CN101591436B - 含二氮杂萘酮联苯结构聚苯并咪唑及其制备方法 - Google Patents
含二氮杂萘酮联苯结构聚苯并咪唑及其制备方法 Download PDFInfo
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Abstract
本发明涉及了一种含二氮杂萘酮联苯结构聚苯并咪唑及其制备方法,属于高分子科学技术领域。以4-[4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮或其衍生物,和芳香族四元胺或其盐酸盐作为缩聚单体,也可同时加入其它二元羧酸或其衍生物,在多聚磷酸中进行溶液缩聚反应,可以制得具有优异耐热性的含二氮杂萘酮联苯结构聚苯并咪唑树脂。这类聚苯并咪唑树脂可用于耐高温纤维、漆、涂料、粘合剂、膜和复合材料等领域,有着广阔的应用前景。
Description
技术领域
本发明属于高分子科学技术领域,涉及到高性能高分子材料及其制备法,特别涉及到一类含二氮杂萘酮联苯结构聚苯并咪唑及其制备法。
背景技术
聚苯并咪唑(Polybenzimidazole)是一类杂环高性能高分子材料,具有很高的玻璃化转变温度、优异的热稳定性、良好的阻燃性、突出的耐化学腐蚀性和优异的机械性能,能够承受非常苛刻的使用环境,这类材料可作为阻燃材料、耐高温粘合剂和涂料等应用于航空航天、海水淡化和膜分离领域。最近,聚苯并咪唑由于在质子交换膜燃料电池和直接甲醇燃料电池领域的应用而受到广泛贯注。然而聚苯并咪唑的熔点很高,而且溶解性差,导致其应用受到限制。商品化的聚苯并咪唑,聚(2,2’-间苯撑-5,5’-联苯并咪唑),是由间苯二甲酸和3,3’-二氨基联苯胺缩聚而成,具有刚性结构,加工性差。
在分子主链中引入柔性基团或体积较大的基团可以改善聚苯并咪唑的溶解性,是一种制备可溶性聚苯并咪唑的方法。例如,Connell J.W.等人【Hergenrother,P.M.;Smith,J.G.;Connell,J.W.Polymer,1993,34,856-865.】通过在聚苯并咪唑的主链中引入醚键,合成聚芳醚苯并咪唑,聚合物具有良好的溶解性,其玻璃化转变温度为264~352℃,比商品化聚苯并咪唑有明显降低;Chuang S.W.等人【Chuang,S.W.;Hsu,S.L.C.,Journal of Polymer Science Parta-Polymer Chemistry 2006,44,(15),45084513.】以2,2-双(4-羧基苯基)六氟丙烷与3,3’-二氨基联苯胺为原料制备含氟聚苯并咪唑,所合成的聚合物可溶解于N-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)和二甲基亚砜(DMSO)等极性溶剂中,5%热失重温度为520℃;Benicewicz B.C.等人【Xiao,L;Zhang,H;Jana,T;Scanlon,E;Chen,R;Choe,E.W;Ramanathan,L.S;Yu,S;Benicewicz,B.C,Fuel Cells 2005,5,(2),287-295】以含吡啶环的二元羧酸合成含氮杂环的聚苯并咪唑,聚合物的溶解性得到明显改善,其初始热失重温度为420℃,与mPBI相比有明显降低;Vernekar S.P.等人【Kulkarni,M;Potrekar,R;Kulkarni,R.A.;Vernekar,S.P,Journal of Polymer Science Part a-Polymer Chemistry 2008,46,(17),5776-5793】在聚苯并咪唑的分子主链上引入体积较大的氨基苯氧基侧基,所合成的聚合物的玻璃化转变温度为376℃,5%热失重温度为516℃,可溶解于NMP、DMAc和DMSO等极性有机溶剂中。
在聚苯并咪唑的分子主链上引入磺酸基以制备磺化聚苯并咪唑,可以赋予聚苯并咪唑较高的质子传导能力。例如,Qing Shengbo等人【Qing,S.B;Huang,W;Yan,D.Y,Journal ofPolymer Science Part a-Polymer Chemistry 2005,43,(19),4363-4372】以含磺酸基和砜基的二元羧酸单体制备磺化聚苯并咪唑,聚合物可溶解于NMP、DMAc和DMSO等极性有机溶剂中,5%热失重温度在430℃以上,玻璃化转变温度为238℃左右。Asensio J.A.等人【Asensio,J.A;Borros,S;Gomez-Romero,P,Journal of Polymer Science Part a-Polymer Chemistry 2002,40,(21),3703-3710】以磺化间苯二甲酸和间苯二甲酸与3,3’-二氨基联苯胺共聚,制备磺化聚苯并咪唑,聚合物具有良好的耐热稳定性、溶解性和质子传导能力,但与商品化PBI相比,热稳定性有明显降低。
