CN108623835A - 液氮法制备聚酰亚胺泡沫工艺 - Google Patents
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Abstract
本发明公开了一种液氮法制备聚酰亚胺泡沫工艺,属于高分子材料应用领域。本发明先以芳香二酐和4‑4’‑二胺基二苯醚为原料,在极性溶剂中搅拌合成聚酰胺酸溶液,聚酰胺酸溶液经溶剂交换后,将聚酰胺酸固体进行干燥处理,取三乙胺加入到干燥后的聚酰胺酸固体中,加水搅拌溶解形成聚酰胺酸盐,经液氮冷冻和高温亚胺化过程,得到聚酰亚胺泡沫。本发明方法所制得的泡沫,其孔径大于5nm,导热系数仅0.08W·m‑1·K‑1,且当分解率为5%时,其分解温度在550℃以上,泡沫的玻璃化转变温度均在320℃左右。此制备工艺,步骤简单,经济环保,所制备的材料耐热性和耐高温性能优良。
Description
技术领域
本发明涉及高分子材料领域,特别是用作航空航天、远航运输、国防和微电子等高新技术领域中的隔热、减震降噪和绝缘等关键材料。
背景技术
聚酰亚胺(PI)泡沫是一种以PI树脂为主要成分的多孔材料,是一种含有微观/介观或宏观尺寸的开孔结构、闭孔结构或开孔/闭孔组合结构的软质或硬质材料。聚酰亚胺泡沫塑料拥有隔热保温、耐高低温以及吸声等性能,同时具有较高承载性能,所以聚酰亚胺泡沫材料在工业领域中的应用比较广泛,具有广阔发展空间。
传统的泡沫塑料,如聚苯乙烯泡沫(EPS)、聚氨酯泡沫(PUF)、聚氯乙烯泡沫(PVC)等都存在自身性能上的弱点,如聚苯乙烯泡沫的韧性较差,其在燃烧时会产生苯乙烯气体,而苯乙烯气体对环境污染极大,且聚苯乙烯泡沫废弃物体积大,不易处理;聚氨酯泡沫的耐热性差,属易燃材料,只能用于100℃以下的场合,燃烧过程中会放出HCN、CO等有毒气体。与传统的泡沫材料相比,聚酰亚胺泡沫具有更好的热稳定性、不燃、耐辐射、韧性好并减少了燃烧后产生的烟、有毒的气体;它还具有良好的机械性能、耐高温性能、耐溶剂性能等。
对于聚酰亚胺泡沫塑料制备工艺的相关研究较多,但是在进行实际应用时还面临较多问题。专利CN200810227146.4公开了一种聚酰亚胺泡沫及其制备方法,该方法首先生成泡沫前体溶液,再由前体溶液与异氰酸酯反应,自由发泡形成泡沫中间体,再经过微波辐射或/和烘箱加热固化后得到固体聚酰亚胺泡沫。此种方法需在氮气保护下进行操作,对反应气氛要求高,且不能大规模生产;专利CN201711305372.5公开了一种异氰酸酯基聚酰亚胺硬质泡沫的制备方法。该方法主要以芳香二酐和异氰酸酯为主要原料合成。但是该方法存在合成过程中,需使用较多种类的催化剂,使用到剧毒化学品,最终生成的泡沫孔径也较大的缺点。专利CN201710935625.0也公开了一种聚酰亚胺泡沫的制备方法,该方法使用多种原料形成混合助剂作为发泡剂,所生成泡沫的保温性能得到提升,但其热稳定性有所下降。
为解决现有技术中存在的问题,本发明需要提供一种液氮法制备聚酰亚胺泡沫的方法,以一种制作工艺简单,所得泡沫孔径均匀,性能稳定的工艺实现拓宽其应用领域的技术效果。
发明内容
本发明的目的是改善现有聚酰亚胺泡沫制备工艺,提出一种步骤简单、绿色环保、经济高效的方式制作出聚酰亚胺泡沫。
为达到上述目的,本发明的技术方案为:
一种液氮法制备聚酰亚胺泡沫工艺,先以芳香二酐和4-4’-二胺基二苯醚(ODA)为原料,在极性溶剂中搅拌合成聚酰胺酸(PAA)溶液,PAA溶液经溶剂交换后,将聚酰胺酸固体进行干燥处理,取三乙胺加入到干燥后的聚酰胺酸固体中,加水搅拌溶解形成聚酰胺酸盐(PAS),经液氮冷冻和高温亚胺化过程得到聚酰亚胺泡沫。
上述芳香二酐优选为均苯四甲酸酐(PMDA),3,3’,4,4’-二苯甲醚四酸二酐(BPDA)和3,3’,4,4’-二苯甲酮四酸二酐(BTDA)中的一种。
上述极性溶剂为二甲基乙酰胺(DMAc)和N-甲基吡咯烷酮(NMP)中的一种。
优选芳香二酐和4-4’-二胺基二苯醚摩尔比为1:1,芳香二酐和4-4’-二胺基二苯醚的用量比直接会影响到聚酰胺酸的聚合度,进而直接决定泡沫能否成型;
在极性溶剂中搅拌合成聚酰胺酸溶液的具体过程如下:将4-4’-二胺基二苯醚(ODA)先加入极性溶剂中,搅拌25-40min,优选0.5h,再将芳香二酐分2-3次加入,每次间隔时间30~40min。
上述溶剂交换为将合成的聚酰胺酸溶液搅拌状态下缓慢倒入去离子水中,在20~35℃温度下超声进行5~8h。
所述的干燥处理是经溶剂交换后得到的聚酰胺酸固体在烘箱中35℃干燥4~5天。
所述的三乙胺与聚酰胺酸固体物质的量之比为1:1。
上述亚胺化过程中采用梯度升温的方式,升温区间为30℃~280℃,最高温度为280℃。
具体为:具体为:30℃经30min升温至120℃,恒温0.5h,120℃经30min升温至200℃,恒温0.5h,200℃经30min升温至280℃,恒温0.5h,280℃经30min降温至室温。
亚胺化过程中,温度过低导致亚胺化不完全。.
