的柔性绝热材料的小分子易迁移、不环保等缺点；本发明提供了一种新型弹性体为基体的绝热材料配方及其制备方法，配方组份按重量计包括新型聚磷腈弹性体100份；活化剂3～5份；无机纤维0～15份；有机纤维0～20份；补强剂15～35份；耐热填料0～30份；耐烧蚀填料0～40份；硫化剂0.2～3份。本发明中的绝热材料相对于传统的三元乙丙、丁腈以及硅橡胶绝热材料具有更优异的阻燃性、耐烧蚀性、界面粘接性以及抗小分子迁移性。
Description
技术领域
本发明属于耐烧蚀材料技术领域，具体涉及一种抗小分子迁移、低发烟阻燃型耐烧蚀绝热材料及其制备方法。
背景技术
绝热层是位于固体火箭发动机燃烧室壳体内表面与推进剂之间的一类热防护材料，起着保护壳体免受推进剂燃烧室产生的高温高压环境对壳体的烧蚀和冲刷作用。随着当代航天及导弹火箭等向超高速运载的方向发展，对发动机的总体性能尤其是热防护材料提出了更严苛的要求。
目前的柔性绝热材料主要以丁腈橡胶(NBR)、三元乙丙橡胶(EPDM)以及硅橡胶绝热层为主。NBR绝热层具有强度高，粘接性能优异的特点，但存在耐烧蚀性能和工艺性能较差等问题；EPDM绝热层以其低密度，可填充性高、耐老化性能优异等优点在近年来得到了越来越广泛的应用，但存在自粘性和互粘性差的缺点；硅橡胶具有热稳定性好、使用温度范围宽等优点，但存在界面性能差，力学和加工性能不佳等问题。且传统的柔性绝热材料均存在阻燃性能差，发烟量高，抗小分子迁移能力较差等问题；针对于传统的绝热材料的高性能化主要通过在材料配方中添加大量的纤维、树脂、阻燃剂以及耐烧蚀填料等以满足绝热层耐烧蚀性能、力学性能以及工艺性能的要求。
聚磷腈是磷、氮原子以单双键交替结构为主链，每个磷原子上连接两个有机基团的有机-无机聚合物。因其独特的主链结构，使得大部分聚磷腈材料具有优异的热稳定性和阻燃性能。通过对聚磷腈侧基结构的调控，可以获得抗小分子迁移、低发烟量、耐烧蚀等级高等诸多优点的绝热材料。国外针对于聚磷腈在固体火箭发动机绝热层方面的应用进行了研究，如专利号为5024860的美国专利介绍了一种低发烟性的聚磷腈绝热材料；专利号为3970533和4116785的美国专利公布了Ethyl公司的一种高交联密度的含不饱和双键的具有优异的抗增塑剂迁移性的芳氧基聚磷腈绝热材料；专利号为5762746的美国专利介绍了法国Thiokol公司的一种具有优异耐烧蚀性的芳氧基聚磷腈绝热材料。国内北京化工大学在聚磷腈在绝热材料上的应用做了相应的研究，如2016年《High Performance Polymers》第225卷536-543页报道了聚磷腈基体本身的耐烧蚀性能便以达到常规三元乙丙和硅橡胶绝热层的水平。2021年《Journal of Applied Polymer Science》低138卷51222页报道了聚磷腈/芳纶纤维绝热材料具有优异的耐烧蚀性能。这充分表明聚磷腈材料在耐烧蚀热防护材料领域具有巨大的应用潜力，为高性能绝热层的开发提供了一种新思路。
发明内容
针对传统的柔性绝热材料基体存在抗小分子迁移性差，耐烧蚀性能调控工艺复杂、阻燃性能差以及发烟量高等问题，本发明以新型聚磷腈弹性体材料为基体，提供了一种抗小分子迁移，低烟阻燃型耐烧蚀绝热材料及其制备方法。
