Entropy‐Driven Ring‐Opening Disulfide Metathesis Polymerization for the Synthesis of Functional Poly(disulfide)s,Macromolecular Rapid Communications

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Entropy‐Driven Ring‐Opening Disulfide Metathesis Polymerization for the Synthesis of Functional Poly(disulfide)s
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2018-01-05 , DOI: 10.1002/marc.201700735
Felix N. Behrendt ₁ , Helmut Schlaad ₁

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Metal‐free entropy‐driven disulfide metathesis polymerization of unsaturated l‐cystine based macrocycles produces high‐molar‐mass heterofunctional poly(disulfide)s, i.e., poly(ester‐disulfide‐alkene) and poly(amide‐disulfide‐alkene); M_w^app = 44–60 kDa, Ð > 1.7. The polymerization is fast and reaches equilibrium within 1–5 minutes (monomer conversion 70–90%) in polar aprotic solvents such as N,N‐dimethylacetamide, dimethylsulfoxide, or γ‐valerolactone. Thiol‐terminated polymers are stable in bulk or when dissolved in weakly polar solvents, but rapidly depolymerize in dilute polar solution.

中文翻译：

熵驱动开环二硫复分解聚合反应合成功能性聚二硫

不饱和的基于l胱氨酸的大环化合物的无金属熵驱动的二硫化物易位聚合产生高摩尔质量的杂官能聚二硫化物，即，聚（酯二硫化物烯烃）和聚（酰胺二硫化物烯烃）；M _w^app = 44–60 kDa，Ð > 1.7。在极性非质子传递溶剂（如N，N-二甲基乙酰胺，二甲基亚砜或γ-戊内酯）中，聚合反应很快并在1-5分钟内达到平衡（单体转化率70-90％）。巯基封端的聚合物在本体中或溶解在弱极性溶剂中时都很稳定，但在稀极性溶液中会迅速解聚。

更新日期：2018-01-05

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