三苯膦引发丙炔醇光聚合

PHOTOPOLYMERIZATION OF PROPARGYL ALCOHOL INITIATED BY TRIPHENYLPHOSPHINE

本文首次应用三苯膦引发丙炔醇光聚合，制得黄色粉末状、具有共轭双键结构的聚丙炔醇。研究了该光聚合反应的动力学行为及机理。发现三苯膦与丙炔醇Ｃ≡Ｃ叁键能形成基态电荷转移络合物，在光照下引发自由基聚合。聚合速率方程为Ｒｐ＝ｋｐ［ＯＨＰ］（０．５）［ＰＰｈ３］（０．７），表观速率常数ｋｐ＝２．９０×１０（－５）Ｌ（０．２）·ｍｏｌ（－０．２）·ｓ（－１），聚合活化能Ｅａ＝２１．７８ｋＪ／ｍｏｌ。

The photopolymerization of propargyl alcohol by UV irradiation in the presence of triphenylphosphine was carried out for the first time. Poly (propargyl alcohol) obtained is a yellow powder with conjugated C=C double bonds.The kinetic behavior and mechanism for this photopolymerization have been investigated. It was thought that charge-transfer complex formed between triphenylphosphine and the C≡C triple bond of the propargyl alcohol absorbs light and initiates the radical polymerization.The apparent rate equation of the polymerization could be expressed as: Rp=Kp[OHP]0.5[PPh3]0.7, where the average apparent rate constant kp = 2. 90×10-5L0.2·mol-0.2·s-1. The overall polymerization activation energy Ea measured was 21. 78 kJ/mol.