本发明所采用的技术方案：
本发明的绝热材料配方如下：一种抗小分子迁移、低发烟阻燃型耐烧蚀绝热材料，以重量份计，包括以下组份：聚磷腈弹性体100份；活化剂3～5份；无机纤维0～15份；有机纤维0～20份；补强剂15～35份；耐热填料0～30份；耐烧蚀填料0～40份；硫化剂0.2～3份。
进一步优选：聚磷腈弹性体100份；活化剂3～5份；无机纤维3～10份；有机纤维3～12份；补强剂20～30份；耐热填料5～14份；耐烧蚀填料5～15份；硫化剂0.5～1.5份。
优选地，所述的聚磷腈弹性体，其取代基基团为芳氧基、芳氨基、萘基、烷氧基或氟代烷氧基中的一种或几种。
优选地，所述的活化剂为氧化锌、氧化镁、硬脂酸、硬脂酸锌、硬脂酸镁中的一种或几种。
优选地，所述的无机纤维为碳纤维、石英纤维中的一种或两种的组合物。
优选地，所述的有机纤维为长纤状或浆粕状的聚酰亚胺纤维(PI)、聚对苯二甲酰对苯二胺(PA)、芳砜纶纤维(PSA)、聚对苯撑苯并双恶唑纤维(PBO)、聚丙烯腈纤维(PAN)、聚苯硫醚纤维(PPS)或酚醛纤维(PF)中的一种及一种以上的组合物。有机纤维长度为1-10mm。
优选地，所述的补强剂为二氧化硅、炭黑或者两者的组合物。
优选地，所述的耐热填料为粉状聚酰亚胺(PI)、酚醛树脂、聚对苯二甲酰对苯二胺(PA)、芳砜纶(PSA)或聚苯硫醚(PPS)中的一种或多种的组合，所述耐热填料的粒度小于100目。
优选地，所述的耐烧蚀填料为碳化硅粉、氧化锆粉、氧化铝粉、氮化硼粉、碳化硼粉、硼粉、云母粉、硅藻土粉、高岭土、硅灰石粉中的一种或多种的组合，所述耐烧蚀填料的粒度小于200目。
优选地，所述的硫化剂为过氧化二异丙苯、2,5-二甲基-2,5-二(过氧化苯甲酯)己烷、2,5-二甲基-2,5-双(叔丁基过氧基)己烷、过氧化二叔丁基、1,1-双(叔丁基过氧基)环己烷及其他有机过氧化物硫化剂。
一种抗小分子迁移、低发烟阻燃型耐烧蚀绝热材料的制备方法，其具体步骤为：
(1)固相混炼法：通过开放式炼胶机将聚磷腈弹性体基体塑炼后，加入活化剂、无机纤维、有机纤维、补强剂、耐热填料、耐烧蚀填料、硫化剂等经开炼机机械剪切力的作用下混炼均匀，薄通数次后出片；或将聚磷腈弹性体基体、活化剂、无机纤维、有机纤维、补强剂、耐热填料、耐烧蚀填料等加入密闭式捏合机中，混炼均匀后在开放式炼胶机上加硫化剂，混合均匀后薄通数次出片；混炼胶在120℃～180℃温度下硫化成型。
或(2)溶液混合法：将聚磷腈弹性体基体、活化剂、补强剂、耐热填料、耐烧蚀填料等置于有机溶剂中充分搅拌均匀后得到聚磷腈混合胶液，待胶液溶剂挥发完全后在开放式炼胶机中加入无机纤维、有机纤维及硫化剂，混合均匀后薄通数次出片，混炼胶在120℃～180℃温度下硫化成型；溶液混合法可以针对某类加工性能较差的聚磷腈弹性，且能够减少粉尘填料尤其是补强剂对环境的污染。
本发明所得绝热材料的应用，作为热防护材料，进一步作为固体火箭发动机燃烧室壳体内表面与推进剂之间的一类热防护材料。
本发明的的聚磷腈绝热材料具有如表1所示的性能：
本发明的有益效果是：制备的聚磷腈绝热材料在阻燃性能、发烟量、耐烧蚀性能以及抗小分子迁移性相较于传统的柔性绝热材料具有明显的优势。
