CN115216009B - 一种热塑性多元杂化聚酰亚胺薄膜的制备方法 - Google Patents
一种热塑性多元杂化聚酰亚胺薄膜的制备方法 Download PDFInfo
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- CN115216009B CN115216009B CN202210988168.2A CN202210988168A CN115216009B CN 115216009 B CN115216009 B CN 115216009B CN 202210988168 A CN202210988168 A CN 202210988168A CN 115216009 B CN115216009 B CN 115216009B
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- diisocyanate
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- thermoplastic
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Abstract
本发明公开了一种热塑性多元杂化聚酰亚胺薄膜的制备方法,包括以下步骤:S1、将芳香二异氰酸酯加入到芳香二元酸酐溶液体系中,得酸酐封端的含有七元环结构聚酰亚胺前驱体溶液,为溶液I;S2、将芳香二元酸酐加入到芳香二元胺溶液体系中,得氨基封端的聚酰胺酸溶液,为溶液II;S3、将溶液I和溶液II进行混合,得均匀的多元聚合溶液;S4、将多元聚合溶液延展成膜后,先后依次在真空烘箱和普通烘箱中分别进行梯度升温固化,得热塑性多元杂化聚酰亚胺薄膜。本发明快速地制备了综合性能更加优良的热塑性多元杂化聚酰亚胺薄膜,制备工艺简单,且有效降低了生产成本。
Description
技术领域
本发明涉及一种高性能膜材料,特别是一种热塑性多元杂化聚酰亚胺薄膜的制备方法。
背景技术
众所周知,聚酰亚胺主要包括酸酐-胺体系聚酰亚胺和异氰酸酯基型聚酰亚胺。酸酐-胺体系聚酰亚胺聚合工艺简单,通过酸酐和二胺合成聚酰胺酸溶液,再通过热固化或者化学脱水环化即可生成聚酰亚胺,但高温固化时聚酰胺酸链易发生部分裂解,使得聚酰亚胺链长小于前驱体聚酰胺酸链长,对薄膜性能造成极大影响。异氰酸酯基型聚酰亚胺制备是以二异氰酸酯和二元酸酐作为反应单体,首先合成七元环中间体,再在高温条件下将七元环转化生成酰亚胺环结构。但由于异氰酸酯和酸酐都是亲电型单体,缩聚反应时链段聚合度不高,异氰酸酯基型聚酰亚胺薄膜的机械性能较差(拉伸强度为60~70MPa),疏水性能也不是很理想(静态水接触角约为66°),极大限制了其在微电子领域的应用,导致电子器件在使用过程中存在吸湿电击穿和封装基材断裂等问题。此外,聚酰亚胺薄膜还普遍存在较差疏水性能较差的问题,这是由于酰亚胺结构中的氧、氮极化率较大,电负性较强,能够作为给电子体与水分子中的氢原子形成稳定的氢键。
