Precise Synthesis of Clickable Poly(n-hexyl isocyanate)
Precise Synthesis of Clickable Poly(n-hexyl isocyanate)
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DOI：
10.1021/ma300555v
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发表时间：
2012-04
期刊：
影响因子：
5.5
通讯作者：
T. Satoh;R. Ihara;Daisuke Kawato;N. Nishikawa;Daichi Suemasa;Yohei Kondo;Keita Fuchise;R. Sakai;T. Kakuchi
中科院分区：
文献类型：
--
作者：
T. Satoh;R. Ihara;Daisuke Kawato;N. Nishikawa;Daichi Suemasa;Yohei Kondo;Keita Fuchise;R. Sakai;T. Kakuchi
以有机钛为催化剂，采用活性配位聚合法制备了以叠氮或炔端基为棒状构筑基团的可点击聚异氰酸酯。将得到的可点击的STIFY进行铜催化的叠氮化物/炔的环加成反应，合成了基于STIFI为棒状聚合物的明确的大分子结构，例如，作为棒状-盘状嵌段共聚物的PHY-b-聚(N-异丙基丙烯酰胺)和作为棒状星形聚合物的4-臂STAR-PHY。此外，以端羟基丙交酯为起始单体，通过L丙交酯和己内酯的开环聚合，分别合成了新型棒-盘式嵌段共聚物--L丙交酯和己内酯。用核磁共振氢谱、MALDI-TOF质谱仪和配备多角度激光光散射仪和粘度检测器的尺寸排阻色谱对产物进行了表征。
Well-defined clickable poly(n-hexyl isocyanate) (PHIC) with an azido or alkyne end group as rod-like building block has been prepared by the living coordination polymerization using organotitanium catalysts. The obtained clickable PHIC was subjected to the Cu-catalyzed azide/alkyne cycloaddition for the synthesis of well-defined macromolecular architectures based on PHIC as a rod polymer, e.g., PHIC-b-poly(N-isopropyl acrylamide) as rod–coil block copolymer and 4-arm star PHIC as a rod star polymer. Additionally, PHIC-b-poly(l-lactide) and PHIC-b-poly(e-caprolactone) as novel rod–coil block copolymers were respectively synthesized by the ring-opening polymerizations of l-lactide and e-caprolactone initiated from hydroxyl end-functionalized PHIC. All products were characterized by 1H NMR spectroscopy, MALDI–TOF mass spectrometry, and size exclusion chromatography equipped with multiangle laser light scattering and viscosity detectors.