发明内容
本发明要解决的技术问题是从分子结构设计和应用角度出发,提供一种含二氮杂萘酮联苯结构聚苯并咪唑及其制备方法,以二元羧酸,4-[4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮或其衍生物为二元羧酸单体,也可同时加入其他二元羧酸或其衍生物,与四元胺或其盐酸盐进行缩聚反应,合成兼具优异耐热性和良好溶解性的聚苯并咪唑树脂;
本发明含二氮杂萘酮联苯结构聚苯并咪唑,其结构表达式如下:
上述聚苯并咪唑分子链中含有A和B两种结构单元,其中两种结构单元的含量分别为:0<A含量≤100%,0≤B含量<100%;
其中,R1、R2、R3和R4可以是氢、卤素取代基、苯基、苯氧基或是含有至少1个碳原子的直链或带支链的烷基或烷氧基,R1、R2、R3和R4的结构可以相同,也可以不同;
Ar1和Ar2结构是对应的芳香四元胺其盐酸盐与二元羧酸或其衍生物反应产生,由所选用不同芳香四元胺的结构决定,这里的Ar1和Ar2的结构可以相同也可以不同。表1列举了Ar1、Ar2的结构以及芳香四元胺的名称:
表1 Ar1、Ar2的结构以及对应芳香四元胺的名称
Ar3的结构由二元羧酸或其衍生物产生,所采用的二元羧酸可以为一种或几种,但必含有4-[4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮或其衍生物,Ar3的结构式如下:
本发明制备含二氮杂萘酮联苯结构聚苯并咪唑的方法是溶液缩聚法,具体制备过程分如下三个阶段:
(1)加料阶段,首先使用惰性气体(如氮气或氩气)在50~200℃对多聚磷酸进行脱氧,然后将芳香四元胺或其盐酸盐的一种或几种与含二氮杂萘酮联苯结构的4-[4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮或其衍生物,也可同时加入其它结构的二元羧酸单体或其衍生物,将反应体系搅拌均匀,上述芳香四元胺或其盐酸盐的摩尔数与二元羧酸单体或其衍生物的摩尔数之和的比值在0.98~1.02之间,此溶液聚合体系中单体质量百分含量在0.2%~60%之间。
(2)聚合反应阶段,采用逐步升温法,在50~250℃进行溶液缩聚反应,反应时间为2~500小时,其中升温温度间隔值控制在5~60℃,在每个温度点,反应持续时间为0.1~100小时之间;
(3)后处理阶段,当聚合反应结束后,将反应溶液直接或加入稀释剂后倒入沉淀剂中,将聚合物凝聚沉淀,然后反复洗涤聚合产物中残存的溶剂,也可用碱或弱碱性无机盐中和聚合产物中残存的溶剂并水洗至中性,最后干燥后即可得到含二氮杂萘酮联苯结构聚苯并咪唑。
本发明合成的含二氮杂萘酮联苯结构聚苯并咪唑树脂所用二元羧酸单体,4-[4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮或其衍生物具有如下的分子结构:
其中,R1、R2、R3和R4可以是氢、卤素取代基、苯基、苯氧基或是含有至少1个碳原子的直链或带支链的烷基或烷氧基,R1、R2、R3和R4的结构可以相同,也可以不同。
本发明采用的聚合反应溶剂为多聚磷酸,其浓度为80%~120%。
本发明使用的稀释剂有磷酸、多聚磷酸、甲磺酸或浓硫酸,其质量用量为初始多聚磷酸的0.1~200倍。
本发明使用的沉降剂包括水、碳酸氢钠水溶液、甲醇、乙醇、四氢呋喃或乙醚。
根据本发明合成的含二氮杂萘酮联苯结构聚苯并咪唑树脂,具有耐热稳定性优异、力学性能好、可溶解和成膜性好等优点,在耐高温的漆、粘合剂、膜、复合材料等领域,有着广阔的应用前景。
附图说明
图1是以4-[4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮和3,3’-二氨基联苯胺为原料合成聚苯并咪唑的红外光谱图。
图2是以4-[4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮和3,3’-二氨基联苯胺为原料合成聚苯并咪唑的热失重图。
具体实施方式
下面的实施例是对本发明的进一步说明,而不是限制本发明的范围。
实施例1:于带有搅拌、回流冷凝管、分水器和导气管的干燥100mL三口烧瓶中,加入9mL116%的多聚磷酸(PPA),通氮气保护,并将三口烧瓶进入到油浴中,升温至100℃,搅拌1小时,以除去体系中的氧气。然后,在三口烧瓶中加入0.4282g(2mmol)的3,3’-二氨基联苯胺(DAB)和0.9562g(2mmol)的4-[4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮,聚合体系在120℃下反应2小时,在150℃下反应10个小时,190℃下反应7个小时,然后将所得的粘稠液体缓慢倒入1L的去离子水中,在倒入的过程中不断地搅拌去离子水,最后得到红褐色的条状固体,用水洗至弱酸型,再用碳酸钠的水溶液浸泡,用去离子水洗至中性,过滤,在100℃真空干燥箱内真空干燥24小时,可得含二氮杂萘酮联苯结构聚苯并咪唑1.2206g,收率为98.4%。聚合物结构经红外光谱分析得到证实,其热稳定性能经TGA进行了表征。
