RAFT polymerisation of renewable terpene (meth)acrylates and the convergent synthesis of methacrylate-acrylate-methacrylate triblock copolymers
RAFT polymerisation of renewable terpene (meth)acrylates and the convergent synthesis of methacrylate-acrylate-methacrylate triblock copolymers
复制标题
DOI：
10.1039/d1py00326g
复制
发表时间：
2021-05-05
影响因子：
4.6
通讯作者：
Howdle, Steven M.
中科院分区：
文献类型：
--
作者：
Atkinson, Rachel L.;Monaghan, Olivia R.;Howdle, Steven M.
萜烯是可持续聚合物原料的理想候选物，因为它们的天然丰度和现有废物流的可用性。以前，我们已经表明，一系列的萜烯（甲基）丙烯酸酯单体可以合成从最常用的萜烯（α-蒎烯，β-蒎烯和柠檬烯），这些容易进行自由基聚合。我们现在报告的合成定义明确的聚合物和精确的二嵌段和多嵌段共聚物的结构，通过使用RAFT控制。观察到萜烯（甲基）丙烯酸酯均聚物的T-g值范围非常宽，从聚（柠檬烯丙烯酸酯）的-3摄氏度到聚（α-蒎烯甲基丙烯酸酯）的+168摄氏度，我们利用这些来创建可再生来源的硬-软嵌段共聚物。我们还报道了双官能聚（α-和β-甲基丙烯酸蒎烯）大分子RAFT试剂的合成和阿坝三嵌段共聚物的制备。观察到由聚（α-甲基丙烯酸蒎烯）和聚（丙烯酸丁酯）嵌段组成的三嵌段共聚物具有良好的粘合性能。还报道了一系列含有聚（柠檬烯丙烯酸酯）软嵌段的完全基于三元共聚物的三嵌段共聚物。
Terpenes are ideal candidates for sustainable polymer feedstocks, due to their natural abundance and availability from existing waste streams. Previously, we have shown that a range of terpene(meth)acrylate monomers can be synthesised from the most commonly available terpenes (alpha-pinene, beta-pinenene and limonene) and that these readily undergo radical polymerisation. We now report the synthesis of well-defined polymers and precise di- and multiblock copolymer architectures by use of RAFT control. A very wide range of T-g values are observed for the terpene (meth)acrylate homopolymers, from -3 degrees C for poly(limonene acrylate), up to +168 degrees C for poly(alpha-pinene methacrylate), and we exploit these to create renewably-sourced hard-soft block copolymers. We also report the synthesis of difunctional poly(alpha- and beta-pinene methacrylate) macro-RAFT agents and the preparation of ABA triblock copolymers. Promising adhesive properties are observed for a triblock copolymer comprised of poly(alpha-pinene methacrylate) and poly(butyl acrylate) blocks. A range of fully terpene-based triblock copolymers containing poly(limonene acrylate) soft blocks are also reported.