Organocatalytic synthesis and post-polymerization functionalization of propargyl-functional poly(carbonate)s
Organocatalytic synthesis and post-polymerization functionalization of propargyl-functional poly(carbonate)s
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DOI：
10.1039/c2py20718d
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发表时间：
2013-01-01
影响因子：
4.6
通讯作者：
Dove, Andrew P.
中科院分区：
文献类型：
--
作者：
Tempelaar, Sarah;Barker, Ian A.;Dove, Andrew P.
在5-methyl-5-propargyloxycarbonyl-1，3-dioxan-2-one(TU)和1，8-二氮杂双环[5.4.0]十二碳-7-烯(DBU)的双重催化体系下，通过1-(3，5-bis(trifluoromethyl)phenyl)-3-cyclohexylthiourea的有机催化开环聚合，合成了具有良好结构的炔丙基功能聚碳酸酯S。所得均聚物表现出低分散性和高端基保真度，远程螺旋共聚物和嵌段共聚物的合成证明了该体系的多功能性。合成的不同聚合度的均聚物通过铜催化的惠斯根-1，3-偶极加成反应和硫醇的自由基硫基化反应与一系列叠氮化合物进行官能化反应，在单一的聚合物支架上合成功能性脂肪族聚碳酸酯S。
The synthesis of well-defined propargyl-functional poly(carbonate)s was achieved via the organocatalytic ring-opening polymerization of 5-methyl-5-propargyloxycarbonyl-1,3-dioxan-2-one (MPC) using the dual catalyst system of 1-(3,5-bis(trifluoromethyl)phenyl)-3-cyclohexylthiourea (TU) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The resulting homopolymers showed low dispersities and high end-group fidelity, with the versatility of the system being demonstrated by the synthesis of telechelic copolymers and block copolymers. The synthesized homopolymers with varying degree of polymerization were functionalized with a range of azides via copper-catalyzed Huisgen-1,3-dipolar addition or thiols via radical thiylation, to produce functional aliphatic poly(carbonate) s from a single polymeric scaffold.