CN113024883B - 一种短切纤维分层增强聚酰亚胺气凝胶的制备方法 - Google Patents
一种短切纤维分层增强聚酰亚胺气凝胶的制备方法 Download PDFInfo
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Abstract
本发明属于纳米多孔材料的制备工艺领域,涉及一种短切纤维分层增强聚酰亚胺气凝胶的制备方法。本发明使用改性短切纤维作为增强体材料,增强短切纤维以层状方式均匀分散在聚酰亚胺气凝胶结构中,短切纤维作为骨架穿插在聚酰亚胺气凝胶基体中,由于纤维添加量较少,且分层铺设在气凝胶基体中,因此在垂直于纤维层方向上避免了纤维与纤维接触在热传导中产生的热桥效应,从而不会降低气凝胶材料本身的隔热性能和可压缩性能,还由于聚酰亚胺气凝胶基体是由纵横交错的阻裂短切纤维支撑,因此极大程度的提高了气凝胶复合材料在水平方向的抗裂性能。制得纤维分层增强聚酰亚胺气凝胶密度为0.09~0.12g/cm3,室温热导率为0.04793~0.04859W/(m·K)。
Description
技术领域
本发明属于纳米多孔材料的制备工艺领域,涉及一种短切纤维分层增强聚酰亚胺气凝胶的制备方法。
背景技术
气凝胶是一种分散介质为气体的凝胶材料,固体相和孔隙结构均为纳米量级,是目前世界上密度最小、热导率最小的固体材料。因此在航空航天轻质耐高温材料、消防服、卫星表面防护材料具有广阔的应用前景。
聚酰亚胺(PI)气凝胶是主链中含有酰亚胺环的一类有机高分子气凝胶,由于主链中含有杂环结构,故其耐高低温性能极为优异,还兼具优异的机械性能、耐磨损性能等优良性能,因此聚酰亚胺(PI)气凝胶的力学性能远优于其他高分子气凝胶,但其力学性能均未达到理想的效果。对此,CN 108794766A公开了一种交联型聚酰亚胺气凝胶及制备方法,由胺基封端的聚酰胺酸与多酐基交联剂进行交联得到中间产物,中间产物经化学亚胺化,得到聚酰亚胺湿凝胶,再经溶剂置换、超临界干燥制得柔性交联聚酰亚胺气凝胶,但作为卫星表面防护系统中的结构材料来说,其支撑性能较差,因此需要制备一种具有更高强度和抗冲击性能的聚酰亚胺气凝胶。对此,一般采用纤维复合增强方式提高聚酰亚胺气凝胶的力学性能,如CN 111253742A便公开了一种纤维毡增强聚酰亚胺气凝胶的制备方法,虽提高其机械性能,但其隔热性能大幅度下降。因此,本发明采用适量短切纤维分层铺设在聚酰亚胺气凝胶基体中,可保持气凝胶隔热性能的同时提高其机械性能。
目前,短切纤维分层增强是一种在保持气凝胶材料隔热性能的同时增加气凝胶材料抗冲击性能的方式,但由于聚酰亚胺湿凝胶的凝胶速度较快,短切纤维与气凝胶基体之间的粘结性较差,使得短切纤维增强聚酰亚胺气凝胶复合材料的制备困难较大,因此从未有过聚酰亚胺气凝胶与短切纤维增强体分层复合的相关报道。
发明内容
本发明的目的是为了改进现有技术的不足而提供一种短切纤维分层增强聚酰亚胺气凝胶的制备方法。
本发明的技术方案为:使用改性玻璃短切纤维作为增强体材料,增强短切纤维以层状方式均匀分散在聚酰亚胺气凝胶结构中,短切纤维作为骨架穿插在聚酰亚胺气凝胶基体中,由于纤维添加量较少,且分层铺设在气凝胶基体中,因此在垂直于纤维层方向上避免了纤维与纤维接触在热传导中产生的热桥效应,从而不会降低气凝胶材料本身的隔热性能和可压缩性能,还由于聚酰亚胺气凝胶基体是由纵横交错的阻裂短切纤维支撑,因此极大程度的提高了气凝胶复合材料在水平方向的抗裂性能。
