CN113881094B - 一种以2,5-呋喃二甲酸为原料的生物基聚酰亚胺气凝胶及其制备方法 - Google Patents
一种以2,5-呋喃二甲酸为原料的生物基聚酰亚胺气凝胶及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种以2,5‑呋喃二甲酸为原料的生物基聚酰亚胺气凝胶及其制备方法,该方法以采用可再生、储量大且价格低廉的2,5‑呋喃二甲酸为原料,经二氯亚砜酰氯化反应以及与二胺分别进行酰胺化反应,合成基于2,5‑呋喃二甲酸的生物基二胺。然后利用乙醇或二氧化碳超临界方法制得生物基聚酰亚胺气凝胶。本发明制备的生物基聚酰亚胺比表面积大,呈现三维网状结构,热稳定性好,光催化性能优良,可有效应对资源枯竭、石化行业环境污染等问题。
Description
技术领域
本发明涉及一种以2,5-呋喃二甲酸为原料的生物基聚酰亚胺气凝胶及其制备方法,属于生物基高分子领域。
背景技术
目前,传统高分子材料绝大多数来源于石化资源,而现阶段石化资源正日益匮乏。同时,传统高分子材料的不可降解性造成日益严重的环境污染,由此极大的限制了高分子行业的发展。
为实现高分子产业绿色环保的可持续发展,全球均在寻找可替代石油的生物基材料。2004年,美国能源部筛选出十二种最有可能实现石油基替代的生物基化合物。其中2,5-呋喃二甲酸(FDCA)是十二种化合物中的唯一一个具有芳环平面、刚性结构的生物基化合物。
利用FDCA开发高附加值的产品可以为绿色环保的高分子产业提供技术支撑;如文献:Influence of the 2,5-Furandicarboxamide Moiety on Hydrogen Bonding inAliphatic-Aromatic Poly(ester amide)s.”Wilsens,Macromolecules,2014,47(18),6196-6206.报道了利用FDCA制备了生物基聚酯,该生物基聚酯的热稳定性以及机械性能提高,表明FDCA可有效替代石油基材料。Preparation of Poly(ether ketone)s Derivedfrom 2,5-Furandicarboxylic Acid by Polymerization in Ionic Liquid.”Kanetaka,Macromolecules.2016,49(4):1012-1016.以FDCA为单体在离子液体中制备了生物基聚醚酮,该生物基聚醚酮的热稳定性提高,耐化学性增强。
又如:中国专利文献201811000455.8提供了一种生物基呋喃二甲酸聚酯,采用呋喃二甲酸环刚性与带有侧链的1,3-丙二醇等二元醇聚合制备出具有优异氧气和二氧化碳阻隔性能的新型生物基聚酯,解决了传统聚酯、聚乙烯、聚丙烯等食品包装薄膜氧气阻隔性能不够好,导致食品保质期短、需要加入大量防腐剂缺点。中国专利文献201810994123公开了一种生物基2,5-呋喃二甲酸聚酰胺酰亚胺薄膜和制备方法。提供的聚酰胺酰亚胺薄膜的的力学性能、玻璃化转变温度优异,避免使用来自石化资源的对苯二甲酸作为原料,从而促进了热塑性高分子材料产业摆脱对石油资源的高度依赖。
