一氧化氮介导的甲基丙烯酸2-（二乙氨基）乙酯（DEAEMA）的聚合,Macromolecules

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一氧化氮介导的甲基丙烯酸2-（二乙氨基）乙酯（DEAEMA）的聚合
Macromolecules ( IF 5.1 ) Pub Date : 2014-12-26 00:00:00 , DOI: 10.1021/ma502175c
Ali Darabi ₁ , Abbas Rezaee Shirin-Abadi ₁ , Philip G. Jessop ₁ , Michael F. Cunningham ₁

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使用正羟基琥珀酰亚胺基BlocBuilder在90°C和大气压下首次在水中以90°C和大气压进行甲基丙烯酸2-（二乙氨基）乙基甲基酯（DEAEMA）与少量丙烯腈（AN）的一氧化氮介导聚合（NMP）（NHS-BB）烷氧基胺，无需添加过量的一氧化氮。相同的反应进行了使用双组分发起的2,2'-偶氮二[2-（2-咪唑啉-2-基）丙烷]二盐酸盐（VA-044）作为引发剂和组成的系统ñ -叔丁基- ñ- （1-二乙基-2,2-二甲基丙基）氮氧自由基（SG1）如氮氧化物。两种聚合反应均得到良好控制，并且表现出优异的活性，这由低摩尔分散度和摩尔质量分布的演变证明。研究了DEAEMA在聚合条件下的水解稳定性以及引发系统，温度，一氧化氮与引发剂的比例，引发剂和单体浓度以及共聚单体类型等参数的影响。在导致我一个一锅法与甲基丙烯酸甲酯（MMA）和苯乙烯（S）所合成的大分子引发剂的链延长Ñ原位形成聚（DEAEMA-共-S） - b -聚（MMA- CO-S）基于聚合诱导的自组装（PISA）过程的二嵌段共聚物。

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Nitroxide-Mediated Polymerization of 2-(Diethylamino)ethyl Methacrylate (DEAEMA) in Water

Nitroxide-mediated polymerization (NMP) of 2-(diethylamino)ethyl methacrylate (DEAEMA) with a small amount of acrylonitrile (AN) as a comonomer was performed for the first time in water at 90 °C and atmospheric pressure using n-hydroxysuccinimidyl BlocBuilder (NHS-BB) alkoxyamine without addition of excess nitroxide. The same reaction was carried out using the bicomponent initiating system composed of 2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (VA-044) as initiator and N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl) nitroxide (SG1) as nitroxide. Both polymerization reactions were well-controlled and exhibited excellent livingness as evidenced by low molar dispersity and evolution of the molar mass distribution. The hydrolytic stability of DEAEMA at the polymerization conditions and the effects of several parameters including initiating system, temperature, ratio of nitroxide to initiator, initiator and monomer concentrations, and comonomer type were investigated. Chain extension of the synthesized macroinitiator with methyl methacrylate (MMA) and styrene (S) in a one-pot process led to the in situ formation of poly(DEAEMA-co-S)-b-poly(MMA-co-S) diblock copolymers based on the polymerization-induced self-assembly (PISA) process.

更新日期：2014-12-26

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