专利CN109762166B公开了一种聚酰亚胺前驱体及聚酰亚胺薄膜的制备方法,使用二胺为桥连剂链接低聚态酐基封端七元环前驱体,成功制备了机械性能改善的异氰酸酯基型聚酰亚胺薄膜,拉伸强度最高达到114MPa,但疏水性能一般。专利CN110358121A公开了一种通过微波辐射低温制备聚酰亚胺薄膜的方法,依靠微波辐照低温酰亚胺化减少聚酰胺酸的降解,使酸酐-胺体系聚酰亚胺薄膜拉伸强度达到121MPa。但受限于微波设备箱体尺寸,以及极长的处理时间,此工艺并不适合聚酰亚胺薄膜的产业化。专利CN114196049A公开了一种强疏水聚酰亚胺薄膜的制备方法,通过含氟疏水改性剂与二氧化硅复配使用,制备出具有良好疏水性能的聚酰亚胺薄膜;专利 CN111635525A公开了一种低介电常数疏水聚酰亚胺薄膜及其制备方法,通过使用含氟单体和改性TS-1分子筛复合制备具有低介电常数和良好疏水性能的聚酰亚胺薄膜;专利CN105315466B公开了一种主链含氟硅结构聚酰亚胺的制备方法,通过全氟异氰酸酯等单体间的共聚反应,成功制备出具有良好疏水性能的聚酰亚胺薄膜。虽然含氟结构的引入能够有效改善聚酰亚胺薄膜的疏水性,但其单体价格明显高于普通二酐单体,大大增加了疏水聚酰亚胺薄膜的生产成本。如:常用的含氟酸酐单体4,4′-(六氟异丙烯)二酞酸酐价格比3,3'4,4'-二苯甲酮四羧酸二酐高5倍以上,比均苯四甲酸二酐高20倍以上。同时,受限于复杂、高成本的制备流程,现有技术路线并不适于工业化。
由此可知,定向分子结构设计以及制备工艺改进是获得高性能本征型聚酰亚胺薄膜最常用的手段。但由于新型结构的设计难度较大、特种结构单体以及复杂制备工艺的生产成本极高,不可避免地为高性能本征型聚酰亚胺薄膜产品低成本工业化生产带来极大阻力。
发明内容
本发明的目的在于,提供一种热塑性多元杂化聚酰亚胺薄膜的制备方法。本发明简单、快速地制备了综合性能更加优良的热塑性多元杂化聚酰亚胺薄膜,且有效降低了生产成本。
本发明的技术方案:一种热塑性多元杂化聚酰亚胺薄膜的制备方法,包括以下步骤:
S1、按照酸酐与异氰酸酯的摩尔比为1.05:1~1.10:1,将芳香二异氰酸酯加入到芳香二元酸酐溶液体系中,于氮气氛围下搅拌反应 8~12h,得酸酐封端的含有七元环结构聚酰亚胺前驱体溶液,为溶液 I;
S2、按照二胺与酸酐的摩尔比为1.04:1~1.08:1,将芳香二元酸酐加入到芳香二元胺溶液体系中,搅拌反应4~8h,得氨基封端的聚酰胺酸溶液,为溶液II;
S3、将溶液I和溶液II按照重量比为1:1.6~1:3.2进行混合,混合反应10~20min后得均匀的多元聚合溶液;
S4、将多元聚合溶液延展成膜后,先后依次在真空烘箱和普通烘箱中分别进行梯度升温固化,冷却后得热塑性多元杂化聚酰亚胺薄膜。
前述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法中,所述溶液I中酸酐封端的含有七元环结构聚酰亚胺前驱体的重量百分比为 15%~25%;溶液II中氨基封端的聚酰胺酸的重量百分比为15%~25%。
前述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法中,所述溶液I的反应温度为90~100℃;所述溶液II的反应温度为-5~25℃;所述步骤S3的混合温度为-15~25℃。
前述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法中,所述步骤S2中,芳香二元酸酐和芳香二元胺溶液的混合方法为:将芳香二元酸酐均匀分为4~6份,分2~4批加入含芳香二元胺的极性溶剂溶液中,待前一批溶解完全后立即加入下一批,每批用量为1~3份。