聚酰亚胺(PI)被称为“黄金高分子材料”,是一类主链上含有酰亚胺基团(酰亚胺环)的芳杂环高分子聚合物。PI应用领域非常广泛,并且在每一个应用领域中都显示出突出性能。PI因其独特的结构具有良好的光催化性能,被用作新型的光催化剂。然而,PI的光催化效率较低。Positive effects of phosphotungstic acid on the in-situ solid-state polymerization and visible light photocatalytic activity of polyimide-based photocatalyst”,Meng,Appllied Catalysis B:Enviromental,2018,226,487-498通过原位聚合的方法制备了聚酰亚胺/磷钨杂多酸复合光催化剂,研究发现,在可见光下,该催化剂具有良好的降解性能,与纯聚酰亚胺相比,光催化效率大大提高。Fabrication,characterization and mechanism of a novelZ-scheme Ag3PO4/NG/Polyimidecomposite photocatalyst formicrocystin-LR degradation”,Guo,Appllied CatalysisB:Enviromental,2018,229,192-203制备了Ag3PO4/氮掺杂石墨烯/聚酰亚胺复合材料,该材料为Z型催化剂,表现出优良的光催化性能,与纯聚酰亚胺相比,光催化效率大大提高。
PI光催化效率的重要影响因素是比表面积。但是PI基催化剂多是粉末材料,比表面积较小(<10m2/g),在催化过程中容易团聚,难以回收利用。聚酰亚胺(PI)气凝胶因超高的柔韧性和吸附性以及超大的比表面积,作为气凝胶中的佼佼者,其性能在不断地被探索开发。PI聚合物作为一种新型光催化剂,由于较高的化学稳定性、成本低和丰富的储量,已经被报道可以光降解有机污染物,并且在可见光照射下,光分解水制氢,在光催化方面展现出极大的优势。但是随着石化资源正日益匮乏,制备聚酰亚胺(PI)气凝胶的成本也越来越高。
因此,亟需研发一种基于可再生资源并且具有良好光催化性能的聚酰亚胺气凝胶。
发明内容
针对现有技术的不足,尤其是目前制备聚酰亚胺(PI)气凝胶原料匮乏的难题,本发明提供一种以2,5-呋喃二甲酸为原料的生物基聚酰亚胺气凝胶及其制备方法。
发明概述:
本发明的制备方法以可再生资源2,5-呋喃二甲酸为原料,2,5-呋喃二甲酸通过酰氯化反应和酰胺化反应制备生物基二胺2,5-呋喃二甲酰二胺,然后2,5-呋喃二甲酰二胺与二酐单体反应,利用乙醇或二氧化碳超临界制备生物基聚酰亚胺气凝胶。
发明详述:
本发明的技术方案如下:
一种以2,5-呋喃二甲酸为原料制备生物基聚酰亚胺气凝胶的方法,包括步骤如下:
(1)2,5-呋喃二甲酰氯的合成:
将2,5-呋喃二甲酸、氯化亚砜(SOCl2)和N,N-二甲基甲酰胺(DMF)混合均匀后,升温回流反应,常温真空处理后,得到2,5-呋喃二甲酰氯;
(2)2,5-呋喃二甲酰二胺的合成
将步骤(1)制得的2,5-呋喃二甲酰氯溶于二甲基乙酰胺DMAC中,得到酰氯的二甲基乙酰胺溶液,将三乙胺、二胺和二甲基甲酰胺DMF混合,得混合物,向混合物中加入酰氯的二甲基乙酰胺溶液,在惰性气氛下,搅拌升温反应,反应结束后,水洗,干燥,得到生物基二胺2,5-呋喃二甲酰二胺;
(3)生物基聚酰亚胺气凝胶的制备
将步骤(2)得到的生物基二胺、二酐单体溶于有机溶剂中,加或不加4,4'-二氨基二苯醚,加入交联试剂搅拌均匀,然后加入亚胺化试剂,搅拌反应5-15min,导入模具成湿凝胶,室温下老化,老化后进行溶剂置换,超临界干燥,得到生物基聚酰亚胺气凝胶。
根据本发明优选的,步骤(1)中,2,5-呋喃二甲酸、氯化亚砜(SOCl2)和N,N-二甲基甲酰胺(DMF)的摩尔比为(10~60):(50~250):1。
根据本发明优选的,步骤(1)中,升温回流反应温度为70~100℃,反应时间为4~12h。
根据本发明优选的,步骤(1)中,常温真空处理时间为5~15h,真空度为-0.08~0.1MPa。