聚合物在Nicolet-20DXB型红外光谱仪上进行FT-IR测试,用KBr压片法制样,红外谱图见图1,从中可以观察到下述特征吸收谱带:
3422cm-1苯并咪唑环上N-H伸缩振动吸收带;
1648cm-1二氮杂萘酮结构中己内酰胺C=O伸缩振动吸收带;
1483cm-1苯并咪唑环和二氮杂萘酮结构中C-N面内弯曲振动峰;
1240cm-1芳醚C-O-C伸缩振动峰;
聚合物热稳定性能测试采用NETZSCH TGA209型热重分析仪,N2氛围下,升温速度20℃/min,测试范围100~800℃。结果见图2。从图2中可以看出,此聚合物具有优异的热稳定性能,聚合物的5%和10%时对应的热失重温度分别为534℃和571℃。
实施例2:于带有搅拌、回流冷凝管、分水器和导气管的干燥100mL三口烧瓶中,加入9mL116%的多聚磷酸(PPA),通氮气保护,并将三口烧瓶进入到油浴中,升温至100℃,搅拌1小时,以除去体系中的氧气。然后,在三口烧瓶中加入0.4282g(2mmol)的3,3’-二氨基联苯胺(DAB)、0.5737g(1.2mmol)的4-[4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮和0.1328g(0.8mmol)的间苯二酸,聚合体系在120℃下反应2小时,在150℃下反应10个小时,190℃下反应7个小时,然后将所得的粘稠液体缓慢倒入1L的去离子水中,在倒入的过程中不断地搅拌去离子水,最后得到红褐色的条状固体,用水洗至弱酸型,再用碳酸钠的水溶液浸泡,用去离子水洗至中性,过滤,在100℃真空干燥箱内真空干燥24小时,可得含二氮杂萘酮联苯结构聚苯并咪唑0.9827g,收率为99.2%。聚合物结构经红外光谱分析得到证实,其热稳定性能经TGA进行了表征。
聚合物在Nicolet-20DXB型红外光谱仪上进行FT-IR测试,用KBr压片法制样,所合成共聚苯并咪唑的红外谱图可以观察到如实例1的特征吸收谱带.
聚合物热稳定性能测试采用NETZSCH TGA209型热重分析仪,测试方法同实例1。聚合物的5%和10%时对应的热失重温度分别为537℃和566℃。
Claims (2)
1.一种含二氮杂萘酮联苯结构聚苯并咪唑,其特征在于聚合物分子链中含有二氮杂萘酮联苯结构和咪唑结构,其结构表达式为:
上述聚苯并咪唑分子链中含有A和B两种结构单元,其中两种结构单元的含量分别为:0<A含量≤100%,0≤B含量<100%;
其中,R1、R2、R3和R4是氢、卤素取代基、苯基、苯氧基或是含有至少1个碳原子的直链或带支链的烷基或烷氧基,R1、R2、R3和R4的结构相同或不同;
Ar1和Ar2的结构式如下:
Ar3的结构式如下:
1,4位、1,5位、2,6位或2,7位;
2.权利要求1所述的含二氮杂萘酮联苯结构聚苯并咪唑的制备方法,其特征在于采用溶液缩聚的方法,具体制备过程如下:
(1)加料阶段,首先使用惰性气体在50~200℃对多聚磷酸进行脱氧,然后加入芳香四元胺或其盐酸盐的一种或几种与含二氮杂萘酮联苯结构的4-[4-(4-羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮或其衍生物,或同时加入其它结构的二元羧酸单体或其衍生物,将反应体系搅拌均匀,上述芳香四元胺或其盐酸盐的摩尔数与二元羧酸单体或其衍生物的摩尔数之和的比值在0.98~1.02之间,此溶液聚合体系中单体质量百分含量在0.2%~60%之间;
(2)聚合反应阶段,采用逐步升温法,在50~250℃进行溶液缩聚反应,反应时间为2~500小时,其中升温温度间隔值控制在5~60℃,在每个温度点,反应持续时间为0.1~100小时之间;
(3)后处理阶段,聚合反应结束后,将反应溶液直接或加入稀释剂后倒入沉淀剂中,将聚合物凝聚沉淀,然后反复洗涤聚合产物中残存的溶剂,也可用碱或弱碱性无机盐中和聚合产物中残存的溶剂并水洗至中性,最后干燥后即可得到含二氮杂萘酮联苯结构聚苯并咪唑;
所采用的缩聚单体中含有如下结构的二酸单体:
其中,R1、R2、R3和R4是氢、卤素取代基、苯基、苯氧基或是含有至少1个碳原子的直链或带支链的烷基或烷氧基,R1、R2、R3和R4的结构相同或不同;
多聚磷酸的浓度在80%~120%之间;稀释剂为磷酸、多聚磷酸、甲磺酸或浓硫酸,加入量为体系中多聚磷酸的0.1~200倍;沉淀剂为水、弱碱或弱碱盐的水溶液、甲醇、乙醇或醇水混合物。
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