摘要
采用核磁共振氢谱,研究了N-苯基马来酰亚胺(NPMI)与对氯甲基苯乙烯(PCMS)在氘代氯仿中的络合性能.以PCMS作为引发剂单体,通过原子转移自由基聚合(ATRP)引发NPMI-PCMS电子转移络合物(CTC)进行活性可控超支化共聚合.考察了单体初始摩尔分数对共聚物组成和其玻璃化转变温度的影响,用Kelen-Tudos法计算得到两种单体的竞聚率分别为rNPMI=0.11和rPCMS=0.25.结果表明,当单体配比fNPMI=0.4～0.7时,共聚物具有交替结构,其耐热性随着NPMI含量的增加而提高.此外还考察了溶剂、聚合温度等对共聚合反应动力学的影响.并进一步用所得超支化交替共聚物作为大分子引发剂,引发甲基丙烯酸甲酯(MMA)聚合,制得了多臂超支化接枝共聚物poly(NPMI-co-PCMS)/poly(MMA).
The complexation properties of N-phenylmaleimide （NPMI） and p-（chloromethyl）styrene （PCMS） were studied by 1^H NMR in CDCl3 firstly. Novel hyperbranched alternating copolymers were successfully synthesized via living controllable radical copolymerization of the charge transfer complex made from NPMI and PCMS while PCMS was used as an inimer. The monomer reactivity ratios were evaluated to be rNPMI =0.11 and rPCMS =0.25 respectively by the Kelen-Tudos method. The resulting hyperbranched copolymers were of alternating structure when the molar fraction of NPMI was varied from 0.4 to 0.7. The glass transition temperature of such hyperbranched copolymer was increased with increasing fNPMI, indicating that the thermal stability of the copolymers had been improved with increasing NPMI. The influences of reaction conditions, such as solvent and the polymerization temperature on the copolymerization kinetics, were also studied. These hyperbranched alternating copolymers were successfully used as functional macroinitiators to synthesize the star-shaped poly（NPMI-co-PCMS）/poly（MMA） block copolymers.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2006年第6期556-562,共7页
Acta Chimica Sinica
基金
国家自然科学基金(No.50233030)
浙江省自然科学基金(Nos.Y405411
Y405500)
浙江省教育厅项目(No.20051336)
上海市基础研究重点项目(Nos.03JC14046
04JC14057)资助项目.
