Adamantane-Containing Poly(dialkyl fumarate)s with Rigid Chain Structures
Adamantane-Containing Poly(dialkyl fumarate)s with Rigid Chain Structures
复制标题
具有刚性链结构的含金刚烷聚(富马酸二烷基酯)
DOI：
10.1038/s41428-019-0228-x
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发表时间：
2019
期刊：
影响因子：
2.8
通讯作者：
and A. Matsumoto
中科院分区：
文献类型：
--
作者：
N. Tsuji;Y. Suzuki;and A. Matsumoto
四种含有庞大的金刚烷基酯基团的二烷基硬脂酸酯，即，采用富马酸二（1-金刚烷基）酯（1）、富马酸二（3，5-二甲基-1-金刚烷基）酯（2）、富马酸1-金刚烷基异丙酯（3）和富马酸3，5-二甲基-1-金刚烷基异丙酯（4）进行聚合，得到具有刚性链结构的聚富马酸二烷基酯（PDRF）。我们在甲苯中或本体中在80或60 °C下在自由基引发剂的存在下进行了这些含金刚烷的DRF的常规自由基聚合。以1，1 ′-（1，2-乙二基）双[2-[[（十二烷硫基）硫氧甲基]硫基]-2-甲基丙酸酯]和2，2，2-三氟乙基2-[[（十二烷硫基）硫氧甲基]硫基]-2-甲基丙酸酯为链转移剂（CTA），进行了可逆加成-断裂链转移（RAFT）聚合。以2-乙基己基丙烯酸酯为第二单体，PDRFs为大分子CTA，末端含有三硫代碳酸酯基团，通过聚合反应合成了由刚性链段和柔性链段组成的三嵌段共聚物。通过在氮气流中的热重分析证实了含金刚烷的PDRF的优异的热稳定性。刚性PDRF链在固态的对齐被揭示的基础上出现的峰在小角度区域的X-射线衍射曲线。
Four dialkyl fumarates containing bulky adamantyl ester groups, i.e., di(1-adamantyl) fumarate (1), bis(3,5-dimethyl-1-adamantyl) fumarate (2), 1-adamantyl isopropyl fumarate (3), and 3,5-dimethyl-1-adamantyl isopropyl fumarate (4), were polymerized to obtain poly(dialkyl fumarate)s (PDRFs) with rigid chain structures. We carried out the conventional radical polymerization of these adamantane-containing DRFs in the presence of a radical initiator either in toluene or in bulk at 80 or 60 °C. Reversible addition-fragmentation chain transfer (RAFT) polymerization was also performed using 1,1′-(1,2-ethanediyl) bis[2-[[(dodecylthio)thioxymethyl]thio]-2-methylpropionate] and 2,2,2-trifluoroethyl 2-[[(dodecylthio)thioxymethyl]thio]-2-methylpropionate as the chain transfer agents (CTAs). Triblock copolymers consisting of rigid and flexible segments were synthesized by the polymerization of 2-ethylhexyl acrylate, which was used as the second monomer, using the PDRFs as the macro-CTA containing trithiocarbonate groups at the chain ends. The excellent thermal stability of the adamantane-containing PDRFs was confirmed by thermogravimetric analysis in a nitrogen stream. The alignment of the rigid PDRF chains in the solid-state was revealed based on the appearance of a peak in the small angle regions of the X-ray diffraction profiles.