具体实施方式
下面结合实施例，对本发明的具体实施方式作进一步的详细描述。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
具体实施例1：聚磷腈弹性体(取代基为芳氧基)，100份；氧化镁，1份；氧化锌3份；二氧化硅，30份；过氧化二异丙苯，1.5份。配方组份制备的绝热材料，其拉伸强度为8.4MPa、断裂伸长率为328％、线烧蚀率为0.067mm/s、质量烧蚀率为0.048g/s、氧指数LOI值为33、阻燃等级V0级、烟密度等级SDR为28.9、浸泡硝酸酯4周后吸收率为0.72％。而且材料的硫化性能优异，混炼工艺性能优良。
具体实施例2：聚磷腈弹性体(取代基为芳氧基)，100份；氧化镁，1份；氧化锌3份；石英纤维，3份；芳纶短切，5份；二氧化硅，30份，酚醛树脂，5份，氧化铝粉，15份；过氧化二异丙苯，1.5份。配方组份制备的绝热材料，其拉伸强度为10.2MPa、断裂伸长率为125％、线烧蚀率为0.036mm/s、质量烧蚀率为0.028g/s、氧指数LOI值为35、阻燃等级V0级、烟密度等级SDR为23.1、浸泡硝酸酯4周后吸收率为0.55％。而且材料的硫化性能优异，混炼工艺性能优良。
具体实施例3：聚磷腈弹性体(取代基为芳氧基)，100份；氧化镁，1份；氧化锌3份；碳纤维，3份；聚酰亚胺浆粕，5份；炭黑，30份，酚醛树脂，5份，氧化铝粉，15份；过氧化二异丙苯，1.5份。配方组份制备的绝热材料，其拉伸强度为8.2MPa、断裂伸长率为172％、线烧蚀率为0.045mm/s、质量烧蚀率为0.037g/s、氧指数LOI值为34、阻燃等级V0级、烟密度等级SDR为20.8、浸泡硝酸酯4周后吸收率为0.52％。而且材料的硫化性能优异，混炼工艺性能优良。
具体实施例4：聚磷腈弹性体(取代基为芳氧基)，100份；氧化镁，1份；氧化锌3份；碳纤维，3份；PBO短切，5份；二氧化硅，30份，聚酰亚胺粉，10份，氧化锆粉，15份；过氧化二异丙苯，1.5份。配方组份制备的绝热材料，其拉伸强度为9.6MPa、断裂伸长率为164％、线烧蚀率为0.028mm/s、质量烧蚀率为0.024/s、氧指数LOI值为36、阻燃等级V0级、烟密度等级SDR为19.7、浸泡硝酸酯4周后吸收率为0.32％。而且材料的硫化性能优异，混炼工艺性能优良。
具体实施例5：聚磷腈弹性体(取代基为芳氧基)，100份；氧化镁，1份；氧化锌3份；芳纶浆粕，10份；二氧化硅，30份，酚醛树脂，9份；过氧化二异丙苯，1.5份。配方组份制备的绝热材料，其拉伸强度为13.5MPa、断裂伸长率为55％、线烧蚀率为0.018mm/s、质量烧蚀率为0.014g/s、氧指数LOI值为39、阻燃等级V0级、烟密度等级SDR为18.7、浸泡硝酸酯4周后吸收率为0.25％。而且材料的硫化性能优异，混炼工艺性能优良。
