活性自由基聚合与聚异戊二烯交联
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摘要
1982年,日本学者Otsu等人提出了Iniferter的概念,并将其成功地运用到自由基聚合,使自由基活性／可控聚合进入一个全新的历史发展时期。它的显著的优点是可聚合单体比其他方法要多,能方便地制备嵌段和接枝共聚物。许多结构新颖的Iniferter已经被合成并用于制备端基功能化聚合物、遥爪聚合物、大分子单体、嵌段和接枝共聚物等。
论文共分为三个部分：
第一章：介绍了活性自由基聚合的几种方法,重点介绍了Iniferter法性质和研究进展,综述了光聚合反应和环氧橡胶的应用研究进展。
第二章：采用Iniferter法,合成了ATRP/Iniferter引发前体60余个,进行了结构表征。以自合成的几种引发前体为引发剂,分别合成了星型二嵌段共聚物聚异戊二烯／聚甲基丙烯酸甲酯(PI/PMMA)、聚异戊二烯／聚苯乙烯(PI/PS)和星型三嵌段共聚物聚异戊二烯／聚甲基丙烯酸甲酯／聚苯乙烯(PI/PMMA/PS)。利用IR和1HNMR对各嵌段共聚物的结构和组成进行了表征,并利用TG-DSC、SEM和AFM对嵌段高聚物的性质和表面形貌进行了表征。
第三章：使用Iniferter法由聚苯乙烯引发环氧化丙烯酸天然橡胶(SEANR)聚合。环氧化丙烯酸天然橡胶首先由丙烯酸接枝环氧化天然橡胶而得到,然后与聚苯乙烯进行了一个利用Iniferter光引发剂聚苯乙烯在紫外光照射下的光聚合反应。并对产物的结构和形貌进行了红外光谱,核磁共振氢谱、扫描电镜和原子力显微镜表征。表征结果表明,成功地获得所需的产品。GPC结果表明,作为光引发剂的Iniferter聚苯乙烯的数均分子量(Mn),体重平均分子量(Mw)和使用分子量分布进行了计算,分别是920,1340,和1.46。AFM结果表明,聚苯乙烯均匀分布于环氧化丙烯酸天然橡胶中。并通过TG／DSC对产品的热性能进行分析。
In 1982, Japanese scholars Otsu et al proposed the concept of Iniferter and successfully applied to the living radical polymerization, free radical living/controlled polymerization into a new period of development historical, whose significant advantage was much more easy to prepare block and graft copolymers than other methods of polymerizable monomer. Many novel structures Iniferter have been synthesized and the preparated for end group functionalized polymers, telechelic polymers, macromonomers, block and graft copolymers.
This dissertation consists of four chapters:
Chapter 1:Describes several methods of living radical polymerization, highlighting the character and research progressof Iniferter, and the research application of photopolymeriz-ation and epoxy nutural rubber.
Chapter 2:Synthesized and characterized more than 60 precursors by ATRP/Iniferter. Star bisblock copolymers polyisoprene/polymethyl methacrylate (PI/PMMA), polyisoprene/polystyrene (PI/PS) and star triblock compolymers polyisoprene/polymethyl methacrylate/polystyrene (PI/PMMA/PS) were synthesized respectively using 1,3,5-tris(ethyldimethylcar-bamodithioate)-2,4,6-trimethylbenzene synthesized by ourselves as initiator by iniferter polymerization. The structure and constituent of copolymers were characterized by IR and 1HNMR.
Chapter 3:Epoxidized acrylated natural rubber crosslinked by polystyrene (SEANR) was synthesized by iniferter polymerization. The epoxidized acrylated natural rubber was firstly obtained by grafting of acrylic acid onto epoxidized natural rubber, and then performed a photocrosslinking reaction with polystyrene using polystyrene iniferter as a photoinitiator under UV irradiation. The structure and morphology were characterized by FT-IR,1H-NMR and SEM. The characterization results show that the desired products were successfully obtained. GPC results show that the number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity of the polystyrene iniferter using as photoinitiator were calculated 920,1340, and 1.46, respectively. AFM results show that polystyrene was uniformly distributed throughout the epoxidized acrylated natural rubber. The thermal performances of the product were evaluated by TG/DSC.
