Synthesis of macrocyclic poly(ε-caprolactone) by intramolecular cross-linking of unsaturated end groups of chains precyclic by the initiation
Synthesis of macrocyclic poly(ε-caprolactone) by intramolecular cross-linking of unsaturated end groups of chains precyclic by the initiation
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DOI：
10.1002/anie.200503961
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发表时间：
2006-01-01
影响因子：
16.6
通讯作者：
Lecomte, P
中科院分区：
文献类型：
--
作者：
Li, HY;Debuigne, A;Lecomte, P
近几十年来，在合成聚合物的主要家族的所谓大分子工程领域中已经见证了稳步增长的进展。[1]环状共聚物由于不存在任何链端而显示出独特的拓扑结构，并表现出与其线性对应物不同的性质，例如玻璃化转变温度、有序-无序转变、降低的粘度和较低的流体动力学体积。[2]在纳米技术领域，大环聚酯非常有希望用于生产具有较小尺寸域的多相材料。[2]然而，只有有限的努力一直致力于有目的的合成大环化合物和更复杂的架构，从他们。大环化合物的通常途径依赖于通过双官能剂Y-Y将直链的两个相同链端（X）单分子偶联。[2]与任何偶联反应一样，相互反应性基团X和Y的1：1摩尔比是最重要的。在这些条件下，环化产率由等式（1）表示，其中Cequal是环化产物的浓度。
Recent decades have witnessed steadily increasing progress in the area of so-called macromolecular engineering of the main families of synthetic polymers.[1] Ring-shaped copolymers show a unique topology as a result of the absence of any chain end and exhibit distinct properties to their linear counterparts, such as glass-transition temperatures, order–disorder transitions, reduced viscosities, and lower hydrodynamic volumes.[2] In the field of nanotechnology, macrocyclic polyesters are very promising for the production of heterophase materials with smaller size domains.[2] However, only a limited effort has been devoted to the purposeful synthesis of macrocycles and more complex architectures derived from them. The usual route towards macrocycles relies on the unimolecular coupling of the two identical chain ends (X) of linear chains by a difunctional agent, Y–Y.[2] The 1: 1 molar ratio of the mutually reactive groups X and Y is of the utmost importance, as is the case for any coupling reaction. Under these conditions, the cyclization yield is expressed by Equation (1), where Cequal is the concentration at which the