本发明的具体技术方案为:一种短切纤维分层增强聚酰亚胺气凝胶的制备方法,其具体步骤如下:
(1)制备聚酰胺酸溶液
量取一定量的二酐单体、二胺单体溶解到极性非质子溶剂当中,得到聚酰胺酸溶液;
(2)短切阻裂纤维表面改性
通过对短切纤维进行湿法表面改性,得到改性的层状短切阻裂纤维(使短切纤维能均匀分散在聚酰亚胺溶胶中);
(3)制备纤维分层增强聚酰亚胺湿凝胶
对步骤(1)中的聚酰胺酸溶液进行化学亚胺化得到聚酰亚胺溶胶,再将聚酰亚胺溶胶倒入模具中,待其开始凝胶后再将步骤(2)中改性的层状短切阻裂纤维铺展在模具中,然后继续倒入聚酰亚胺溶胶,重复上述步骤1~4次,待其凝胶完全后得到纤维分层增强聚酰亚胺湿凝胶;
(4)纤维分层增强聚酰亚胺湿凝胶的老化及干燥
将步骤(3)中所得的纤维分层增强聚酰亚胺湿凝胶加入到老化液中进行溶剂置换和老化,而后干燥即得短切纤维分层增强聚酰亚胺气凝胶。
优选步骤(1)中所述的二酐至少为3,3’,4,4’-联苯四甲酸二酐、3,3’,4,4’-二苯酮四酸二酐或均苯四甲酸二酐中的一种;所述的二胺至少为4,4’-二氨基二苯醚、1,4-对苯二胺或2,2'-二甲基-4,4'-二氨基联苯中的一种;其中二酐单体与二胺单体的摩尔比为1:(0.7~1)。二酐与二胺单体和溶剂混合后的反应温度为室温,搅拌时间是12~24h。
优选步骤(1)中所述的极性非质子溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮或二甲基亚砜(DMSO)中的任意一种或两种。
优选步骤(2)中所述短切阻裂纤维为玻璃短切纤维、凯夫拉短切纤维或聚丙烯短切纤维;纤维长度为6~12mm,直径为15~45nm。
优选步骤(2)中短切纤维进行湿法表面改性为:改性试剂为硝酸,并在60~75℃下对短切纤维进行改性,时间为2~4h,硝酸改性后的短切纤维用乙醇和去离子水洗涤干净后,在真空干燥箱中干燥,干燥温度为40~55℃,干燥时间为6~9h。
优选步骤(3)中聚酰胺酸溶液进行化学亚胺化为:选择催化剂吡啶试剂和脱水剂醋酸酐试剂来进行化学亚胺化,其中催化剂吡啶、脱水剂醋酸酐与二酐的摩尔比为8:(8~8.3):(0.7~1)。
优选步骤(3)中层状短切阻裂纤维铺展的方式为将短切纤维用纤维梳理机梳理成层状,然后将层状纤维铺展在聚酰亚胺湿凝胶中,层数为1~4层,每层厚度为0.4~0.8mm;改性的层状短切阻裂纤维的总质量分数为气凝胶总质量的6~24%。
优选步骤(4)中所述的老化液为乙醇溶液,老化时间为48~72h,期间每4~12h换一次老化液。
优选步骤(4)中所述的干燥方法为冷冻干燥或CO2超临界干燥中的一种。CO2超临界干燥时干燥温度是35~50℃,压力是10~15Mpa。
制得纤维分层增强聚酰亚胺气凝胶密度为0.09~0.12g/cm3,室温热导率为0.04793~0.04859W/(m·K)。
有益效果:
(1)相比较于传统的抗冲击纤维增强聚酰亚胺气凝胶复合材料,本发明制备得到的短切纤维分层增强聚酰亚胺气凝胶,具有优异的减震降噪、隔热和尺寸稳定性,特别是在需要抗冲击应用领域,具有广阔的应用前景。
(2)相比较于传统纤维增强聚酰亚胺气凝胶制备工艺,本发明使用短切纤维分层铺展在聚酰亚胺气凝胶基体当中,即在垂直于纤维层方向上保持气凝胶材料的隔热性能和可压缩性能,又增强了气凝胶复合材料在水平方向上的阻裂性能。操作简单,且生产出的样品稳定性好,有望实现批量生产。