根据本发明优选的,步骤(2)中,2,5-呋喃二甲酰氯与二甲基乙酰胺DMAC的质量体积比为(1~3):(10~60),单位,g/mL。
根据本发明优选的,步骤(2)中,2,5-呋喃二甲酰氯与二胺的摩尔比为(0.1~2):1。
根据本发明优选的,步骤(2)中,三乙胺与二胺的质量比为(1-3):(1~6)。
根据本发明优选的,步骤(2)中,二胺与DMF的质量体积比(3-6):(10~60),单位,g/mL。
根据本发明优选的,步骤(2)中,二胺为4,4'-二氨基二苯醚。
根据本发明优选的,步骤(2)中,惰性气氛为氮气,升温温度为10~60℃,反应时间为1~48h。
进一步优选的,步骤(2)中,升温温度为20~40℃,反应时间为8~20h。
根据本发明优选的,步骤(3)中,二酐单体为3,3',4,4'-联苯四甲酸二酐。
根据本发明优选的,步骤(3)中,亚胺化试剂包括催化剂和脱水剂,催化剂选自吡啶、甲基吡啶、三乙胺其中之一,脱水剂选自醋酸酐、乙酰氯、氯化亚砜、磷的卤化物、有机硅化合物、二环己基碳酰亚胺其中之一。
根据本发明优选的,步骤(3)中,交联试剂为1,3,5-苯三甲酰氯(BTC)或1,3,5-三(4-氨基苯氧基)苯(TAB)或3-氨丙基三乙氧基硅烷(APTES)。
根据本发明优选的,步骤(3)中,所述的有机溶剂为N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)或二甲基乙酰胺(DMAc)。
根据本发明优选的,步骤(3)中,生物基二胺与二酐单体物质的量比为(0.5~3.0):1。
根据本发明优选的,步骤(3)中,当加入4,4'-二氨基二苯醚时,4,4'-二氨基二苯醚与二酐单体物质的量比为(0.05~1.0):1。
根据本发明优选的,步骤(3)中,交联试剂与二胺单体物质的量之比为(0.01~0.5):1。
根据本发明优选的,步骤(3)中,亚胺化试剂中脱水剂与二胺单体的质量比为(2~10):1,催化剂与二胺单体的质量比为(2~10):1。
根据本发明优选的,步骤(3)中,老化时间为12h-2天。
根据本发明优选的,步骤(3)中,溶剂置换为加入乙醇或丙酮进行溶剂置换,置换时间为5-8天。置换过程中24小时更换一次试剂。
根据本发明优选的,步骤(3)中,所述超临界干燥为乙醇或二氧化碳超临界干燥,乙醇超临界条件为温度220-300℃,压强6-13MPa,二氧化碳超临界条件为温度40-80℃,压强6-12MPa。
本发明得到的生物基聚酰亚胺气凝胶具有较大的比表面积,良好的光催化性能。
与现有技术相比,本发明具有如下有益效果:
本发明提供的聚酰亚胺气凝胶是首次以生物基单体2,5-呋喃二甲酸为原料的生物基聚酰亚胺气凝胶,比表面积较大,光催化性能较好。本发明制备的生物基聚酰亚胺气凝胶为有机聚合物催化剂的研发提供了新的思路。
附图说明
图1为聚酰亚胺PI及生物基聚酰亚胺气凝胶PI-3的红外光谱图,
图2聚酰亚胺PI及生物基聚酰亚胺气凝胶PI-3的XRD谱图,
图3为聚酰亚胺气凝胶的扫描电子显微镜照片,a为对比例1纯聚酰亚胺气凝胶PI,b为生物基聚酰亚胺PI-1,c为生物基聚酰亚胺PI-2,d为生物基聚酰亚胺气凝胶PI-3;放大倍率50000倍;
图4为聚酰亚胺气凝胶的光催化降解曲线。
具体实施方式
为便于理解本发明,本发明列举实施例如下。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
实施例1
一种以2,5-呋喃二甲酸为原料制备生物基聚酰亚胺气凝胶的方法,步骤如下:
(1)生物基二胺的制备:
①2,5-呋喃二甲酰氯的合成:呋喃二甲酸3.0g,SOCl210.0ml,DMF300ul加入100ml圆底烧瓶中,70℃反应回流4小时。常温真空5小时,将过量的SOCl2和DMF除去,将剩余物高真空升华提纯;
