含1-(萘-1-磺酰基)萘结构聚芳醚的合成及表征

Synthesis and Characterization of Poly(Aryl Ether)s Containing 1-(Naphthalene-1-Ylsulfonyl)Naphthylene Moiety in One Repeat Unit

以氯苯、α-氯代萘、氯磺酸、二氯亚砜为原料,合成了4-氯-1-萘磺酰氯,经Frield-Craft磺酰基化反应,合成了含两个1,4-萘结构的4-氯-1-(4′-氯-1-萘磺酰基)萘(CCNSN)。CCNSN分别与双酚A、酚酞、对苯二酚及4-(4-羟基苯基)-2,3-二氮杂萘-1-酮经溶液亲核取代逐步聚合反应,合成了4种含1-(萘-1-磺酰基)萘结构的聚芳醚(Pa^Pd)。用NMR、FT-IR对单体和聚合物进行了表征,证明其结构正确;用DSC、TGA和WAXD等方法对聚合物的热性能及结晶性进行了表征,结果表明,聚合物的玻璃化转变温度在226℃~318℃之间,氮气环境下,5%热失重的起始温度均在450℃以上,说明具有良好的热稳定性;考察了聚合物的溶解性能,除Pc不溶于常见的有机溶剂外,Pa、Pb、Pd皆可溶于氯仿(CHCl3)、1,1,2,2-四氯乙烷(TCE)和N,N-二甲基乙酰胺(DMAC)、N-甲基吡咯烷酮(NMP)等非质子极性溶剂。

A symmetric monomer 1-chloro-4-（4-chloronaphtholsulfonyl） naphthalene（CCNSN） was synthesized from 1-chloronaphthalene,chlorosulfonic acid and thionyl chloride via the Friedel-Crafts reaction.Four poly（aryl ether）s（named as Pa,Pb,Pc,Pd） containing 1-（naphthalene-1-ylsulfonyl）naphthylene moiety were then prepared by the nucleophilic substitution reaction of 1-chloro-4-（4-chloronaphtholsulfonyl） naphthalene（CCNSN） with 4,4′-isopropylidenediphenol,phenolphthalein,1,4-hydroquinone and 4-（4-hydroxyphenyl）（2H） phthalazin-1-one,respectively.The structures of the monomer CCNSN and its polymers were confirmed by FT-IR,1H-NMR and 13C-NMR.Thermal properties and crystallinity of the obtained polymers were studied by DSC,TGA and WAXD,respectively.Glass transition temperatures are in the range of 226 ℃～318 ℃ and 5% mass loss starts at the temperature above 450 ℃,indicating the polymers have good thermostability.The crystallinity of Pc from the reaction of CCNSN and 1,4-hydroquinone is 16.7% calculated by the equation of crystallinity,while the other three polymers are amorphous.These polymers are soluble in chloroform,1,1,2,2-tetrachloro ethane,N,N-dimethyl aceamide and N-methyl pyrrolidione,except Pc.