前述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法中,所述步骤S1中的芳香二异氰酸酯包括2,4'-二苯基甲烷二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,2'-亚甲基二苯基二异氰酸酯、甲苯-2,4-二异氰酸酯、甲苯-2,5-二异氰酸酯、甲苯-2,6-二异氰酸酯、甲苯-3,4-二异氰酸酯、甲苯-3,5-二异氰酸酯、3,3'-二甲基联苯基-4,4'-二异氰酸酯、间苯二异氰酸酯、对苯二异氰酸酯、邻苯二甲基二异氰酸酯、萘基二异氰酸酯、苯二亚甲基二异氰酸酯和四甲基苯二亚甲基二异氰酸酯中一种或多种的混合物。
前述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法中,所述步骤S1和步骤S2中的芳香二元酸酐包括均苯四甲酸二酐、二溴均苯四甲酸二酐、4,4'-联苯醚二酐、3,3',4,4'-二苯醚四甲酸二酐、3,3',4,4'-二苯基砜四羧酸二酸酐、3,3',4,4'-联苯四甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、2,3,3',4'-二苯醚四甲酸二酐、3,3',4,4'-三苯双醚四甲酸二酐、 4,4'-(4,4'-异丙基二苯氧基)四甲酸酐、2,2'-二甲基-3,3',4,4'-联苯四甲酸二酐、2,2'-二苯基-3,3',4,4'-联苯四甲酸二酐和5,5'-亚甲基双(异苯并呋喃-1,3-二酮)中的一种或多种的混合物。
前述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法中,所述步骤S2中的芳香二元胺包括3,4'-二氨基二苯醚、4,4'-二氨基二苯醚、 4,4'-二氨基二苯甲酮、1,3-二(3-氨基苯氧基)苯、1,3-二(4-氨基苯氧基)苯、间苯二胺、对苯二胺、3,3'-二氨基二苯砜、4,4'-二氨基二苯基砜、4-二(4-双氨基苯氧基)二苯基砜、4-二(3-双氨基苯氧基) 苯基砜、4,4'-二(3-氨基苯氧基)联苯、4,4'-二(4-氨基苯氧基)联苯、4,4'-二氨基二苯基甲烷和二乙基甲苯二胺中一种或多种的混合物。
前述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法中,所述步骤S4中的梯度升温固化包括第一梯度升温阶段和第二梯度升温阶段,第一梯度升温阶段为:在真空烘箱中依次升温至80~90℃、 100~110℃、130~140℃,每个温度段均固化2~3h,期间保持真空度为75~85kPa;第二梯度升温阶段为:在普通烘箱中依次升温至 160~180℃、190~210℃、240~260℃、290~310℃和320~340℃,每个温度段均固化1~2h。
与现有技术相比,本发明的有益效果为:
本发明提供了一种通过多元杂化复合实现本征力学、疏水性能增强的热塑性聚酰亚胺薄膜及制备方法。本发明将廉价单体合成的酸酐封端的含有七元环结构聚酰亚胺前驱体溶液以及氨基封端的聚酰胺酸溶液,再次进行混合反应,利用两类短直链封端聚酰亚胺前驱体间的端基反应、溶液配比及固化温度的阶段性控制,在不改变短直链原有结构的条件下,一步实现两类聚酰亚胺结构的杂化复合与化学键合,快速制备出热性能良好、本征力学性能和疏水性能显著增强的热塑性多元杂化聚酰亚胺薄膜。解决了纯异氰酸酯基型聚酰亚胺薄膜耐热、力学的问题(50~70MPa,亲水)以及酸酐-胺体系聚酰亚胺薄膜前驱体高温固化过程所存在的结构易裂解等问题。
同时,短直链增长和分子量增加,一方面弥补了聚酰亚胺高温断链所引起的分子量和力学性能降低问题,使膜的力学性能得到改善;另一方面可以提高局部结晶度、改善直链取向度,有效降低了水分子的透过率,大幅提高了膜的疏水性能,解决两大体系不含氟型聚酰亚胺薄膜疏水性差的通病。
