Novel Polymers by the Radical Polymerization via Addition-Abstraction Mechanism

我们开发了一种新型的自由基聚合，它通过添加-抽象机制进行聚合。制备了三种适合加成萃取聚合的单体，并对它们的聚合行为进行了研究。3,3-二氰丙基乙烯基醚（DCPVE）是一种乙烯基醚，很容易与过氧化叔丁基聚合。所得聚合物的分子量在3000-4000之间。^ 1h -和^<13>C-NMR分析表明，聚合几乎是通过加成-抽象机制定量进行的。根据单体反应率和共聚物的结构考察了DCPVE与乙烯基单体的自由基共聚反应。共聚反应在很大程度上还涉及加成-抽象机理。用自由基引发剂聚合富马酸邻甲酰苯基乙酯（EFPF），收率较高。聚合过程是一个复杂的过程，包括乙烯基加成和分子内的氢提取。聚合物（EFPF）的分子量在1600-2900之间。聚合体系涉及esr观察到的自由基传播。在ESR数据的基础上估计了传播速率常数和终止速率常数。还研究了EFPF与乙烯基单体的共聚反应。以乙二醇为原料合成了o-（4-苯基-1,3-二恶唑兰-2-基）富马酸苯乙酯（EPDPF）。EFDPF也发生了自由基聚合。聚（EFDPF）的^1H-和^<13>C-NMR分析表明，聚合过程包括乙烯基加成，分子内抽氢，以及在较高温度下环缩醛的进一步开环。

We have developed a novel type of radical polymerization which propagates through addition-abstraction mechanism. Three monomers suitable for the addition-abstraction polymerization were prepared and their polymerization behaviors were investigated.3,3-Dicyanopropyl vinyl ether (DCPVE), a vinyl ether, was easily polymerized with t-butyl peroxide. The molecular weight of the resulting polymer was in the range of 3000-4000. ^1H-and ^<13>C-NMR analysis of polymer structure revealed that the polymerization almost quantitatively proceeds through addition-abstraction mechanism. Radical copolymerization of DCPVE with some vinyl monomers were examined on the basis of monomer reactivity ratios and structures of copolymers. The copolymerizations also involve the addition-abstraction mechanism to a considerable extent.Ethyl o-formylphenyl fumarate (EFPF) was polymerized by radical initiators in a fairly yield. The polymerization was found to proceed in a complicated manner involving vinyl addition and intramolecular hydrogen-abstraction. The molecular weight of poly (EFPF) was in the range of 1600-2900. The polymerization system involved ESR-observed propagating radicals. The rate constants of propagation and termination were estimated on the basis of ESR data. Copolymerizations of EFPF with vinyl monomers were also examined.Ethyl o- (4-phenyl-1,3-dioxolan-2-yl) phenyl fumarate (EPDPF) was synthesized from EFPF and stirene glycol. EFDPF was also radically polymerized. ^1H- and ^<13>C-NMR analysis of poly (EFDPF) showed that the polymerization proceed in a manner involving vinyl addition, intramolecular hydrogen-abstraction, and further ring-opening of cyclic acetal at higher temperatures.