接枝共聚合（Graft copolymerization）在高分子合成上是一個很重要的方法。近年來在高分子材料的合成上，環烯類開環複分解聚合（ROMP）與原子轉移自由基聚合（ATRP）為功能性高分子的合成打開新的一頁，其中包括帶各式官能基高分子材料的合成。一種具雙官能型單體[5-(2-chloropropionate methylene)bicycle[2,2,1]hept-2-ene (NBMECl)]可藉由開環複分解聚合（ROMP）與原子轉移自由基聚合（ATRP）技術製備出一系列具有高穩定性、有機可溶的篩狀接枝聚合物。首先，一種高穩定性的巨起始劑（Macroinitiator）可利用開環複分解聚合（ROMP）以及氫化反應成功製備，再藉由原子轉移自由基聚合（ATRP）技術，與甲基丙烯酸甲酯和苯乙烯單體合成得到一系列具有高穩定性、有機可溶的篩狀接枝聚合物。並討論聚合物的熱性質、分子量、分子量分佈與溶解度。

A novel difunctional monomer 5-(2-chloropropionate methylene)bicycle[2,2,1]hept-2-ene (NBMECl) for synthesis of stable, organosoluble and comb-shaped copolymers via ring-opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP) was prepared by reaction of 5-norbornene-2-methanol (NBMOH) and 2-chloropropionyl chloride. It is proposed to investigate the ROMP of NBMECl under catalyzed condition of (PCy3)2(Cl)2Ru=CHPh (catalyst I) and IMesH2(Pcy3)(Cl)2Ru (catalyst II) [IMesH2 = 1,3-dimesityl-4,5- dihydroimidazol-2-ylidene] and compare their reactivity. Although catalyst II is the more reactive catalyst at temperatures of 45—75 ℃ than catalyst I, it also affords polymers with high molecular weight of poly(NBMECl) in 15 minutes at 30 ℃. Poly(NBMECl) and poly(HNBMECl) were used as macroinitiators in the ATRP polymerization of MMA and styrene and novel comb-shaped copolymers were prepared. Stability of all densely grafted copolymers with saturated polynorbornene was very high under atmosphere. Grafting efficiency of MMA onto the poly(HNBMECl) was better than styrene under ATRP condition. The number-average molecular weight of densely grafted copolymers obtained from ATRP reaction in bulk and solution were more than 1 × 105. The grafted copolymers were soluble in common organic solvents, even in DMSO on heating.

1 ABSTRACT-------------------------------------------------------------- 1
2 INTRODUCTION------------------------------------------------------- 2
3 EXPERIMENTAL------------------------------------------------------- 5
3.1 Materials------------------------------------------------------------ 5
3.2 Monomer synthesis------------------------------------------------ 5
3.2.1 Synthesis of NBMECl---------------------------------- 6
3.3 Polymer synthesis ------------------------------------------------- 6
3.3.1 Ring-opening metathesis polymerization of NBMECl------------------------------------------------- 6
3.3.2 Hydrogenation of poly(NBMECl)------------------- 10
3.3.3 Sythesis of comb-shaped copolymer with PMMA segment derived from poly(NBMECl) as a macrointiator via ATRP ------------------------------ 13
3.3.4 Sythesis of comb-shaped copolymer with PMMA segment derived from poly(HNBMECl) as a macrointiator via ATRP ------------------------------ 15
3.3.5 Sythesis of comb-shaped copolymer with PS segment derived from poly(HNBMECl) as a macrointiator via ATRP --------------------------------------------------- 18
3.4 CHRACTERIZATION METHODS--------------------------- 24
4 RESULT AND DISCUSSION---------------------------------------- 25
4.1 Synthesis and characterization of monomer NBMECl------ 25
4.2 Synthesis and characterization of poly(NBMECl)----------- 25
4.3 Synthesis and characterization of poly(HNBMECl)--------- 27
4.4 Synthesis and characterization of comb-shaped copolymer-------------------------------------------------------- 28
4.5 GPC analysis------------------------------------------------------ 31
4.6 NMR analysis----------------------------------------------------- 34
4.7 Thermal property------------------------------------------------- 34
4.8 Solubility---------------------------------------------------------- 36
5 CONCLUSIONS------------------------------------------------------- 38
6 REFERENCES--------------------------------------------------------- 39
附 錄----------------------------------------------------------------------- 41
作者簡介----------------------------------------------------------------------- 42

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