所制备的热塑性多元杂化聚酰亚胺薄膜,拉伸强度为 101.40~126.04MPa,相较于单独由酸酐封端的含有七元环结构聚酰亚胺前驱体溶液制得的异氰酸酯基型薄膜以及单独由氨基封端的聚酰胺酸溶液制得的酸酐-胺体系聚酰亚胺薄膜,其拉升强度分别提高53%~91%和3%~28%。同时,热塑性多元杂化聚酰亚胺薄膜还具有良好的本征疏水性能,在不含任何含氟官能团的条件下的静态水接触角为98~100°。
本发明在不引入特种单体、其他高分子链段以及高性能疏水填料的前提下,仅通过合成与固化工艺的创新和优化,成功制备出综合性能更加优良,尤其是疏水性能更加优异的热塑性聚酰亚胺薄膜,制备工艺简单,改性策略巧妙,具备实现工业化潜力。同时,有效降低高性能聚酰亚胺薄膜生产原材料成本,提高生产企业的利润率。
附图说明
图1是本发明实施实例与对比案例制备的系列聚酰亚胺薄膜数码照片;
图2是本发明实施实例所制备的薄膜静态水接触角;
图3是本发明实施实例与对比案例制备的系列聚酰亚胺薄膜应力应变曲线。
具体实施方式
一种热塑性多元杂化聚酰亚胺薄膜的制备方法,包括以下步骤:
S1、按照酸酐与异氰酸酯的摩尔比为1.05:1~1.10:1,将芳香二异氰酸酯缓慢滴加到芳香二元酸酐溶液体系中,于氮气氛围下搅拌反应 8~12h,反应温度为90~100℃,得酸酐封端的含有七元环结构聚酰亚胺前驱体溶液,为溶液I;溶液I中酸酐封端的含有七元环结构聚酰亚胺前驱体的重量百分比为15%~25%。
S2、按照二胺与酸酐的摩尔比为1.04:1~1.08:1,将芳香二元酸酐均匀分为4~6份,分2~4批加入含芳香二元胺的极性溶剂溶液中,待前一批溶解完全后立即加入下一批,每批用量1~3份,有效保证聚合度以及分子量,搅拌反应4~8h,反应温度为-5~25℃,得氨基封端的聚酰胺酸溶液,为溶液II;溶液II中氨基封端的聚酰胺酸的重量百分比为15%~25%。
S3、将溶液I和溶液II按照重量比为1:1.6~1:3.2进行混合,混合温度为-15~25℃,混合反应10~20min后得均匀的多元聚合溶液;
S4、将多元聚合溶液延展成膜后,先后依次在真空烘箱和普通烘箱中分别进行梯度升温固化,具体包括第一梯度升温阶段和第二梯度升温阶段,第一梯度升温阶段为:在真空烘箱中依次升温至80~90℃、 100~110℃、130~140℃进行固化,每个温度段均固化2~3h,期间保持真空度为75~85kPa;该阶段控制溶剂和二氧化碳的挥发速率,减少薄膜表面气泡产生,保证表观品质。
第二梯度升温阶段为:在普通烘箱中依次升温至160~180℃、 190~210℃、240~260℃、290~310℃和320~340℃进行固化,每个温度段均固化1~2h;该阶段实现溶剂全去除及酰亚胺结构的完全转变。
冷却后得热塑性多元杂化聚酰亚胺薄膜。
芳香二异氰酸酯包括2,4'-二苯基甲烷二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,2'-亚甲基二苯基二异氰酸酯、甲苯-2,4-二异氰酸酯、甲苯-2,5-二异氰酸酯、甲苯-2,6-二异氰酸酯、甲苯-3,4-二异氰酸酯、甲苯-3,5-二异氰酸酯、3,3'-二甲基联苯基-4,4'-二异氰酸酯、间苯二异氰酸酯、对苯二异氰酸酯、邻苯二甲基二异氰酸酯、萘基二异氰酸酯、苯二亚甲基二异氰酸酯和四甲基苯二亚甲基二异氰酸酯中一种或多种的混合物。
