可裂解丙烯酸酯-乙烯基醚二乙烯基单体通过氮氧化物介导的自由基聚合的环聚合反应：超出反应比的共聚物,ACS Macro Letters

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可裂解丙烯酸酯-乙烯基醚二乙烯基单体通过氮氧化物介导的自由基聚合的环聚合反应：超出反应比的共聚物
ACS Macro Letters ( IF 5.1 ) Pub Date : 2017-06-26 00:00:00 , DOI: 10.1021/acsmacrolett.7b00368
Yuki Kametani ₁ , Marina Nakano ₁ , Taizo Yamamoto ₁ , Makoto Ouchi _{1,

2} , Mitsuo Sawamoto ₁

Affiliation

二乙烯基单体的环聚合，其中两个不同的乙烯基，即丙烯酸酯和乙烯基醚，通过酯键连接，在稀释条件下使用氮氧自由基聚合自由基聚合（NMP）进行。在合适的条件下，两个乙烯基基团以几乎相同的速率被消耗，尽管两个乙烯基基团之间固有的交叉传播能力在自由基共聚中相当低。此外，在一定程度上控制聚合以得到具有单峰分子量分布的聚合物。结果明显不同于与构成二乙烯基单体、丙烯酸2-甲氧基乙酯和2-乙酰氧基乙基乙烯基醚的乙烯基单体的共聚和均聚。结构分析表明形成了环聚合物，但环效率不完美，表明掺入了一些烯属悬挂单元。最终，环单元的酯键断裂，转化为丙烯酸和2-羟乙基乙烯基醚组成的共聚物，其组成比（DP_丙烯酸/DP _VE ) 为 55:45。该共聚物的玻璃化转变温度高于从均聚物的组成比和T _g值估计的值，这可能是由于在以交替方式排列的羧酸和羟基之间形成了准环状聚合物。

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Cyclopolymerization of Cleavable Acrylate-Vinyl Ether Divinyl Monomer via Nitroxide-Mediated Radical Polymerization: Copolymer beyond Reactivity Ratio

Cyclopolymerization of a divinyl monomer, where two different vinyl groups, that is, acrylate and vinyl ether, are connected via an ester bond, was performed under diluted condition with nitroxide-meditated radical polymerization (NMP). Both vinyl groups were consumed at almost same rate under suitable condition, although the inherent cross-propagation ability between the two vinyl groups are pretty low in radical copolymerization. Furthermore, the polymerization was controlled to some extent to give polymers of unimodal molecular weight distributions. The results obviously differed from copolymerization and homopolymerization with vinyl monomers that constitutes the divinyl monomer, 2-methoxyethyl acrylate and 2-acetoxyethyl vinyl ether. Structural analyses indicated formation of the cyclopolymer but the cyclo-efficiency was imperfect indicating that some units of olefinic dangling were incorporated. Eventually, the ester bonds of the cyclo units were cleaved to convert into the copolymer consisting of acrylic acid and 2-hydroxy ethyl vinyl ether and the composition ratio (DP_acryl/DP_VE) was 55:45. The copolymer showed higher glass transition temperature than that estimated from the composition ratio and T_g values of the homopolymers, which is likely due to the formation of quasi-cyclopolymer between carboxylic acid and hydroxy groups aligned in alternating fashion.

更新日期：2017-06-26

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