CN105671671B - 一种含对称双嘧啶结构聚酰亚胺纤维的制备方法 - Google Patents
一种含对称双嘧啶结构聚酰亚胺纤维的制备方法 Download PDFInfo
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Abstract
本发明涉及一种含对称双嘧啶结构聚酰亚胺纤维的制备方法,包括:将2,2'‑(1,4‑亚苯基)二[5‑(4‑氨基苯基)]嘧啶和无水氯化亚锡加入到多聚磷酸中,加入芳香族二酐单体,然后加入P2O5,170~200℃反应4~6h,然后升温至200~240℃反应3~6h,得到液晶型聚酰亚胺纺丝液;采用双螺杆挤出设备,将聚酰亚胺纺丝液进行纺丝,多凝固浴成型,水洗,卷绕,得到聚酰亚胺初生纤维,干燥后在氮气保护下,三级热牵伸,即得。本发明制备的聚酰亚胺纤维具有优异的力学性能,且克服了传统酚类、多卤代苯类溶剂毒性大,两步法加工非质子溶剂难以去除等合成、加工问题,应用前景广阔。
Description
技术领域
本发明属于聚酰亚胺纤维制备领域,特别涉及一种含对称双嘧啶结构聚酰亚胺纤维的制备方法。
背景技术
聚酰亚胺纤维作为高性能纤维的一个品种,有较高的理论强度与模量,具有耐高温、抗溶剂、化学稳定、耐辐照等多种优点,被认为是综合性能最优异的聚合物材料之一,已广泛应用于航空、航天、微电子等高新领域。聚酰亚胺纤维结构具有极强的可控性,调控单体结构和种类可得形貌、性质各异的聚酰亚胺纤维。高性能化的聚酰亚胺纤维通常具有刚性的化学结构,聚集态结构有序程度高,而且普遍具有较高的耐热性能,其玻璃化温度通常在300℃以上,这些高性能化的特点均有益于聚酰亚胺纤维的应用。但是,高的电子堆积密度及玻璃化转变温度也意味着聚酰亚胺难以溶解于常规溶剂、难以熔融加工。传统的聚酰亚胺溶剂多为酚类、多卤代苯类溶剂,如US5378420,CN201110185147.9采用间甲酚、对氯苯酚为溶剂,制备了聚酰亚胺材料。但该类溶剂普遍具有刺激性气味、毒性大、环境友好性差等诸多缺点。通过非质子极性溶剂(N,N-二甲基甲酰胺,N,N-二甲基乙酰胺,N-甲基吡咯烷酮)制备聚酰胺酸前驱液,再经环化制备聚酰亚胺,也是高性能聚酰亚胺材料的一种制备方法。但该方法往往伴随着与聚合物络合的极性溶剂难以去除充分,材料理化性能降低等诸多缺点。
通过结构设计及溶剂选择制备可溶性聚酰亚胺是制备高性能聚酰亚胺纤维的重要途径。其中,将对称性全芳香族结构单体引入聚合物中是提高聚合物材料性能的一种重要、有效的方法。如CN201010572496.1中将2-(4-氨基苯基)-5-氨基苯并咪唑刚性杂环引入聚酰亚胺主链,制备拉伸强度达2.5GPa的聚酰亚胺纤维,俄罗斯专利RU2062276C1以半对称的2,5-二(4-氨基苯基)嘧啶为刚性单元,制备了强度达348MPa的聚酰亚胺膜材料;中国专利CN200510017072.8制备了半对称的2-氨基-5-(4-氨基苯基)嘧啶,2-(4-氨基苯基)-5-氨基嘧啶,制备了性能优异的聚酰亚胺材料。
对文献报道及国内外专利(FR9314042,JP28506092A,KR20070010956A,CN200810201195.0,CN201210005140.9等)调研发现,多聚磷酸体系是许多难溶聚合物(PBI,PBO,PI)的良溶剂,并且通过结构调控可制备液晶型聚合物溶液。利用聚合物在溶剂中的液晶性质,可制备高性能的聚合物材料,如利用芳香族聚酰胺在浓硫酸中的液晶性质,聚对苯撑苯并二噁唑(PBO)在多聚磷酸中的液晶性质,可制备高性能的Kevlar,PBO纤维。
发明内容
本发明所要解决的技术问题是提供一种含对称双嘧啶结构聚酰亚胺纤维的制备方法,该方法制备的聚酰亚胺纤维具有优异的力学性能,且克服了传统酚类、多卤代苯类溶剂毒性大,两步法加工非质子溶剂难以去除等合成、加工问题,应用前景广阔。