芳香二元酸酐包括均苯四甲酸二酐、二溴均苯四甲酸二酐、4,4'- 联苯醚二酐、3,3',4,4'-二苯醚四甲酸二酐、3,3',4,4'-二苯基砜四羧酸二酸酐、3,3',4,4'-联苯四甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、 2,3,3',4'-二苯醚四甲酸二酐、3,3',4,4'-三苯双醚四甲酸二酐、4,4'-(4,4'- 异丙基二苯氧基)四甲酸酐、2,2'-二甲基-3,3',4,4'-联苯四甲酸二酐、2,2'- 二苯基-3,3',4,4'-联苯四甲酸二酐和5,5'-亚甲基双(异苯并呋喃-1,3-二酮)中的一种或多种的混合物。
芳香二元胺包括3,4'-二氨基二苯醚、4,4'-二氨基二苯醚、4,4'-二氨基二苯甲酮、1,3-二(3-氨基苯氧基)苯、1,3-二(4-氨基苯氧基) 苯、间苯二胺、对苯二胺、3,3'-二氨基二苯砜、4,4'-二氨基二苯基砜、 4-二(4-双氨基苯氧基)二苯基砜、4-二(3-双氨基苯氧基)苯基砜、 4,4'-二(3-氨基苯氧基)联苯、4,4'-二(4-氨基苯氧基)联苯、4,4'- 二氨基二苯基甲烷和二乙基甲苯二胺中一种或多种的混合物。
下面结合实施实例对本发明作进一步的说明,但并不作为对本发明限制的依据。
实施实例1:
S1、将油浴锅预热至95℃,向装有57.6g的N-甲基吡咯烷酮的三口烧瓶中加入8.4g的3,3',4,4',-二苯甲酮四甲酸二酐(0.026mol)。待搅拌溶解完全后,将6.0g的二苯甲烷二异氰酸酯(0.024mol)缓慢滴加入三口烧瓶中,通氮气保护,并冷凝回流,搅拌反应10h,得到酸酐封端的含有七元环结构的聚酰亚胺前驱体的重量百分比为20%的溶液,即溶液I。
S2、25℃条件下,向装有73.33g的N-甲基吡咯烷酮的三口烧瓶中加入5.21g的4,4'-二氨基二苯醚(0.026mol)。待搅拌溶解完全后,将7.73g的3,3',4,4',-二苯甲酮四甲酸二酐(0.024mol)均匀分为4份,并分4批加入到三口烧瓶中,待前一批溶解完全后立即加入下一批,每批1份,搅拌反应6h,得到氨基封端的聚酰胺酸的重量百分比为 15%的溶液,即溶液II。
S3、将10g的溶液II和5g的溶液I依次加入烧杯中,在25℃条件下搅拌反应12min后得到均匀的二元聚合溶液。
S4、将二元聚合溶液倒在洁净的玻璃板上流延成膜,将湿膜放入真空烘箱中进行第一梯度升温阶段的升温固化,具体为依次升温至 80℃、110℃和140℃,每次固化时间为3h,真空度为80kPa;再将薄膜转移至普通烘箱中进行第二梯度升温阶段的升温固化,具体为依次升温至170℃、200℃、250℃、300℃和330℃,固化时间分别为 2h、2h、1h、1h和1h进行固化。冷却后得到热塑性多元杂化聚酰亚胺薄膜。
实施实例2:
S1、将油浴锅预热至95℃,再向装有56g的N-甲基吡咯烷酮的三口烧瓶中加入8g的4,4'-联苯醚二酐(0.026mol)。待搅拌溶解完全后,将6g的二苯甲烷二异氰酸酯(0.024mol)缓慢滴加入三口烧瓶中,通氮气保护,并冷凝回流,搅拌反应10h,得到酸酐封端的含有七元环结构的聚酰亚胺前驱体的重量百分比为20%的溶液,即溶液I。
S2、25℃条件下,向装有71.68gN-甲基吡咯烷酮的三口烧瓶中加入5.21g的4,4'-二氨基二苯醚(0.026mol)。待搅拌溶解完全后,将 7.44g的4,4'-联苯醚二酐(0.024mol)均匀分为4份,并分4批加入到三口烧瓶中,待前一批溶解完全后立即加入下一批,每批1份,搅拌反应6h,得到氨基封端的聚酰胺酸的重量百分比为15%的溶液,即溶液II。
S3、将10.38g的溶液II和4.38g的溶液I依次加入烧杯中,在 25℃条件下搅拌反应12min后得到均匀的二元聚合溶液。