(3)本发明制得的纤维分层增强聚酰亚胺气凝胶可用于卫星表面防护系统中的支撑层材料,可提高防护系统面临空间碎片冲击下的利用率,还可对空间碎片进行拦截。
附图说明
图1为所制备的短切纤维分层增强聚酰亚胺气凝胶实物图;
图2为实例1~4产物的应力-应变图。
具体实施方式
下面结合实例对本发明作进一步说明,但保护范围并不限于此。
实例1
(1)将2.05g 2,2'-二甲基-4,4'-二氨基联苯(DMBZ)溶入到装有95mL的N-甲基吡咯烷酮(NMP)溶剂当中,在室温下搅拌20min后,待其完全溶解后加入2.95g 3,3’,4,4’-联苯四甲酸二酐(BPDA),于25℃进行缩合聚合反应24h,得到酐基封端的聚酰胺酸溶液(二酐单体与二胺单体摩尔比为1:0.7)。
(2)在60℃下将短切纤维浸泡在硝酸中改性,改性时间为2h,取出后,先后用乙醇和去离子水洗涤干净,然后在干燥箱中干燥,干燥温度是40℃,干燥时间是6h。
(3)对步骤(1)中得到的聚酰胺酸溶液进行化学亚胺化,将催化剂吡啶7mL和脱水剂醋酸酐8mL(吡啶和醋酸酐与二酐单体摩尔比是8:8:0.7)加入到聚酰胺酸溶液当中,搅拌2min得到聚酰亚胺溶胶。
(4)将步骤(3)中的聚酰亚胺溶胶倒入一半至模具当中,待其即将凝胶时,在模具里铺展1层步骤(2)中改性的短切纤维,短切纤维层厚度为0.6mm,短切纤维质量分数占气凝胶总质量的6%,然后将剩余聚酰亚胺溶胶倒入到模具当中,静置一段时间后可得短切纤维增强聚酰亚胺湿凝胶。
(5)纤维分层增强聚酰亚胺湿凝胶经老化、溶剂置换、超临界干燥得到抗冲击性短切纤维增强聚酰亚胺气凝胶。所述老化温度为25℃,溶剂置换溶液为乙醇溶液,置换时间为72h,期间每12h换一次老化液。超临界干燥压力为10Mpa,干燥时间为24h,干燥温度为50℃。所制得的材料密度为0.09g/cm3,厚度为50mm,室温热导率为0.04793W/(m·K),命名为PI-6。
图1为实例1所制备的短切纤维分层增强聚酰亚胺气凝胶实物图,从图2中可看出PI-6在75%应变时应力为0.49MPa,且外观平整无裂纹。
实例2
(1)将2.10g 1,4-对苯二胺溶入到装有95mLN,N-二甲基甲酰胺(DMF)溶剂当中,在室温下搅拌20min后,待其完全溶解后加入2.93g 3,3’,4,4’-二苯酮四酸二酐,于25℃进行缩合聚合反应21h,得到酐基封端的聚酰胺酸溶液(二酐单体与二胺单体摩尔比为1:0.8)。
(2)在65℃下将短切纤维浸泡在硝酸中改性,改性时间为2.5h,取出后,先后用乙醇和去离子水洗涤干净,然后在干燥箱中干燥,干燥温度是45℃,干燥时间是7h。
(3)对步骤(1)中得到的聚酰胺酸溶液进行化学亚胺化,将催化剂吡啶6.6mL和脱水剂醋酸酐7.8mL(吡啶和醋酸酐与二酐单体摩尔比是8:8.1:0.8)加入到聚酰胺酸溶液当中,搅拌2min得到聚酰亚胺溶胶。
(4)将步骤(2)中改性的短切纤维分2层铺展在步骤(3)中的聚酰亚胺溶胶中,其中短切纤维总质量分数占气凝胶总质量的12%,2层短切纤维质量分数分别占气凝胶总质量的5%和7%,短切纤维层厚度分别为0.5mm和0.7mm,静置一段时间后可得短切纤维增强聚酰亚胺湿凝胶。
