Synthesis of poly(naphthalenecarboxamide)s with low polydispersity by chain-growth condensation polymerization
作者:Koichiro Mikami、Hiroaki Daikuhara、Jyunya Kasama、Akihiro Yokoyama、Tsutomu Yokozawa
DOI:10.1002/pola.24737
日期:2011.7.15
Condensation polymerization of 6‐(N‐substituted‐amino)‐2‐naphthoic acid esters (1) was investigated as an extension of chain‐growth condensation polymerization (CGCP). Methyl 6‐(3,7‐dimethyloctylamino)‐2‐naphthoate (1b) was polymerized at −10 °C in the presence of phenyl 4‐methylbenzoate (2) as an initiator and lithium 1,1,1,3,3,3‐hexamethyldisilazide (LiHMDS) as a base. When the feed ratio [1a]0/[2]0
的6-缩聚(ñ -取代-氨基)-2-萘甲酸的酯(1)进行了调查作为链增长缩聚(CGCP)的延伸。6-(3,7- dimethyloctylamino)-2-萘(1B)中的溶液在-10℃下在苯基4-甲基苯甲酸甲酯(的存在下聚合2)作为引发剂和锂1,1,1,3,3-, 3-六甲基二硅叠氮化物(LiHMDS)作为碱。进给比[ 1a ] 0 / [ 2 ] 0时当其为10或20时,获得具有确定的分子量和低多分散性的聚(萘甲酰胺),以及少量的环状三聚体。但是,在聚合过程中,聚合物在类似条件下以[ 1a ] 0 / [ 2 ] 0 = 34沉淀。为了增加聚合物的溶解度,改为使用具有三乙二醇(TEG)单甲基醚侧链的单体1c和1d。合成了3,7-二甲基辛基侧链。甲基酯单体1c的聚合进展不佳,仅提供低聚物而未反应的1c,而苯基酯单体1d的聚合在[ 1d ] 0 / [ 2 ] 0 = 10和29中得到定义明