与现有技术比较本发明的有益效果:本发明方法制作工艺简单,所得聚酰亚胺泡沫孔径均匀,平均孔径大于5nm,导热系数仅0.08W·m-1·K-1,且当分解率为5%时,其分解温度在550℃以上,泡沫的玻璃化转变温度均在320℃左右。此制备工艺,步骤简单,经济环保,在保证保温性能的同时热稳定性好,实现了拓宽聚酰亚胺泡沫应用领域的目的。
附图说明
下面结合附图和实施例对本发明做进一步说明。
图1是所制得的聚酰亚胺泡沫的扫描电子显微镜图片;
图2是所制得的聚酰亚胺泡沫的热失重曲线图。
具体实施方式
为了对本发明的技术特征有更加清楚的理解,现对本发明的技术方案进行以下详细说明,但不能理解为对本发明的可实施范围的限定。
实施例1
将3.5897g 4-4’-二胺基二苯醚(ODA)加入到42.5g的N-甲基乙酰胺(NMP)中,充分搅拌半个小时,再将3.9103g均苯四甲酸酐(PMDA)分三次加入,每次间隔时间30~40min,全部加完后,再搅拌4-6h即可得到聚酰胺酸(PAA)溶液。将PAA溶液缓慢倒入去离子水中,并置于超声中20~35℃温度下进行溶剂交换处理,超声时长为5~8h。待DMAc完全交换出去,捞出PAA固体置于烘箱中35℃干燥4~5天。称取0.5843g的三乙胺、2.4157g的PAA固体、17g的水于烧杯中,放入磁力搅拌器中搅拌使其完全溶解。所得溶液转入模具中并加入液氮,使溶液中的水分升华从而除去聚酰胺酸盐中所含的水,所得样品放入烘箱中,30~280℃温度范围内梯度升温进行高温热亚胺化处理,具体为:30℃经30min升温至120℃,恒温0.5h,120℃经30min升温至200℃,恒温0.5h,200℃经30min升温至280℃,恒温0.5h,280℃经30min降温至室温,即可得到聚酰亚胺泡沫。
实施例2
将3.5897g 4-4’-二胺基二苯醚(ODA)加入到42.5g的二甲基乙酰胺(DMAc)中,充分搅拌半个小时,再将3.9103g的均苯四甲酸酐(PMDA)分三次加入,每次间隔时间30~40min,全部加完后,再搅拌4-6h即可得到聚酰胺酸(PAA)溶液。将PAA溶液缓慢倒入去离子水中,并置于超声中20~35℃温度下进行溶剂交换处理,超声时长为5~8h。待DMAc完全交换出去,捞出PAA固体置于烘箱中35℃干燥4~5天。称取0.5843g的三乙胺、2.4157g的PAA固体、17g的水于烧杯中,放入磁力搅拌器中搅拌使其完全溶解。所得溶液转入模具中并加入液氮,使溶液中的水分升华,所得样品放入烘箱中,30~280温度范围内梯度升温,进行高温热亚胺化处理,具体为:30℃经30min升温至120℃,恒温0.5h,120℃经30min升温至200℃,恒温0.5h,200℃经30min升温至280℃,恒温0.5h,280℃经30min降温至室温,即可得到聚酰亚胺泡沫。
实施例3
将3.8290g 4-4’-二胺基二苯醚(ODA)加入到42g的二甲基乙酰胺(DMAc)中,充分搅拌半个小时,再将4.1710g的均苯四甲酸酐(PMDA)分三次加入,每次间隔时间30~40min,全部加完后,再搅拌4-6h即可得到聚酰胺酸(PAA)溶液。将PAA溶液缓慢倒入去离子水中,并置于超声中20~35℃温度下进行溶剂交换处理,超声时长为5~8h。待DMAc完全交换出去,捞出PAA固体置于烘箱中35℃干燥4~5天。称取0.5843g的三乙胺、2.4157g的PAA固体、17g的水于烧杯中,放入磁力搅拌器中搅拌使其完全溶解。所得溶液转入模具中并加入液氮,使溶液中的水分升华,所得样品放入烘箱中,30~280温度范围内梯度升温进行高温热亚胺化处理,具体为:30℃经30min升温至120℃,恒温0.5h,120℃经30min升温至200℃,恒温0.5h,200℃经30min升温至280℃,恒温0.5h,280℃经30min降温至室温;即可得到聚酰亚胺泡沫。
