Direct Photolysis RAFT Polymerization of (Metha)acrylate with 2-Cyano-2-propyldodecyl Trithiocarbonate as Mediator
Direct Photolysis RAFT Polymerization of (Metha)acrylate with 2-Cyano-2-propyldodecyl Trithiocarbonate as Mediator
复制标题
以2-氰基-2-丙基十二烷基三硫代碳酸酯为介体的(甲基)丙烯酸酯的直接光解RAFT聚合
DOI：
10.1002/macp.202100340
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发表时间：
2022
影响因子：
2.5
通讯作者：
Wnatai Yang
中科院分区：
文献类型：
--
作者：
Jianxiong Zhang;Junjing Duan;Dong chen;Yuhong Ma;Wnatai Yang
以2‐氰基‐2‐丙基十二烷基三硫代碳酸盐（TTP）为引发剂和链转移剂，进行了甲基丙烯酸酯的直接光解可逆加成-裂解链转移（RAFT）聚合反应。蓝光可以有效地激活聚合反应，同时保持mnvs转化率的线性增加。以聚甲基丙烯酸甲酯- TTP （PMMA - TTP,Mn= 6700 g mol-1，Ð= 1.29）为前体，通过扩链法制备了分子量更高的PMMA (Mn= 14 600 g mol-1，Ð= 1.67)，以及一系列嵌段共聚物，包括聚甲基丙烯酸甲酯- b -聚（甲基丙烯酸缩水甘油酯）、聚甲基丙烯酸甲酯- b -聚（甲基丙烯酸叔丁基）和聚甲基丙烯酸甲酯- b -聚（甲基丙烯酸苄酯）（PMMA - b - PBnMA）。TheMn，NMR= 14 900 g mol - 1的PMMA‐b‐经NMR测得的PMMA非常接近toMn，GPC= 14 200 g mol - 1经凝胶渗透色谱测定。此外，与聚甲基丙烯酸酯（Ð= 1.10-1.80）相比，丙烯酸酯的聚合在分散性方面具有更高的可控性（Ð< 1.20）。以聚丙烯酸甲酯（PMA‐TTP,Mn= 11 900 g mol-1，Ð= 1.09）为macro‐RAFT试剂，通过扩链法制备了分子量更高的PMA （Mn= 23 500 g mol-1，Ð= 1.28）和PMA‐b‐PBnA （Mn= 26 500 g mol-1，Ð= 1.19）。在高温下表观聚合速率的提高证明了正的协同效应。例如，当温度从32℃升高到50℃时，MA的表观聚合速率从0.0860 h - 1增加到0.115 h - 1。
A direct photolysis reversible addition‐fragmentation chain transfer (RAFT) polymerization of (meth)acrylates is developed with 2‐cyano‐2‐propyldodecyl trithiocarbonate (TTP), which plays the dual role as photoinitiator and chain transfer agent. The polymerizations can be efficiently activated by blue light while maintaining a linear increase inMnversus conversion. With poly(methyl methacrylate)‐TTP (PMMA‐TTP,Mn= 6700 g mol–1,Ð= 1.29) as precursor, a higher molecular weight PMMA (Mn= 14 600 g mol–1,Ð= 1.67) by chain extension, and a series of block copolymers, including poly(methyl methacryalte)‐b‐poly(glycidyl methacrylate), poly(methyl methacrylate)‐b‐poly(tert‐butyl methacrylate), and poly(methyl methacrylate)‐b‐poly(benzyl meacrylate)(PMMA‐b‐PBnMA), are prepared. TheMn,NMR= 14 900 g mol–1of PMMA‐b‐PBnMA measured by NMR is very close toMn,GPC= 14 200 g mol–1determined by gel permeation chromatography. Furthermore, the polymerization of acrylates exhibits higher controllability in regarding to dispersity (Ð< 1.20) compared to those of polymethacrylates (Ð= 1.10–1.80). With poly(methyl acrylate) (PMA‐TTP,Mn= 11 900 g mol–1,Ð= 1.09) as macro‐RAFT agent, a higher molecular weight PMA (Mn= 23 500 g mol–1,Ð= 1.28) by chain extension, and PMA‐b‐PBnA (Mn= 26 500 g mol–1,Ð= 1.19) are also prepared. A positive synergic effect is demonstrated by enhanced apparent polymerization rates at elevated temperature. For example, the apparent polymerization rates of MA increases from 0.0860 to 0.115 h–1with temperature rising from 32 to 50 °C.