本发明的一种含对称双嘧啶结构聚酰亚胺纤维的制备方法,包括:
(1)将二胺单体2,2'-(1,4-亚苯基)二[5-(4-氨基苯基)]嘧啶和无水氯化亚锡加入到澄清粘稠多聚磷酸中,加入芳香族二酐单体(非特别说明,下文所述二酐均为芳香族二酐),然后加入P2O5,170~200℃反应4~6h,然后升温至200~240℃反应3~6h,得到液晶型聚酰亚胺纺丝液;其中,二胺与二酐单体的摩尔比为1:0.99~1:1.02;二胺和二酐的总质量占反应体系总质量(包括二胺、二酐、无水氯化亚锡、P2O5以及多聚磷酸的总质量)的11~30%;
(2)采用双螺杆挤出设备,将步骤(1)中的聚酰亚胺纺丝液进行湿法纺丝或干-湿法纺丝,多凝固浴成型,水洗,卷绕,干燥,得到聚酰亚胺初生纤维;将聚酰亚胺初生纤维干燥后在氮气保护下,三级热牵伸,得到含对称双嘧啶结构聚酰亚胺纤维;其中,热牵伸倍数为2~9倍。
所述步骤(1)中2,2'-(1,4-亚苯基)二[5-(4-氨基苯基)]嘧啶的结构式为
所述步骤(1)中无水氯化亚锡的加入量占二胺单体和二酐单体质量之和的0.5%~6%;
所述步骤(1)中多聚磷酸所含P2O5质量分数为75%~80%;加入芳香族二酐单体后加入的P2O5质量占多聚磷酸质量的10%~100%。
所述步骤(1)中二酐为
中的至少一种。
所述步骤(2)中双螺杆设备的挤出温度分三个温区,温度分别设定为155~165℃、170~185℃、190~210℃。
所述步骤(2)中纺丝过程中纺丝头的喷丝孔直径为0.05~0.6mm,喷丝孔数目为10~100孔。
所述步骤(2)中多凝固浴为:第一凝固浴为磷酸/水混合体系,体积比为10/90~35/65,凝固浴长度为2~4m,凝固浴温度为35~70℃;第二凝固浴为水浴,凝固浴长度为3~6m,温度为40~90℃,牵伸倍率为1~5.5倍。
所述步骤(2)中卷绕速度为3~60m/min;干燥温度为60~120℃,干燥时间为6~12h。
所述步骤(2)中三级热牵伸的温度分别为350~380℃,400~420℃,440~460℃。
本发明包括聚酰亚胺液晶溶液的制备、纤维的纺丝成形、拉伸后处理等过程;以多聚磷酸为溶剂,含对称刚性结构的聚酰亚胺在溶剂中形成液晶相,经纺丝及后续热牵伸,纤维晶区趋向完善,制备的聚酰亚胺纤维具有优异的力学性能,且克服了传统酚类、多卤代苯类溶剂毒性大,两步法加工非质子溶剂难以去除等合成、加工问题,应用前景广阔。
本发明在多聚磷酸溶剂中构筑刚性聚酰亚胺液晶体系,采用液晶纺丝的方法克服了聚酰亚胺的在传统有机溶剂毒性大、两步法纺丝后环化复杂等问题,是一种简单、有效的高性能聚酰亚胺纤维制备方法。
有益效果
(1)本发明制备了新型含对称双嘧啶结构的聚酰亚胺纤维,采用的多聚磷酸体系,解决了刚性聚酰亚胺溶解性问题,对环境破坏较小,液晶纺丝的方法有利于实现聚酰亚胺纤维的高性能化;
(2)本发明的方法得到的含对称双嘧啶结构聚酰亚胺纤维具有优异的力学性能,且克服了传统酚类、多卤代苯类溶剂毒性大,两步法加工非质子溶剂难以去除等合成、加工问题,应用前景广阔。
附图说明
图1为本发明中聚酰亚胺纤维的纺丝示意图;其中,图中液晶前驱液为发明中的高粘度液晶型聚酰亚胺纺丝液。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
在氮气保护下,将500g P2O5含量80%的多聚磷酸加入到1L反应釜中,加热至150搅拌1.5h,得澄清多聚磷酸溶液。