论文共分为三个部分：
第一章：介绍了活性自由基聚合的几种方法,重点介绍了Iniferter法性质和研究进展,综述了光聚合反应和环氧橡胶的应用研究进展。
第二章：采用Iniferter法,合成了ATRP/Iniferter引发前体60余个,进行了结构表征。以自合成的几种引发前体为引发剂,分别合成了星型二嵌段共聚物聚异戊二烯／聚甲基丙烯酸甲酯(PI/PMMA)、聚异戊二烯／聚苯乙烯(PI/PS)和星型三嵌段共聚物聚异戊二烯／聚甲基丙烯酸甲酯／聚苯乙烯(PI/PMMA/PS)。利用IR和1HNMR对各嵌段共聚物的结构和组成进行了表征,并利用TG-DSC、SEM和AFM对嵌段高聚物的性质和表面形貌进行了表征。
第三章：使用Iniferter法由聚苯乙烯引发环氧化丙烯酸天然橡胶(SEANR)聚合。环氧化丙烯酸天然橡胶首先由丙烯酸接枝环氧化天然橡胶而得到,然后与聚苯乙烯进行了一个利用Iniferter光引发剂聚苯乙烯在紫外光照射下的光聚合反应。并对产物的结构和形貌进行了红外光谱,核磁共振氢谱、扫描电镜和原子力显微镜表征。表征结果表明,成功地获得所需的产品。GPC结果表明,作为光引发剂的Iniferter聚苯乙烯的数均分子量(Mn),体重平均分子量(Mw)和使用分子量分布进行了计算,分别是920,1340,和1.46。AFM结果表明,聚苯乙烯均匀分布于环氧化丙烯酸天然橡胶中。并通过TG／DSC对产品的热性能进行分析。
In 1982, Japanese scholars Otsu et al proposed the concept of Iniferter and successfully applied to the living radical polymerization, free radical living/controlled polymerization into a new period of development historical, whose significant advantage was much more easy to prepare block and graft copolymers than other methods of polymerizable monomer. Many novel structures Iniferter have been synthesized and the preparated for end group functionalized polymers, telechelic polymers, macromonomers, block and graft copolymers.
This dissertation consists of four chapters:
Chapter 1:Describes several methods of living radical polymerization, highlighting the character and research progressof Iniferter, and the research application of photopolymeriz-ation and epoxy nutural rubber.
Chapter 2:Synthesized and characterized more than 60 precursors by ATRP/Iniferter. Star bisblock copolymers polyisoprene/polymethyl methacrylate (PI/PMMA), polyisoprene/polystyrene (PI/PS) and star triblock compolymers polyisoprene/polymethyl methacrylate/polystyrene (PI/PMMA/PS) were synthesized respectively using 1,3,5-tris(ethyldimethylcar-bamodithioate)-2,4,6-trimethylbenzene synthesized by ourselves as initiator by iniferter polymerization. The structure and constituent of copolymers were characterized by IR and 1HNMR.
Chapter 3:Epoxidized acrylated natural rubber crosslinked by polystyrene (SEANR) was synthesized by iniferter polymerization. The epoxidized acrylated natural rubber was firstly obtained by grafting of acrylic acid onto epoxidized natural rubber, and then performed a photocrosslinking reaction with polystyrene using polystyrene iniferter as a photoinitiator under UV irradiation. The structure and morphology were characterized by FT-IR,1H-NMR and SEM. The characterization results show that the desired products were successfully obtained. GPC results show that the number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity of the polystyrene iniferter using as photoinitiator were calculated 920,1340, and 1.46, respectively. AFM results show that polystyrene was uniformly distributed throughout the epoxidized acrylated natural rubber. The thermal performances of the product were evaluated by TG/DSC.
引文
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