吩噻嗪类不饱和单体与过氧化物氧化还原体系引发的两烯腈聚合

Polymerization of Acrylonitrile Initiated by Acrylic Monomers Bearing Phennothiazine and Peroxide System

研究了丙烯酰吩噻嗪（ Ａ Ｐ Ｔ） 及其衍生物丙烯酰吩噻嗪砜（ Ａ Ｐ Ｔ Ｏ） 与过氧化苯甲酰（ Ｂ Ｐ Ｏ） 组成氧化还原体系引发丙烯腈的光聚合，研究发现 Ａ Ｐ Ｔ－ Ｂ Ｐ Ｏ 比 Ａ Ｐ Ｔ Ｏ— Ｂ Ｐ Ｏ 引发能力高，而前者引发得到的聚合物相对分子质量比后者引发得到的要低．二者引发丙烯腈光聚合的动力学方程为： Ｒｐ ∝［ Ａ Ｐ Ｔ］０ ．４９［ Ｂ Ｐ Ｏ］０ ．５２［ Ａ Ｎ］０ ．９９ ， Ｅａ ＝ ３８ ．８０ｋ Ｊ／ｍｏｌ； Ｒｐ ∝［ Ａ Ｐ Ｔ Ｏ］０ ．４８［ Ｂ Ｐ Ｏ］０ ．４７［ Ａ Ｎ］１ ．０４ ， Ｅａ ＝ ４３ ．９５ｋ Ｊ／ｍｏｌ．通过紫外分析发现， Ａ Ｐ Ｔ 或 Ａ Ｐ Ｔ Ｏ 不仅参与引发反应，而且参与聚合反应。

The polymerization of Acrylonitrile(AN) initiated by N_acrylyl_phenothizaine(APT) and N_acrylyl_phenothiazine sulfoxide(APTO) with oxide(BPO) was studied respectively.The polymerization rate equations and their overall activation energies were obtained as follows: R p∝[APT] 0.49 [BPO] 0.52 [AN] 0.99 , E a=38.80kJ/mol; R p∝[APTO] 0.48 [BPO] 0.47 [AN] 1.04 , E a=43.95kJ/mol. The initiation ability of APT_BPO is higher than that of APTO_BPO,but molecular weight of PAN initiated by APT_BPO is lower than that of APTO_BPO.The UV spectrum of P(AN) initiated by the APT_BPO system indicates that APT not only initiates the polymerization of AN,but also enteres into the P(AN) polymer chains.