依次加入62.4g(0.15mol)的二胺单体2,2'-(1,4-亚苯基)二[5-(4-氨基苯基)]嘧啶,20g的无水氯化亚锡,48.3g(0.15mol)的3,3’,4,4’-二苯酮四酸二酐(BTDA),并补充加入166g的P2O5,二胺和二酐的质量占反应体系总质量的14.2%,P2O5质量占多聚磷酸溶液质量的85%。升高温度,反应体系在180℃反应5h,220℃反应5h,得液晶型聚酰亚胺纺丝液。溶液黄色透明,特性粘数为1.77dL/g(浓硫酸为溶剂,25℃测定)。
将液晶纺丝原液,输送至L/D=30的双螺杆挤出机,挤出设备三个温区温度设置在160℃、180℃、195℃。计量泵输出速度为80g/min。脱泡后,输出至50×0.1mm喷丝板进行液晶纺丝,第一凝固浴为磷酸/水(10/90,体积比),温度60℃,凝固浴长度2m;第二凝固浴为长度5m的水溶液,纤维在70℃下牵伸2倍。水洗后卷绕,卷绕速度为20m/min,得初生聚酰亚胺纤维。
初生纤维在100℃干燥6h后,在氮气保护下,在360℃、400℃、440℃的热管中牵伸,牵伸倍率3.8倍,得高强度聚酰亚胺纤维,纤维纤度6.3dtex,拉伸强度1.7GPa,拉伸模量达77GPa。
实施例2
在氮气保护下,将500g P2O5含量80%的多聚磷酸加入到1L反应釜中,加热至150搅拌1.5h,得澄清多聚磷酸溶液。
依次加入58.2g(0.14mol)的二胺单体2,2'-(1,4-亚苯基)二[5-(4-氨基苯基)]嘧啶,18g的无水氯化亚锡,41.1g(0.14mol)的3,3',4,4'-联苯四羧酸二酐(BPDA),并补充加入269g P2O5。二胺和二酐的质量占反应体系总质量的11.4%,P2O5质量占多聚磷酸溶液质量的87%。随后升温,反应体系在190℃反应4h,230℃反应5h,得液晶型聚酰亚胺纺丝液。溶液黄色透明,特性粘数为2.21dL/g(浓硫酸为溶剂,25℃测定)。
将液晶纺丝原液,输送至L/D=30的双螺杆挤出机,挤出设备三个温区温度设置在165℃、185℃、200℃。计量泵输出速度为80g/min。脱泡后,输出至50×0.1mm喷丝板进行液晶纺丝,第一凝固浴为磷酸/水(10/90,体积比),温度60℃,凝固浴长度2m;第二凝固浴为水溶液,长度为5m,温度70℃,纤维在第二凝固浴中牵伸3倍。水洗后卷绕,卷绕速度为30m/min,得初生聚酰亚胺纤维。
初生纤维在100℃干燥6h后,在氮气保护下,在360℃、420℃、450℃三级热管中牵伸,牵伸倍率4.1倍,得高强度聚酰亚胺纤维,纤维纤度4.5dtex,拉伸强度2.8GPa,拉伸模量达107GPa。
实施例3
在氮气保护下,将500g P2O5含量80%的多聚磷酸加入到1L反应釜中,加热至150搅拌1.5h,得澄清多聚磷酸溶液。
依次加入70.4g(0.17mol)的二胺单体2,2'-(1,4-亚苯基)二[5-(4-氨基苯基)]嘧啶,25g的无水氯化亚锡,37.1g(0.14mol)的均苯四甲酸二酐(PMDA)和240g的P2O5至反应体系,二胺和二酐的质量占反应体系总质量的12.7%,P2O5占多聚磷酸溶液总质量的86.5%。升高温度,反应体系在175℃反应5h,220℃反应5h,得液晶型聚酰亚胺纺丝液。溶液黄色透明,特性粘数为2.05dL/g(浓硫酸为溶剂,25℃测定)。
将液晶纺丝原液,输送至L/D=30的双螺杆挤出机,挤出设备三个温区温度设置在160℃、185℃、195℃。计量泵输出速度为80g/min。脱泡后,输出至50×0.1mm喷丝板进行液晶纺丝,第一凝固浴为磷酸/水(15/85,体积比),温度60℃,凝固浴长度2m,第二凝固浴为水,长度为5m,温度70℃,纤维在第二凝固浴中牵伸2倍。水洗后卷绕,卷绕速度为40m/min,得初生聚酰亚胺纤维。
初生纤维在100℃干燥6h后,在氮气保护下,在355℃、420℃、450℃三级热管中牵伸,牵伸倍率4.4倍,得高强度聚酰亚胺纤维,纤维纤度4.7dtex,拉伸强度2.6GPa,拉伸模量达110GPa。