实施例4
将3.2397g 4-4’-二胺基二苯醚(ODA)加入到42g的N-甲基乙酰胺(NMP)中,充分搅拌半个小时,再将4.7603g的3,3’,4,4’-二苯甲醚四酸二酐(BPDA)分三次加入,每次间隔时间30~40min,全部加完后,再搅拌4-6h即可得到聚酰胺酸(PAA)溶液。将PAA溶液缓慢倒入去离子水中,并置于超声中20~35℃温度下进行溶剂交换处理,超声时长为5~8h。待DMAc完全交换出去,捞出PAA固体置于烘箱中35℃干燥4~5天。称取0.5843g的三乙胺、2.4157g的PAA固体、17g的水于烧杯中,放入磁力搅拌器中搅拌使其完全溶解。所得溶液转入模具中并加入液氮,使溶液中的水分升华,所得样品放入烘箱中,30~280温度范围内梯度升温,具体为:30℃经30min升温至120℃,恒温0.5h,120℃经30min升温至200℃,恒温0.5h,200℃经30min升温至280℃,恒温0.5h,280℃经30min降温至室温,进行高温热亚胺化处理,即可得到聚酰亚胺泡沫。
本发明实施例1所制得的聚酰亚胺泡沫的形貌图如图1所示,图a为500倍下的形貌图,图b为800倍下的形貌图。从图a中可以看出,在泡沫的内部大大小小的孔洞交错重叠在一起,形成交叠的网络结构,这种结构有效的阻止甚至延迟了热量的传递。从图b可以看出聚酰亚胺泡沫内部的孔洞多为开孔结构。本发明所制聚酰亚胺泡沫的热失重曲线如图2所示,图中可以看出,在分解率在5%时,分解温度在572℃,这表明材料具有优异的热稳定性。另外,测试得到材料的导热系数仅0.075W·m-1·K-1,导热系数低,材料的保温性能好。
Claims (8)
1.一种液氮法制备聚酰亚胺泡沫工艺,其特征在于先以芳香二酐和4-4’-二胺基二苯醚为原料,在极性溶剂中搅拌合成聚酰胺酸溶液,聚酰胺酸溶液经溶剂交换后,将聚酰胺酸固体进行干燥处理,取三乙胺加入到干燥后的聚酰胺酸固体中,加水搅拌溶解形成聚酰胺酸盐,经液氮冷冻和高温亚胺化过程,得到聚酰亚胺泡沫。
2.根据权利要求1所述的液氮法制备聚酰亚胺泡沫,其特征在于所述的芳香二酐为均苯四甲酸酐,3,3’,4,4’-二苯甲醚四酸二酐和3,3’,4,4’-二苯甲酮四酸二酐中的一种。
3.根据权利要求1所述的液氮法制备聚酰亚胺泡沫工艺,其特征在于上述极性溶剂为二甲基乙酰胺和N-甲基吡咯烷酮中的一种。
4.根据权利要求1所述的液氮法制备聚酰亚胺泡沫工艺,其特征在于在极性溶剂中搅拌合成聚酰胺酸溶液的具体过程如下:将4-4’-二胺基二苯醚先加入极性溶剂中,搅拌25-40min后,再将芳香二酐分2-3次加入,每次间隔时间30~40min。
5.根据权利要求1所述的液氮法制备聚酰亚胺泡沫工艺,其特征在于所述的溶剂交换为将合成的聚酰胺酸溶液搅拌状态下缓慢倒入去离子水中,在20~35℃温度下超声进行5~8h。
6.根据权利要求1所述的液氮法制备聚酰亚胺泡沫工艺,其特征在于所述的干燥处理是经溶剂交换后得到的聚酰胺酸固体在烘箱中35℃干燥4~5天。
7.根据权利要求1所述的液氮法制备聚酰亚胺泡沫工艺,其特征在于所述的的三乙胺与聚酰胺酸固体物质的量之比为1:1。
8.根据权利要求1所述的液氮法制备聚酰亚胺泡沫工艺,其特征在于亚胺化过程中采用梯度升温的方式,升温区间为30℃~280℃。
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