具体实施例6：聚磷腈弹性体(取代基为芳氧基)，100份；氧化镁，1份；氧化锌3份；碳纤维，10份；二氧化硅，30份，PSA粉，15份；过氧化二异丙苯，1.5份。配方组份制备的绝热材料，其拉伸强度为7.6MPa、断裂伸长率为287％、线烧蚀率为0.049mm/s、质量烧蚀率为0.041g/s、氧指数LOI值为34、阻燃等级V0级、烟密度等级SDR为23.6、浸泡硝酸酯4周后吸收率为0.45％。而且材料的硫化性能优异，混炼工艺性能优良。
Claims (6)
1.一种抗小分子迁移、低发烟阻燃型耐烧蚀绝热材料，其特征在于，以重量份计，包括以下组份：
聚磷腈弹性体100份；活化剂3～5份；无机纤维3～10份；有机纤维3～12份；补强剂20～30份；耐热填料5～14份；耐烧蚀填料5～15份；硫化剂0.5～1.5份；
所述的耐热填料选自粉状聚酰亚胺PI、酚醛树脂、聚对苯二甲酰对苯二胺PA、芳砜纶PSA或聚苯硫醚PPS中的一种或多种的组合，所述耐热填料的粒度小于100目；
所述的聚磷腈弹性体，其取代基团为芳氧基、芳氨基、萘基、烷氧基或氟代烷氧基中的一种或几种；
所述的耐烧蚀填料为碳化硅粉、氧化锆粉、氧化铝粉、氮化硼粉、碳化硼粉、硼粉、云母粉、硅藻土粉、高岭土、硅灰石粉中的一种或多种的组合，所述耐烧蚀填料的粒度小于200目；
所述的无机纤维为碳纤维、石英纤维中的一种或两种的组合物；所述的有机纤维为1-10mm长纤状或浆粕状的聚酰亚胺纤维PI、聚对苯二甲酰对苯二胺PA、芳砜纶纤维PSA、聚对苯撑苯并二噁唑纤维PBO、聚丙烯腈纤维PAN、聚苯硫醚纤维PPS或酚醛纤维PF中的一种及一种以上的组合物；
所述的活化剂为氧化锌、氧化镁、硬脂酸、硬脂酸锌、硬脂酸镁中的一种或几种。
2.根据权利要求1所述的绝热材料，其特征在于：所述的补强剂选自二氧化硅、炭黑或者两者的组合物。
3.根据权利要求1所述的绝热材料，其特征在于：所述的硫化剂为过氧化二异丙苯、2,5-二甲基-2,5-二(过氧化苯甲酯)己烷、2,5-二甲基-2,5-双(叔丁基过氧基)己烷、过氧化二叔丁基、1,1-双(叔丁基过氧基)环己烷及其他有机过氧化物硫化剂。
4.权利要求1-3任一项所述的一种抗小分子迁移、低发烟阻燃型耐烧蚀绝热材料的制备方法，其特征在于，包含以下方法：
(1)固相混炼法：通过开放式炼胶机将聚磷腈弹性体基体塑炼后，加入活化剂、无机纤维、有机纤维、补强剂、耐热填料、耐烧蚀填料、硫化剂经开炼机机械剪切力的作用下混炼均匀，薄通数次后出片；或将聚磷腈弹性体基体、活化剂、无机纤维、有机纤维、补强剂、耐热填料、耐烧蚀填料加入密闭式捏合机中，混炼均匀后在开放式炼胶机上加硫化剂，混合均匀后薄通数次出片；混炼胶在120℃～180℃温度下硫化成型；
或(2)溶液混合法：将聚磷腈弹性体基体、活化剂、补强剂、耐热填料、耐烧蚀填料置于有机溶剂中充分搅拌均匀后得到聚磷腈混合胶液，待胶液溶剂挥发完全后在开放式炼胶机中加入无机纤维、有机纤维及硫化剂，混合均匀后薄通数次出片，混炼胶在120℃～180℃温度下硫化成型。
5.权利要求1-3任一项所述的一种抗小分子迁移、低发烟阻燃型耐烧蚀绝热材料作为热防护材料的应用。
6.根据权利要求5所述的应用，其特征在于，作为固体火箭发动机燃烧室壳体内表面与推进剂之间的一类热防护材料的应用。
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