实施例4
在氮气保护下,将500g P2O5含量80%的多聚磷酸加入到1L反应釜中,加热至150搅拌1.5h,得澄清多聚磷酸溶液备用。
依次加入70.74g(0.17mol)的二胺单体2,2'-(1,4-亚苯基)二[5-(4-氨基苯基)]嘧啶,28g的无水氯化亚锡,52.7g(0.17mol)的4,4'-联苯醚二酐(ODPA)和157g的P2O5至反应体系。二胺和二酐的质量占反应物总质量的15.8%,P2O5质量占多聚磷酸溶液质量的84.8%。升高温度,反应体系在190℃反应5h,230℃反应5h,得液晶型聚酰亚胺纺丝液。溶液黄色透明,特性粘数为1.94dL/g(浓硫酸为溶剂,25℃测定)。
将液晶纺丝原液,输送至L/D=30的双螺杆挤出机,挤出设备三个温区温度设置在160℃、180℃、200℃。计量泵输出速度为80g/min。脱泡后,输出至50×0.1mm喷丝板进行液晶纺丝,第一凝固浴为磷酸/水(10/90,体积比),温度65℃,凝固浴长度2m;第二凝固浴为水,长度为5m,温度70℃,纤维牵伸2.3倍。充分水洗后卷绕,卷绕速度为25m/min,得初生聚酰亚胺纤维。
初生纤维在100℃干燥6h后,在氮气保护下,在370℃、420℃、460℃中热牵伸,牵伸倍率4.2倍的高强度聚酰亚胺纤维,纤维纤度5.2dtex,拉伸强度1.9GPa,拉伸模量达90GPa。
实施例5
在氮气保护下,将500g P2O5含量80%的多聚磷酸加入到1L反应釜中,加热至150搅拌1.5h,得澄清多聚磷酸溶液,冷却至100℃备用。
依次加入62.4g(0.15mol)的二胺单体2,2'-(1,4-亚苯基)二[5-(4-氨基苯基)]嘧啶,28g的无水氯化亚锡,29.4g(0.1mol)3,3',4,4'-联苯四羧酸二酐(BPDA)与10.8g(0.05mol)的均苯四甲酸二酐(PMDA)和157g的P2O5至反应体系,二胺和二酐的质量占反应物总质量的17.0%,P2O5质量占多聚磷酸溶液质量的84.8%。升高温度,体系在185℃反应4h,220℃反应5h,得液晶型聚酰亚胺纺丝液。溶液黄色透明,特性粘数为1.94dL/g(浓硫酸为溶剂,25℃测定)。
将液晶纺丝原液,输送至L/D=30的双螺杆挤出机,挤出设备三个温区温度设置在160℃、180℃、195℃。计量泵输出速度为80g/min。脱泡后,输出至50×0.1mm喷丝板进行液晶纺丝,第一凝固浴为磷酸/水(20/80,体积比),温度60℃,凝固浴长度2m;第二凝固浴为水,长度为5m,温度70℃,纤维牵伸3倍。充分水洗后卷绕,卷绕速度为25m/min,得初生聚酰亚胺纤维。
初生纤维在100℃干燥6h后,在氮气保护下,在370℃、420℃、460℃中热牵伸,牵伸倍率6倍,得高强度聚酰亚胺纤维,纤维纤度3.7dtex,拉伸强度2.9GPa,拉伸模量达115GPa。
Claims (8)
1.一种含对称双嘧啶结构聚酰亚胺纤维的制备方法,包括:
(1)将二胺单体2,2'-(1,4-亚苯基)二[5-(4-氨基苯基)]嘧啶和无水氯化亚锡加入到多聚磷酸中,加入芳香族二酐单体,然后加入P2O5,170~200℃反应4~6h,然后升温至200~240℃反应3~6h,得到液晶型聚酰亚胺纺丝液;其中,二胺与二酐单体的摩尔比为1:0.99~1:1.02;二胺和二酐的总质量占反应体系总质量的11~30%;反应体系总质量为:二胺、二酐、无水氯化亚锡、P2O5以及多聚磷酸的总质量;
(2)采用双螺杆挤出设备,将步骤(1)中的聚酰亚胺纺丝液进行湿法纺丝或干-湿法纺丝,多凝固浴成型,水洗,卷绕,得到聚酰亚胺初生纤维;将聚酰亚胺初生纤维干燥后在氮气保护下,三级热牵伸,得到含对称双嘧啶结构聚酰亚胺纤维;其中,热牵伸倍数为2~9倍,多凝固浴为:第一凝固浴为磷酸/水混合体系,体积比为10/90~35/65,凝固浴长度为2~4m,凝固浴温度为35~70℃;第二凝固浴为水浴,凝固浴长度为3~6m,温度为40~90℃,牵伸倍率为1~5.5倍。