S4、将二元聚合溶液倒在洁净的玻璃板上流延成膜,将湿膜放入真空烘箱中进行第一梯度升温阶段的升温固化,具体为依次升温至80℃、110℃和140℃,每次固化时间为3h,真空度为80kPa;再将薄膜转移至普通烘箱中进行第二梯度升温阶段的升温固化,具体为依次升温至170℃、200℃、250℃、300℃和330℃进行固化,固化时间分别为2h、2h、1h、1h和1h。冷却后得到热塑性多元杂化聚酰亚胺薄膜。
对比案例1:
将油浴锅预热至95℃,再向装有27g的N-甲基吡咯烷酮的三口烧瓶中加入5g的4,4'-联苯醚二酐(0.016mol)。待搅拌溶解完全后,将4.0g的二苯甲烷二异氰酸酯(0.016mol)缓慢滴加入三口烧瓶中,通氮气保护,并冷凝回流,搅拌反应10h,得到含七元环结构的聚酰亚胺前驱体的重量百分比为25%的溶液。取10g的聚酰亚胺前驱体溶液,在洁净的玻璃板上流延成膜。将湿膜放入真空烘箱依次升温至 80℃、110℃和140℃进行固化,每次固化时间为3h,真空度为80kPa。再将薄膜转移至普通烘箱中依次升温至170℃、200℃、220℃进行固化,固化时间分别为2h、2h、1h。冷却后得到异氰酸酯基型聚酰亚胺薄膜。
对比案例2:
25℃条件下,向装有38.28g的N-甲基吡咯烷酮的三口烧瓶中加入5g的4,4'-二氨基二苯醚(0.025mol)。待搅拌溶解完全后,将7.76g 的4,4'-联苯醚二酐(0.025mol)均匀分为4份,并分4批加入到三口烧瓶中,待前一批溶解完全后立即加入下一批,每批1份,搅拌反应 6h,得到聚酰胺酸的重量百分比为25%的溶液。取10g的聚酰胺酸溶液,在洁净的玻璃板上流延成膜。将湿膜放入真空烘箱依次升温至 80℃、110℃和140℃进行固化,每个温度下均保持固化时间为3h,真空度为80kPa。再将薄膜转移至普通烘箱中依次升温至170℃、 200℃、250℃、300℃、330℃进行固化,固化时间分别为2h、2h、 1h、1h、1h。冷却后得到酸酐-胺体系聚酰亚胺薄膜。
对比案例3:
将油浴锅预热至95℃,再向装有27g的N-甲基吡咯烷酮的三口烧瓶中加入5g的4,4'-联苯醚二酐(0.016mol)。待搅拌溶解完全后,将4.0g的二苯甲烷二异氰酸酯(0.016mol)缓慢滴加入三口烧瓶中,通氮气保护,并冷凝回流,搅拌反应10h,得到含七元环结构的聚酰亚胺前驱体的重量百分比为25%的溶液。取10g的聚酰亚胺前驱体溶液,在洁净的玻璃板上流延成膜。将湿膜先放入真空烘箱中依次升温至80℃、120℃、160℃进行固化,每次固化时间为2h,保持真空度为80kPa。再将薄膜转移至普通烘箱中依次升温至200℃、250℃和 300℃进行固化,每次固化时间为1h。冷却后得到异氰酸酯基型聚酰亚胺薄膜。
对比案例4:
将油浴锅预热至95℃,再向装有27g的N-甲基吡咯烷酮的三口烧瓶中加入5g的4,4'-联苯醚二酐(0.016mol)。待搅拌溶解完全后,将4.0g的二苯甲烷二异氰酸酯(0.016mol)缓慢滴加入三口烧瓶中,通氮气保护,并冷凝回流,搅拌反应10h,得到含七元环结构的聚酰亚胺前驱体的重量百分比为25%的溶液。取10g的聚酰亚胺前驱体溶液,在洁净的玻璃板上流延成膜。将湿膜放入真空烘箱中依次升温至 80℃、110℃、140℃进行固化,每次固化时间为3h,保持真空度为 80kPa。再将薄膜转移至普通烘箱中依次升温至170℃、200℃、250℃、300℃和330℃进行固化,每次固化时间分别为2h、2h、1h、1h和1h。冷却后得到异氰酸酯基型聚酰亚胺薄膜。
薄膜的性能测试试验:
