[1]俞 梅,俞 娥.镍体系(NiCl2/PPh3)催化的表面引发反向原子转移自由基聚合制备有机/无机杂化材料[J].南京师范大学学报(工程技术版),2007,07(01):046-50.
 Yu Mei,Yu E.Surface Initiated Reverse ATRP to Prepare Organic/Inorganic Hybrid Composite Catalyzed by NiCl2/PPh3 System[J].Journal of Nanjing Normal University(Engineering and Technology),2007,07(01):046-50.
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镍体系(NiCl2/PPh3)催化的表面引发反向原子转移自由基聚合制备有机/无机杂化材料
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南京师范大学学报(工程技术版)[ISSN:1006-6977/CN:61-1281/TN]

卷:
07卷
期数:
2007年01期
页码:
046-50
栏目:
出版日期:
2007-03-30

文章信息/Info

Title:
Surface Initiated Reverse ATRP to Prepare Organic/Inorganic Hybrid Composite Catalyzed by NiCl2/PPh3 System
作者:
俞 梅1 俞 娥2
1. 兰州城市学院中专部, 甘肃兰州730070; 2. 兰州大学化学化工学院, 甘肃兰州730000
Author(s):
Yu Mei1Yu E2
1.Specialized Middle School Department,Lanzhou City College,Lanzhou 730070,China;2.School of Chemistry and Chemical Engineering,Lanzhou University,Lanzhou 730000,China
关键词:
纳米SiO2 NiCl2/PPh3 反向ATRP 有机/无机杂化材料
Keywords:
nano-s ilica n icke l based cata lyst ( N iC l2 /PPh3 ) reverseATRP o rganic / inorgan ic hybrid com po site
分类号:
TQ316.322
摘要:
考察了以过氧基团改性的纳米SiO2为引发剂,NiCl2/PPh3为催化体系的甲基丙烯酸甲酯(MMA)的反向原子转移自由基聚合(ATRP).通过纳米SiO2与氯化亚砜反应,得到了表面由氯-硅基团改性的纳米SiO2,然后再将其与叔丁基过氧化氢(TBHP)反应,在纳米二氧化硅表面成功引入过氧基团,得到了过氧基团改性的纳米SiO2粒子.结果表明,通过调控Ni2+和Ni+之间的变价关系,使得整个聚合反应具有活性自由基聚合的特征.通过酯交换反应,即将聚甲基丙烯酸甲酯接枝的纳米SiO2杂化粒子与氢氟酸反应,可将聚合物层从二氧化硅粒子表面成功解离.GPC结果表明,该纳米材料聚合物接枝层的分子量基本可控,分子量与单体转化率呈线性关系,ln([M0]/[M])与反应时间成正比,两者成线性关系.AFM分析表明,聚合后聚合物链均匀接枝到纳米SiO2表面,得到了分散稳定的以二氧化硅粒子为核,聚甲基丙烯酸甲酯为壳的核壳杂化粒子.
Abstract:
In th is w ork, reve rse a tom transfe r radical po lym eriza tion o fm ethy lm e thacry late w as investiga ted by using the perox ide g roups treated nano-silica as the in itiato r and N iC l2 /PPh3 as the n ickel based cata ly st. The introduction of perox ide groups on to the silica surface w as ach ieved by the reaction of hydrogen perox ide w ith chloro sily l g roups, w hich w ere introduced by the treatm ent of silica w ith th ionyl ch lo ride. The results indicate tha t through contro l the relationsh ip o f N i2+ and N i+ , the po lym er ization w as close ly controlled and partly has the cha racter istic of / liv ing0 / contro lled radica l polym er ization. H ydro lysis o f silica co res by hydro fluoric ac id treatment enabled characteriza tion o f cleaved po lym er us ing GPC. TheGPC ana lys is ind ica ted tha t theM nGPC of PMMA ( g ra fted) inc reases linea rly w ith the increase o f conversion and them o lecularw e ight d istributions are re la tive ly na rrow. The k inetics o f the po lym er ization show ed one order, suggesting that the active spec ies kept constant during the polym e rization. AFM results ind-i cate thatw e l-l de fined po lyme r cha ins w ere g rown from the nanopartic le surfaces to y ield indiv idua l partic les com posed of a s ilica core and aw e l-l de fined oute r po lym e r lay er

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备注/Memo

备注/Memo:
基金项目: 甘肃省自然科学基金( 3ZS042 - B25 - 049)资助项目.
作者简介: 俞 梅( 1979-) , 女, 助教, 主要从事纳米材料的教学与研究. E-ma il:yum ei0931@ 126. com
更新日期/Last Update: 2013-04-29