(5)纤维分层增强聚酰亚胺湿凝胶经老化、溶剂置换、超临界干燥得到抗冲击性短切纤维增强聚酰亚胺气凝胶。所述老化温度为25℃,溶剂置换溶液为乙醇溶液,置换时间为66h,期间每8h换一次老化液。超临界干燥压力为11Mpa,干燥时间为24h,干燥温度为45℃。所制得的材料密度为0.096g/cm3,厚度为52mm,室温热导率为0.048096W/(m·K),命名为PI-12。
从图2中可以看出PI-12在75%应变时应力为1.24MPa。
实例3
(1)将2.15g 4,4’-二氨基二苯醚溶入到装有95mL二甲基亚砜(DMSO)溶剂当中,在室温下搅拌20min后,待其完全溶解后加入2.96g均苯四甲酸二酐,于25℃进行缩合聚合反应18h,得到酐基封端的聚酰胺酸溶液(二酐单体与二胺单体摩尔比为1:0.9)。
(2)在70℃下将短切纤维浸泡在硝酸中改性,改性时间为3h,取出后,先后用乙醇和去离子水洗涤干净,然后在干燥箱中干燥,干燥温度是50℃,干燥时间是8h。
(3)对步骤(1)中得到的聚酰胺酸溶液进行化学亚胺化,将催化剂吡啶6.2mL和脱水剂醋酸酐7.5mL(吡啶和醋酸酐与二酐单体摩尔比是8:8.2:0.9)加入到聚酰胺酸溶液当中,搅拌2min得到聚酰亚胺溶胶。
(4)将步骤(2)中改性的短切纤维分3层铺展在步骤(3)中的聚酰亚胺溶胶中,其中短切纤维总质量分数占气凝胶总质量的18%,三层短切纤维质量分数分别占气凝胶总质量的4%、6%和8%,短切纤维层厚度分别为0.4mm、0.6mm和0.8mm,静置一段时间后可得短切纤维增强聚酰亚胺湿凝胶。
(5)纤维分层增强聚酰亚胺湿凝胶经老化、溶剂置换、超临界干燥得到抗冲击性短切纤维增强聚酰亚胺气凝胶。所述老化温度为25℃,溶剂置换溶液为乙醇溶液,置换时间为60h,期间每6h换一次老化液。超临界干燥压力为13Mpa,干燥时间为24h,干燥温度为40℃。所制得的材料密度为0.112g/cm3,厚度为54mm,室温热导率为0.04829W/(m·K),命名为PI-18。
从图2中可以看出PI-18在75%应变时应力为1.13MPa。
实例4
(1)将2.20g1,4-对苯二胺溶入到装有95mLN,N-二甲基乙酰胺(DMAc)溶剂当中,在室温下搅拌20min后,待其完全溶解后加入2.92g 3,3’,4,4’-二苯酮四酸二酐,于25℃进行缩合聚合反应12h,得到酐基封端的聚酰胺酸溶液(二酐单体与二胺单体摩尔比为1:1)。
(2)在75℃下将短切纤维浸泡在硝酸中改性,改性时间为4h,取出后,先后用乙醇和去离子水洗涤干净,然后在干燥箱中干燥,干燥温度是55℃,干燥时间是9h。
(3)对步骤(1)中得到的聚酰胺酸溶液进行化学亚胺化,将催化剂吡啶5.8mL和脱水剂醋酸酐7.2mL(吡啶和醋酸酐与二酐单体摩尔比是8:8.3:1)加入到聚酰胺酸溶液当中,搅拌2min得到聚酰亚胺溶胶。
(4)将步骤(2)中改性的短切纤维分4层铺展在步骤(3)中的聚酰亚胺溶胶中,其中短切纤维总质量分数占气凝胶总质量的24%,4层短切纤维质量分数分别占气凝胶总质量的4%、5%、7%和8%,短切纤维层厚度分别为0.4mm、0.5mm、0.7mm和0.8mm,静置一段时间后可得短切纤维增强聚酰亚胺湿凝胶。
(5)纤维分层增强聚酰亚胺湿凝胶经老化、溶剂置换、超临界干燥得到抗冲击性短切纤维增强聚酰亚胺气凝胶。所述老化温度为25℃,溶剂置换溶液为乙醇溶液,置换时间为48h,期间每4h换一次老化液。超临界干燥压力为15Mpa,干燥时间为24h,干燥温度为35℃。所制得的材料密度为0.12g/cm3,厚度为56mm,室温热导率为0.04859W/(m·K),命名为PI-24。
