Synthesis of core cross-linked star polymers carrying helical poly(phenyl isocyanide) arms via "core-first" strategy and their surface chiral recognition ability
Synthesis of core cross-linked star polymers carrying helical poly(phenyl isocyanide) arms via "core-first" strategy and their surface chiral recognition ability
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“核优先”策略合成携带螺旋聚异氰苯酯臂的核交联星形聚合物及其表面手性识别能力
DOI：
10.1016/j.polymer.2017.12.057
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发表时间：
2018
期刊：
影响因子：
4.6
通讯作者：
Wu Zong Quan
中科院分区：
文献类型：
--
作者：
Wang Qian;Huang Jian;Jiang Zhi Qiang;Zhou Li;Liu Na;Wu Zong Quan
设计并合成了降冰片烯功能化炔-Pd（II）配合物，该配合物与双降冰片烯交联剂通过开环复分解聚合（ROMP）共聚得到交联Pd（II）宏观引发剂。用Pd（II）高分子引发剂对苯基异氰酸酯进行活性聚合，形成了带螺旋聚苯基异氰酸酯支链的核交联星形聚合物。由于Pd（II）引发苯基异氰化物聚合的活性，制备了一系列结构可控、组成可调的星形聚合物。用对映纯苯基异氰酸酯单体制备了具有超单手螺旋臂的光学活性星形聚合物。该星形聚合物具有优异的手性识别能力。星形聚合物的接触角强烈依赖于D/ l -苯基甘二醇液滴的手性。对映体选择性表面识别可进一步应用于外消旋D/ l -苯甘二醇的手性拆分。分离的对映体的对映体过量量（ee）可达75%。手性星型聚合物还可用于诱导外消旋boc -丙氨酸的对映选择性结晶。对映体的ee值可达91%。
A norbornene functionalized alkyne-Pd(II) complex was designed and synthesized, which copolymerized with a bisnorbornene cross linker via ring-opening metathesis polymerization (ROMP) afforded a cross-linked Pd(II) macroinitiator. Living polymerization of phenyl isocyanides with the Pd(II) macroinitiator lead to the formation of well-defined core cross-linked star polymer carrying helical poly(phenyl isocyanide)s arms. Because of the living nature of Pd(II)-initiated phenyl isocyanide polymerization, a series of star polymers with controlled structure and tunable compositions was readily prepared. Optically active star polymers with excess of one handed helical arms were obtained by using enantiopure phenyl isocyanide monomers. Such star polymer exhibited excellent chiral recognition ability. The contact angle of the star polymer is strongly dependent on the chirality of the D/L-phenylglycinol droplets. The enantioselective surface recognition can be further applied to the chiral resolution of racemic D/L-phenylglycinol. The enantiomeric excess (ee) of the isolated enantiomer is up to 75%. The chiral star polymers can also be used to induce enantioselectively crystallization of racemic Boc-alanine. The ee value of the induced enantiomer can be up to 91%.