②2,5-呋喃二甲酰二胺的合成:盛有三乙胺2.0g和4,4'-二氨基二苯醚4.8g的三口烧瓶中加入DMF20.0ml,逐滴加入溶有2,5-呋喃二甲酰氯1.8g的DMAc40.0ml,常温下,通氮气12小时。将混合物加入水中,出现沉淀,过滤,水洗,100℃真空干燥。
(2)生物基聚酰亚胺气凝胶的制备
①生物基聚酰亚胺湿凝胶的制备:将2,5-呋喃二甲酰二胺1.5g和4,4'-二氨基二苯醚0.5g加入NMP30mL中,待其溶解完全后加入3,3',4,4'-联苯四甲酸二酐BPDA4.0g,待反应物变透明后,加入溶有交联剂1,3,5-苯三甲酰氯BTC0.025g的NMP50.0ml,搅拌均匀,然后加入脱水剂醋酸酐6.0mL,搅拌均匀后,加入催化剂三乙胺1.0ml,搅拌反应15min,得到湿凝胶,倒入模具中;
②生物基聚酰亚胺湿凝胶的老化:待其凝胶并室温下老化1天,将老化后的凝胶浸泡在乙醇中进行溶剂置换,置换时间为1周,在此期间平均每天更换一次乙醇,
③生物基聚酰亚胺气凝胶的制备:老化后的气凝胶二氧化碳超临界干燥,二氧化碳超临界干燥压力为7.5MPa;温度40℃,干燥时间为4h,得到生物基聚酰亚胺气凝胶;记作生物基聚酰亚胺气凝胶PI-1。
实施例2
一种以2,5-呋喃二甲酸为原料制备生物基聚酰亚胺气凝胶的方法,步骤如下:
(1)生物基二胺的制备:
①2,5-呋喃二甲酰氯的合成:2,5-呋喃二甲酸2.0g,12.0mlSOCl2,DMF100ul加入100ml圆底烧瓶中,90℃反应回流8小时。常温真空12小时,将过量的SOCl2和DMF除去。将剩余物高真空升华提纯。
②2,5-呋喃二甲酰二胺的合成:三乙胺1.0g和4,4'-二氨基二苯醚3.0g三口烧瓶中加入30.0mlDMF,逐滴加入溶有2,5-呋喃二甲酰氯1.0g的DMAc15.0ml,常温下,通氮气8小时。将混合物加入水中,出现沉淀,过滤,水洗,80℃真空干燥。
(2)生物基聚酰亚胺气凝胶的制备
①生物基聚酰亚胺湿凝胶的制备:将2,5-呋喃二甲酰二胺1.8g和4,4'-二氨基二苯醚0.1g加入NMP40mL中,待其溶解完全后加入3,3',4,4'-联苯四甲酸二酐BPDA3.0g,待反应物变透明后,加入溶有交联剂1,3,5-苯三甲酰氯BTC 0.035g的NMP40.0ml,搅拌均匀,然后加入脱水剂醋酸酐8.0mL,搅拌均匀后,加入催化剂三乙胺1.2ml,搅拌反应15min,得到湿凝胶,倒入模具中;
②生物基聚酰亚胺湿凝胶的老化:待其凝胶并室温下老化1天,将老化后的凝胶浸泡在乙醇中进行溶剂置换,置换时间为1周,在此期间平均每天更换一次乙醇,
③生物基聚酰亚胺气凝胶的制备:老化后的气凝胶二氧化碳超临界干燥,二氧化碳超临界干燥压力为8.5MPa;温度50℃,干燥时间为3h,得到生物基聚酰亚胺气凝胶。记作生物基聚酰亚胺气凝胶PI-2。
实施例3
一种以2,5-呋喃二甲酸为原料制备生物基聚酰亚胺气凝胶的方法,步骤如下:
(1)生物基二胺的制备:
①2,5-呋喃二甲酰氯的合成:2,5-呋喃二甲酸6.0g,15mlSOCl2,DMF500ul加入100ml圆底烧瓶中,750℃反应回流5小时。常温真空9小时,将过量的SOCl2和DMF除去。将剩余物高真空升华提纯。
②2,5-呋喃二甲酰二胺的合成:三乙胺3.0g和4,4'-二氨基二苯醚5.8g三口烧瓶中加入50mlDMF,逐滴加入溶有2,5-呋喃二甲酰氯3.0g的DMAc80ml,常温下,通氮气12小时。将混合物加入水中,出现沉淀,过滤,水洗,100℃真空干燥。
(2)生物基聚酰亚胺气凝胶的制备
