含氮给体结构对丙烯腈电荷转移光聚合的影响

<正> 对于正性烯类单体,主要是乙烯基咔唑的电荷转移聚合,诚田已作过详细综述。负性烯类单体的电荷转移聚合主要研究的单体是丙烯腈(AN)及甲基丙烯酸甲酯(MMA)。Barton等研究了芳烃为引发剂的MMA光聚合。我们研究了芳胺为引发剂的光聚合。 芳胺,尤其是芳叔胺,是较强的电子给体,与负性单体在光照下经激基复合物而引发聚合,我们的实验表明,吡啶及其同系物(喹啉与吖啶)并不象吡咯及其同系物(吲哚与咔唑)那样有效地引发AN等负性单体的光聚合(见表1)。从图1所示的结构看,它们有

THE EFFECTS OF THE STRUCTURE OF NITROGEN-CONTAINING DONORS ON THE CHARGE TRANSFER PHOTOPOLYMERIZATION OF ACRYLONITRILE

Aniline, pyrrole and their derivatives can initiate photopolymerization of acrylonitrile and form charge transfer complex (CTC) with tetracyanoethylene (TCNE), their initiation rates and abilities to form CTC are related to the twist angle between the n orbit of nitrogen atom and the p orbit of benzene ring or pyrrole ring. The greater the twist angle, the lower the polymerization rate and the more difficult forming CTC. These results are explained with the relation between n-p conjugation and the twist angle.