测试样品:实施实例1、实施实例2、对比案例1、对比案例2、对比案例3和对比案例4制得的薄膜。
测试方法与标准具体如下:
力学性能的拉伸测试根据GB/T 13022-1991测试标准,样品为 10*150mm的长条形试样,拉伸速率为2mm/min。
热重测试的升温速率为20℃/min。DSC测试的升温速率为10℃/min。
数码照片拍摄时的放大倍数为1.5倍。
水接触角测试根据GB/T 30693-2014测试标准,水滴体积为1μL,测试温度为23℃,相对湿度为52%。
薄膜的拉伸性能测试结果见表1,薄膜的热性能测试结果见表2,表2中,T5%和T10%是指样品在热分析测试过程中质量损失5%和10%所对应的温度,用来表征多元杂化聚酰亚胺薄膜的热稳定性。薄膜的数码照片见图1,薄膜的静态水接触角测试结果见图2,薄膜的应力应变性能结果见图3。
表1本发明实施实例与对比案例中聚酰亚胺薄膜的力学性能数据
表1中,增幅1和增幅2是指实施实例1和实施实例2分别相较于对比案例1和对比案例2的拉伸强度的提升比例。
表2本发明实施实例中系列聚酰亚胺薄膜的热性能数据
样品 | T5%/℃ | T10%/℃ | Tg/℃ |
实施实例1 | 541 | 564 | 262 |
实施实例2 | 549 | 568 | 265 |
实验结论:由图1的数码照片可以看出,实施实例1和实施实例 2中的多元杂化聚酰亚胺薄膜表面平整光滑,具有良好的成膜效果。对比案例1、3和4相当于单独由溶液I制备得到的异氰酸酯基型聚酰亚胺薄膜,对比案例2相当于单独由溶液II制备得到的酸酐-胺体系聚酰亚胺薄膜,通过对比案例1、3和4可以发现,在普通梯度升温固化程序和本发明的梯度升温固化程序下,单独由溶液I制备的异氰酸酯基型聚酰亚胺薄膜在高温下均无法成膜,存在大量气泡以及碎裂等情况,只有在最高固化温度为220℃下可以成膜。
由图3和表1中的数据可以看出,实施实例1和实施实例2中的多元杂化聚酰亚胺薄膜具有显著增强的机械性能。其中,拉伸强度分别为126.04MPa、101.40MPa,相较于对比案例1和对比案例2,分别提高了91%、28%和53%、3%。
由表2中的热性能数据可以看出,实施实例1、实施实例2中的多元杂化聚酰亚胺薄膜具有良好的热稳定性能。同时,由图2可以看出实施实例1、实施实例2中的多元杂化聚酰亚胺薄膜还具有良好的本征疏水性能,在不含任何含氟官能团的条件下的静态水接触角分别达到了100.49°、97.56°。
Claims (7)
1.一种热塑性多元杂化聚酰亚胺薄膜的制备方法,其特征在于:包括以下步骤:
S1、按照酸酐与异氰酸酯的摩尔比为1.05:1~1.10:1,将芳香二异氰酸酯加入到芳香二元酸酐溶液体系中,于氮气氛围下搅拌反应8~12h,得酸酐封端的含有七元环结构聚酰亚胺前驱体溶液,为溶液I;所述溶液I中酸酐封端的含有七元环结构聚酰亚胺前驱体的重量百分比为15%~25%;
S2、按照二胺与酸酐的摩尔比为1.04:1~1.08:1,将芳香二元酸酐加入到芳香二元胺溶液体系中,搅拌反应4~8h,得氨基封端的聚酰胺酸溶液,为溶液II;溶液II中氨基封端的聚酰胺酸的重量百分比为15%~25%;
S3、将溶液I和溶液II按照重量比为1:1.6~1:3.2进行混合,混合反应10~20min后得均匀的多元聚合溶液;
S4、将多元聚合溶液延展成膜后,先后依次在真空烘箱和普通烘箱中分别进行梯度升温固化,冷却后得热塑性多元杂化聚酰亚胺薄膜。