①生物基聚酰亚胺湿凝胶的制备:将2,5-呋喃二甲酰二胺3.2g加入NMP20mL中,待其溶解完全后加入3,3',4,4'-联苯四甲酸二酐BPDA3.5g,待反应物变透明后,加入溶有交联剂1,3,5-苯三甲酰氯BTC0.050g的NMP30.0ml,搅拌均匀,然后加入脱水剂醋酸酐9.0mL,搅拌均匀后,加入催化剂三乙胺2.2ml,搅拌反应15min,得到湿凝胶,倒入模具中;
②生物基聚酰亚胺湿凝胶的老化:待其凝胶并室温下老化1天,将老化后的凝胶浸泡在乙醇中进行溶剂置换,置换时间为1周,在此期间平均每天更换一次乙醇,
③生物基聚酰亚胺气凝胶的制备:老化后的气凝胶二氧化碳超临界干燥,二氧化碳超临界干燥压力为10.0MPa;温度45℃,干燥时间为6h,得到生物基聚酰亚胺气凝胶。记作生物基聚酰亚胺气凝胶PI-3。
对比例1
一种聚酰亚胺气凝胶的制备方法,该制备方法不加入生物基二胺,直接由4,4'-二氨基二苯醚和二酐反应制备气凝胶,具体包括如下步骤:
①聚酰亚胺湿凝胶的制备:将4,4'-二氨基二苯醚2.0g加入NMP30.0mL中,待其溶解完全后加入BPDA4.0g。待反应物变透明后,加入脱水剂醋酸酐6.0mL,搅拌均匀后,加入三乙胺1.0ml,15min后,加入溶有BTC0.025g的NMP50ml,搅拌均匀后将反应物倒入模具中。
②聚酰亚胺凝胶的老化:待其凝胶并室温下老化1天。将老化后的凝胶浸泡在乙醇中进行溶剂置换(置换时间大约为1周,在此期间平均每天更换一次乙醇),
③聚酰亚胺气凝胶的制备:二氧化碳超临界干燥获得聚酰亚胺气凝胶。
二氧化碳超临界获得生物基聚酰亚胺气凝胶,压力为7.5MPa;温度40℃,干燥时间为4h。记作聚酰亚胺气凝胶PI。
聚酰亚胺气凝胶PI以及生物基聚酰亚胺气凝胶PI-3的红外光谱图及XRD谱图见图1、图2所示,从图1中可以看出对比例1的聚酰亚胺气凝胶PI以及生物基聚酰亚胺气凝胶PI-3谱图中1773cm-1,1713cm-1分别对应亚胺环中C=O键的伸缩振动峰,1373cm-1对应C-N伸缩振动峰,1500cm-1对应苯环的振动峰,1240-cm1对应C-O-C的振动峰。生物基聚酰亚胺气凝胶PI-3谱图中出现1578cm-1处新峰,对应呋喃环中C=C的伸缩振动峰。以上表明成功合成了生物基聚酰亚胺气凝胶。
从图2中可以看出,对比例1的聚酰亚胺气凝胶PI及生物基聚酰亚胺气凝胶PI-3的XRD都出现了聚酰亚胺的典型宽泛的衍射峰,说明生物基聚酰亚胺气凝胶结构是无定形的。
应用实验例:
1、BET测试结果:
实施例1产品PI-1比表面积为274m2/g,孔容量为1.15m2/g,孔径为19.1nm。
实施例2产品PI-2比表面积为251m2/g,孔容量为0.74m2/g,孔径为11.5nm。
实施例3产品PI-3比表面积为220m2/g,孔容量为0.75m2/g,孔径为13.3nm。
对比例1产品PI比表面积为249m2/g,孔容量为0.89m2/g,孔径为14.4nm。
本发明以生物基单体2,5-呋喃二甲酸为原料的生物基聚酰亚胺气凝胶的比表面积和聚酰亚胺气凝胶的比表面积相当,可以完全替代现有的石油基原料;并且,生物基聚酰亚胺气凝胶的比表面积远高于通用的聚酰亚胺粉末的比表面积(<10m2/g)。
2、聚酰亚胺气凝胶的扫描电子显微镜照片见图3所示,从图3可以看出聚酰亚胺(a)和生物基聚酰亚胺(b-d)都为三维网状结构。
3、光催化测试:
对实施例1-3生物基聚酰亚胺气凝胶和对比例1的聚酰亚胺气凝胶进行光催化测试;测试结果见图4,从光催化降解的曲线中可以看出,聚酰亚胺以及生物基聚酰亚胺具有良好的光催化的性能,经过180min后,纯聚酰亚胺气凝胶用于光催化后的溶液剩余浓度为48%,降解效率为52%,实施例3中,生物基聚酰亚胺气凝胶用于光催化后的溶液的剩余浓度为40%,降解效率为60%,比聚酰亚胺的降解效率提高了8%。综上所述,本发明可以用作超大比表面积的生物基聚酰亚胺光催化材料。
