化学研究与应用
化學研究與應用
화학연구여응용
Chemical Research and Application
2015年
10期
1489-1497
,共9页
聚砜%氯酰氯%Friedel-Crafts酰基化反应,%亲核取代反应%侧链链长
聚砜%氯酰氯%Friedel-Crafts酰基化反應,%親覈取代反應%側鏈鏈長
취풍%록선록%Friedel-Crafts선기화반응,%친핵취대반응%측련련장
polysulfone%chloroacetyl chloride%Friedel-Crafts acylation%nucleophilic substitution%side chain length
以氯乙酰氯和氯丁酰氯为亲电试剂,通过Friedel-Crafts酰基化反应,在聚砜( PSF)主链引入了含氯的且碳原子数目不同的(分别为2和4)柔性侧链,然后以对羟基苯磺酸钠(HBSS)为试剂,通过亲核取代反应制备了侧链型磺化聚砜2PSF-BSS和4PSF-BSS。采用佛尔哈德分析法、红外光谱(FT-IR)以及核磁氢谱(1H-NMR)对侧链型磺化聚砜的化学结构和性能进行了表征,重点考察主要因素对Friedel-Crafts酰基化和亲核取代反应的影响,实验结果表明：以无水AlCl3为催化剂,CH2 Cl2为反应溶剂,反应温度50℃,CAPSF和CBPSF中氯含量分别达到2．03mmol/g和2．07mmol/g,第2步亲核取代反应遵循SN1机理,在强极性溶剂DMSO中磺酸基键合量分别为1．48mmol/g和1．46mmol/g。同时初步探索侧链链长对质子交换膜的质子传导率的影响,随着侧链长度的增长,侧链的柔性增强,亲水微区与疏水微区微相分离的程度增强,导致交换膜的质子传导率增大。
以氯乙酰氯和氯丁酰氯為親電試劑,通過Friedel-Crafts酰基化反應,在聚砜( PSF)主鏈引入瞭含氯的且碳原子數目不同的(分彆為2和4)柔性側鏈,然後以對羥基苯磺痠鈉(HBSS)為試劑,通過親覈取代反應製備瞭側鏈型磺化聚砜2PSF-BSS和4PSF-BSS。採用彿爾哈德分析法、紅外光譜(FT-IR)以及覈磁氫譜(1H-NMR)對側鏈型磺化聚砜的化學結構和性能進行瞭錶徵,重點攷察主要因素對Friedel-Crafts酰基化和親覈取代反應的影響,實驗結果錶明：以無水AlCl3為催化劑,CH2 Cl2為反應溶劑,反應溫度50℃,CAPSF和CBPSF中氯含量分彆達到2．03mmol/g和2．07mmol/g,第2步親覈取代反應遵循SN1機理,在彊極性溶劑DMSO中磺痠基鍵閤量分彆為1．48mmol/g和1．46mmol/g。同時初步探索側鏈鏈長對質子交換膜的質子傳導率的影響,隨著側鏈長度的增長,側鏈的柔性增彊,親水微區與疏水微區微相分離的程度增彊,導緻交換膜的質子傳導率增大。
이록을선록화록정선록위친전시제,통과Friedel-Crafts선기화반응,재취풍( PSF)주련인입료함록적차탄원자수목불동적(분별위2화4)유성측련,연후이대간기분광산납(HBSS)위시제,통과친핵취대반응제비료측련형광화취풍2PSF-BSS화4PSF-BSS。채용불이합덕분석법、홍외광보(FT-IR)이급핵자경보(1H-NMR)대측련형광화취풍적화학결구화성능진행료표정,중점고찰주요인소대Friedel-Crafts선기화화친핵취대반응적영향,실험결과표명：이무수AlCl3위최화제,CH2 Cl2위반응용제,반응온도50℃,CAPSF화CBPSF중록함량분별체도2．03mmol/g화2．07mmol/g,제2보친핵취대반응준순SN1궤리,재강겁성용제DMSO중광산기건합량분별위1．48mmol/g화1．46mmol/g。동시초보탐색측련련장대질자교환막적질자전도솔적영향,수착측련장도적증장,측련적유성증강,친수미구여소수미구미상분리적정도증강,도치교환막적질자전도솔증대。
With chloroacetyl chloride and chlorobutyryl chloride as electrophilic reagents, a flexible side chain with exchangeable chlorine was bonded on the backbone of polysulfone ( PSF ) via Friedel-Crafts acylation reaction. Subsequently, with sodium 4-hydroxybenzenesulfonate(HBSS)as reagent,two kinds of sulfonated polysulfones with side-chain-type(2PSF-BSS and 4PSF-BSS) were obtained via nucleophilic substitution. The chemical structure and properties of the target polymer PSF-sas were characterized by Vilhard methods,FT-IR and 1 H-NMR. The effects of various factors on the Friedel-Crafts acylation reaction and nucleophilic sub-stitution reaction were mainly investigated. The experimental results show that the degree of chloride ( DC ) of CAPSF and CBPSF could reach to 2. 03mmol/g and 2. 07mmol/g at 50℃ with AlCl3(0. 90 g)as catalyst and CH2Cl2as solvent,respectively. The sec-ond step is a unimolecular nucleophilic substitution reaction,i. e. SN1. CAPSF-sas with a sulfonate bonding amount of 1. 48mmol/g and CBPSF-sas sulfonate with a sulfonate bonding amount of 1. 46mmol/g were obtained with dimethyl sulfoxide( DMSO) as sol-vent. At the same time, the relationship between the length of the side chains and proton conductivity was preliminary ex-plored. Along with the increase of the length of the side chains,the flexibility of the side chains strengthens and the degree of micro-phase separation increases. It leads to the increase of the proton conductivity of the proton exchange membranes.