从图2中可以看出PI-24在75%应变时应力为2.18MPa。
以上实施例1~4应力-应变图如图2所示,从图中可以看出随着短切纤维质量分数和层数的适量增加,气凝胶在同一应力条件下其应变是逐渐降低的,且其应变最大可以达到75%左右,因此具有不错的抗冲击性。
Claims (9)
1.一种短切纤维分层增强聚酰亚胺气凝胶的制备方法,其具体步骤如下:
(1)制备聚酰胺酸溶液
量取一定量的二酐单体、二胺单体溶解到极性非质子溶剂当中,得到聚酰胺酸溶液;
(2)短切阻裂纤维表面改性
通过对短切纤维进行湿法表面改性,得到改性的层状短切阻裂纤维;
(3)制备纤维分层增强聚酰亚胺湿凝胶
对步骤(1)中的聚酰胺酸溶液进行化学亚胺化得到聚酰亚胺溶胶,再将聚酰亚胺溶胶倒入模具中,待其开始凝胶后再将步骤(2)中改性的层状短切阻裂纤维铺展在模具中,然后继续倒入聚酰亚胺溶胶,重复上述步骤1~4次,待其凝胶完全后得到纤维分层增强聚酰亚胺湿凝胶;
(4)纤维分层增强聚酰亚胺湿凝胶的制备
将步骤(3)中所得的纤维分层增强聚酰亚胺湿凝胶加入到老化液中进行溶剂置换和老化,而后干燥即得短切纤维分层增强聚酰亚胺气凝胶。
2.根据权利要求1所述的制备方法,其特征在于步骤(1)中所述的二酐至少为3,3’,4,4’-联苯四甲酸二酐、3,3’,4,4’-二苯酮四酸二酐或均苯四甲酸二酐中的一种;所述的二胺至少为4,4’-二氨基二苯醚、1,4-对苯二胺或2,2'-二甲基-4,4'-二氨基联苯中的一种;其中二酐单体与二胺单体的摩尔比为1:(0.7~1)。
3.根据权利要求1所述的制备方法,其特征在于步骤(1)中所述的极性非质子溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮或二甲基亚砜(DMSO)中的任意一种或两种。
4.根据权利要求1所述的制备方法,其特征在于步骤(2)中所述短切阻裂纤维为玻璃短切纤维、凯夫拉短切纤维或聚丙烯短切纤维;纤维长度为6~12mm,直径为15~45nm。
5.根据权利要求1所述的制备方法,其特征在于步骤(3)中聚酰胺酸溶液进行化学亚胺化为:选择催化剂吡啶试剂和脱水剂醋酸酐试剂来进行化学亚胺化,其中催化剂吡啶、脱水剂醋酸酐与二酐的摩尔比为8:(8~8.3):(0.7~1)。
6.根据权利要求1所述的制备方法,其特征在于步骤(3)中层状短切阻裂纤维铺展的方式为将短切纤维用纤维梳理机梳理成层状,然后将层状纤维铺展在聚酰亚胺湿凝胶中,层数为1~4层,每层厚度为0.4~0.8mm;改性的层状短切阻裂纤维的总质量分数为气凝胶总质量的6~24%。
7.根据权利要求1所述的制备方法,其特征在于步骤(4)中所述的老化液为乙醇溶液;老化时间48~72h,期间每4~12h换一次老化液。
8.根据权利要求1所述的制备方法,其特征在于步骤(4)中所述的干燥方法为冷冻干燥或CO2超临界干燥中的一种。
9.根据权利要求1所述的制备方法,其特征在于制得的短切纤维分层增强聚酰亚胺气凝胶的密度为0.09~0.12g/cm3,热导率为0.04793~0.04859W/(m·K)。
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