Polymerization of ε-caprolactone initiated by Nd(BH4)3(THF)3:: Synthesis of hydroxytelechelic poly(ε-caprolactone)

被引:142
作者
Guillaume, SM [1 ]
Schappacher, M [1 ]
Soum, A [1 ]
机构
[1] Univ Bordeaux 1, ENSCPB, CNRS, UMR 5629,Lab Chim Polymeres Organ, F-33607 Pessac, France
关键词
D O I
10.1021/ma020993g
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
The ring-opening polymerization of is an element of-caprolactone initiated by Nd(BH4)(3)(THF)(3), 1a, has been investigated, The polymerization occurs rapidly ( <5 min) and quantitatively at room temperature to give, in high yields, polymers which exhibit controlled molecular weights and relatively low polydispersities. Initially, 3 mol of is an element of-caprolactone may coordinate the neodymium center to form the Nd(BH4)(3)(is an element of-caprolactone)(3) complex, 1b. Then, is an element of-caprolactone inserts into the metal-borohydride hydrogen bond of 1a or 1b to give the intermediate [(BH4)(2)Nd[O(CH2)(5)C(O)(HBH3)]], [i], in which each (HBH3) unit immediately interacts with the a-carbonyl group to form the corresponding neodymium(trisalkoxide) derivative [Nd[O(CH2)(5)CH2(OBH2)](3)], 2a. Polymerization of is an element of-caprolactone by 2a then proceeds via a pseudoanionic mechanism through the alkoxide attack at the monomer resulting in the oxygen-acyl bond cleavage. Further treatment of the resulting product with benzyl alcohol gives alpha,omega-telechelic poly(is an element of-caprolactone) diols, HO(CH2)(5)C(O){O(CH2)(5)C(O)}(n)O(CH2)(6)OH. The proposed mechanism is supported by H-1 and C-13 NMR, SEC, and MALDI-TOF analyses of the polymers.
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页码:54 / 60
页数:7
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