本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程,但本发明并不局限于上述详细工艺设备和工艺流程,即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (4)
1.一种以2,5-呋喃二甲酸为原料制备生物基聚酰亚胺气凝胶的方法,包括步骤如下:
(1)2,5-呋喃二甲酰氯的合成:
将2,5-呋喃二甲酸、氯化亚砜和N,N-二甲基甲酰胺混合均匀后,升温回流反应,常温真空处理后,得到2,5-呋喃二甲酰氯;2,5-呋喃二甲酸、氯化亚砜和N,N-二甲基甲酰胺的摩尔比为(10~60):(50~250):1;升温回流反应温度为70~100℃,反应时间为4~12h,常温真空处理时间为5~15h,真空度为-0.08~0.1MPa;
(2)2,5-呋喃二甲酰二胺的合成
将步骤(1)制得的2,5-呋喃二甲酰氯溶于二甲基乙酰胺中,得到酰氯的二甲基乙酰胺溶液,将三乙胺、二胺和二甲基甲酰胺混合得混合物,向混合物中加入酰氯的二甲基乙酰胺溶液,在惰性气氛下,搅拌升温反应,反应结束后,水洗,干燥,得到生物基二胺2,5-呋喃二甲酰二胺;2,5-呋喃二甲酰氯与N,N-二甲基乙酰胺的质量体积比为(1~3):(10~60),单位g/mL; 2,5-呋喃二甲酰氯与二胺的摩尔比为(0.1~2):1;
三乙胺与二胺的质量比为(1-3):(1~6),二胺与DMF的质量体积比(3-6):(10~60),单位g/mL;二胺为4,4'-二氨基二苯醚;
惰性气氛为氮气,升温温度为10~60℃,反应时间为1~48h;
(3)生物基聚酰亚胺气凝胶的制备
将步骤(2)得到的生物基二胺、二酐单体溶于有机溶剂中,加入 4,4'-二氨基二苯醚,加入交联试剂搅拌均匀,然后加入亚胺化试剂,亚胺化试剂包括催化剂和脱水剂,搅拌反应5-15min,导入模具成湿凝胶,室温下老化,老化后进行溶剂置换,超临界干燥,得到生物基聚酰亚胺气凝胶;
生物基二胺与二酐单体物质的量比为(0.5~3.0):1,当加入4,4'-二氨基二苯醚时,4,4'-二氨基二苯醚与二酐单体物质的量比为(0.05~1.0):1,交联试剂与二胺单体物质的量之比为(0.01~0.5):1,亚胺化试剂中脱水剂与二胺单体的质量比为(2~10):1,催化剂与二胺单体的质量比为(2~10):1。
2.根据权利要求1所述的方法,其特征在于,步骤(3)中,二酐单体为3,3',4,4'-联苯四甲酸二酐;催化剂选自吡啶、甲基吡啶、三乙胺其中之一,脱水剂选自醋酸酐、乙酰氯、氯化亚砜、磷的卤化物、有机硅化合物、二环己基碳酰亚胺其中之一;交联试剂为1,3,5-苯三甲酰氯或1,3,5-三(4-氨基苯氧基)苯或3-氨丙基三乙氧基硅烷,所述的有机溶剂为N-甲基吡咯烷酮、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺。
3.根据权利要求1所述的方法,其特征在于,步骤(3)中,老化时间为0.5-3h,溶剂置换为加入乙醇或丙酮进行溶剂置换,置换时间为5-8天;所述超临界干燥为乙醇或二氧化碳超临界干燥,乙醇超临界条件为温度220-300℃,压强6-13MPa,二氧化碳超临界条件为温度40-80℃,压强6-12MPa。
4.一种以2,5-呋喃二甲酸为原料的生物基聚酰亚胺气凝胶,采用权利要求1所述的方法制得。
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