2.根据权利要求1所述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法,其特征在于:所述溶液I的反应温度为90~100℃;所述溶液II的反应温度为-5~25℃;所述步骤S3的混合温度为-15~25℃。
3.根据权利要求1所述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法,其特征在于:所述步骤S2中,芳香二元酸酐和芳香二元胺溶液的混合方法为:将芳香二元酸酐均匀分为4~6份,分2~4批加入含芳香二元胺的极性溶剂溶液中,每批用量为1~3份。
4.根据权利要求1所述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法,其特征在于:所述步骤S1中的芳香二异氰酸酯包括2,4'-二苯基甲烷二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、2,2'-亚甲基二苯基二异氰酸酯、甲苯-2,4-二异氰酸酯、甲苯-2,5-二异氰酸酯、甲苯-2,6-二异氰酸酯、甲苯-3,4-二异氰酸酯、甲苯-3,5-二异氰酸酯、3,3'-二甲基联苯基-4,4'-二异氰酸酯、间苯二异氰酸酯、对苯二异氰酸酯、邻苯二甲基二异氰酸酯、萘基二异氰酸酯、苯二亚甲基二异氰酸酯和四甲基苯二亚甲基二异氰酸酯中一种或多种的混合物。
5.根据权利要求1所述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法,其特征在于:所述步骤S1和步骤S2中的芳香二元酸酐包括均苯四甲酸二酐、二溴均苯四甲酸二酐、4,4'-联苯醚二酐、3,3',4,4'-二苯醚四甲酸二酐、3,3',4,4'-二苯基砜四羧酸二酸酐、3,3',4,4'-联苯四甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、2,3,3',4'-二苯醚四甲酸二酐、3,3',4,4'-三苯双醚四甲酸二酐、4,4'-(4,4'-异丙基二苯氧基)四甲酸酐、2,2'-二甲基-3,3',4,4'-联苯四甲酸二酐、2,2'-二苯基-3,3',4,4'-联苯四甲酸二酐和5,5'-亚甲基双(异苯并呋喃-1,3-二酮)中的一种或多种的混合物。
6.根据权利要求1所述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法,其特征在于:所述步骤S2中的芳香二元胺包括3,4'-二氨基二苯醚、4,4'-二氨基二苯醚、4,4'-二氨基二苯甲酮、1,3-二(3-氨基苯氧基)苯、1,3-二(4-氨基苯氧基)苯、间苯二胺、对苯二胺、3,3'-二氨基二苯砜、4,4'-二氨基二苯基砜、4-二(4-双氨基苯氧基)二苯基砜、4-二(3-双氨基苯氧基)苯基砜、4,4'-二(3-氨基苯氧基)联苯、4,4'-二(4-氨基苯氧基)联苯、4,4'-二氨基二苯基甲烷和二乙基甲苯二胺中一种或多种的混合物。
7.根据权利要求1所述的一种热塑性多元杂化聚酰亚胺薄膜的制备方法,其特征在于:所述步骤S4中的梯度升温固化包括第一梯度升温阶段和第二梯度升温阶段,第一梯度升温阶段为:在真空烘箱中依次升温至80~90℃、100~110℃、130~140℃,每个温度段均固化2~3h,期间保持真空度为75~85kPa;第二梯度升温阶段为:在普通烘箱中依次升温至160~180℃、190~210℃、240~260℃、290~310℃和320~340℃,每个温度段均固化1~2h。
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