2.根据权利要求1所述的一种含对称双嘧啶结构聚酰亚胺纤维的制备方法,其特征在于,所述步骤(1)中无水氯化亚锡的加入量占二胺单体和芳香族二酐单体质量之和的0.5%~6%。
3.根据权利要求1所述的一种含对称双嘧啶结构聚酰亚胺纤维的制备方法,其特征在于,所述步骤(1)中所述多聚磷酸所含P2O5质量分数为75%~80%;加入芳香族二酐单体后加入的P2O5质量占多聚磷酸质量的10%~100%。
4.根据权利要求1所述的一种含对称双嘧啶结构聚酰亚胺纤维的制备方法,其特征在于,所述步骤(1)中芳香族二酐为
中的至少一种。
5.根据权利要求1所述的一种含对称双嘧啶结构聚酰亚胺纤维的制备方法,其特征在于,所述步骤(2)中双螺杆设备的挤出温度分三个温区,温度分别设定为155~165℃、170~185℃、190~210℃。
6.根据权利要求1所述的一种含对称双嘧啶结构聚酰亚胺纤维的制备方法,其特征在于,所述步骤(2)中纺丝过程中纺丝头的喷丝孔直径为0.05~0.6mm,喷丝孔数目为10~100孔。
7.根据权利要求1所述的一种含对称双嘧啶结构聚酰亚胺纤维的制备方法,其特征在于,所述步骤(2)中卷绕速度为3~60m/min;干燥温度为60~120℃,干燥时间为6~12h。
8.根据权利要求1所述的一种含对称双嘧啶结构聚酰亚胺纤维的制备方法,其特征在于,所述步骤(2)中三级热牵伸的温度分别为350~380℃,400~420℃,440~460℃。
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Citations (4)
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---|---|---|---|---|
CN101407594A (zh) * | 2008-11-25 | 2009-04-15 | 北京市射线应用研究中心 | 一种改性聚酰亚胺泡沫及其制备方法 |
CN102586930A (zh) * | 2012-01-09 | 2012-07-18 | 东华大学 | 一种利用液晶纺丝制备聚酰亚胺纤维的方法 |
CN103204847A (zh) * | 2013-04-02 | 2013-07-17 | 上海交通大学 | 侧链型咪唑基联苯胺的制备方法 |
CN104195666A (zh) * | 2014-09-12 | 2014-12-10 | 东华大学 | 一种基于邻甲基芳酰胺酰亚胺化制备聚酰亚胺纤维的方法 |
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CN101407594A (zh) * | 2008-11-25 | 2009-04-15 | 北京市射线应用研究中心 | 一种改性聚酰亚胺泡沫及其制备方法 |
CN102586930A (zh) * | 2012-01-09 | 2012-07-18 | 东华大学 | 一种利用液晶纺丝制备聚酰亚胺纤维的方法 |
CN103204847A (zh) * | 2013-04-02 | 2013-07-17 | 上海交通大学 | 侧链型咪唑基联苯胺的制备方法 |
CN104195666A (zh) * | 2014-09-12 | 2014-12-10 | 东华大学 | 一种基于邻甲基芳酰胺酰亚胺化制备聚酰亚胺纤维的方法 |
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