非水凝胶原位聚合制备Tb(OP_r^i)_3掺杂的P(MMA-co-St)共聚物的研究

Copolymer of P(MMA-co-St) Doped with Triisoproyloxyl Terbium Prepared by Non-Aqueous Gel In-Situ Polymerization

将三异丙氧基铽[Tb(OPri)3]直接掺入甲基丙烯酸甲酯(MMA)与苯乙烯(St)的混合单体中,混匀后会立即形成白色凝胶体,通过原位聚合后即获得掺杂Tb(OPri)3的P(MMA co St)共聚物。采用FT IR,DMTA,TG,FS,ESEM等手段对其进行表征。FT IR分析表明,共聚物中Tb3+离子与羰基和苯环间存在着配位作用;MMA与St主要以交替共聚为主。DMTA,TG表明,Tb(OPri)3的掺入,使共聚物的玻璃化温度下降、贮能模量和耐热性能提高。FS分析表明,当Tb含量为1.0%时,共聚物在381nm处发射宽而强的荧光,其强度约是纯P(MMA co St)的14倍,同时在489,544,584nm处发射很强的Tb3+离子5D4→7F6,5D4→7F5,5D4→7F4跃迁的特征荧光。ESEM表明,共聚物呈现交联网络状的微观形貌,未见聚集体,Tb3+离子在体系中是均匀分布的。

The copolymer of P(MMAcoSt) containing Tb was prepared by the insitu polymerization of gel, which was obtained by doping directly triisopropoxyl terbium in the monomer mixtures of methyl methacrylate and styrene. The copolymer was characterized by FTIR, dynamical mechanical thermal analysis (DMTA), TG, fluorescence spectra (FS), ESEM etc. There are coordination interactions between terbium(Ⅲ) ion and carboxyl or phenyl group in the P(MMAcoSt)/Tb. The glass transition temperature (Tg) of P(MMAcoSt) is reduced by the doping of triisopropoxyl terbium, while the storage modulus (E′) and heat resistance of the copolymer are improved. As Tbcontent is 1%, the copolymer can emit very strong fluorescence in 381 nm, the fluorescence strength is 14 times higher than that of pure P(MMAcoSt), moreover exhibits strong characteristic luminescence of terbium ion 5D4→7F6, 7D4→7F5, 5D4→7F4 in 489, 544, 584 nm. ESEM reveal the crosslinking network structure of P(MMAcoSt)/Tb and there is no conglomerate, the terbium(Ⅲ) ion is uniformly distributed in P(MMAcoSt)/Tb.