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以2-(6-氧化-6-氢-二苯基(c,e)<1,2>氧杂磷酰基)-1,4-二羟基苯(ODOPB)结构单元为中心,在两侧通过酯化反应分别引入4-乙烯基苯甲酰基和4-戊氧基苯甲酰基,并作为苯乙烯衍生物单体(MED),在AIBN引发下,聚合得到了含9,10-二氢-9-氧杂-10-磷酰杂菲-10-氧化物(简称磷酰杂菲,DOPO)基团的聚苯乙烯衍生物(PED).因侧链之间具有较强的相互作用以及聚苯乙烯主链的刚性而易形成聚集形态,使分子量超出GPC的正常检测范围;同时表现出良好的热稳定性,MED和PED失重5%时的对应温度分别为339℃和345℃.也正是这两种作用同时存在,并相互制约,侧基之间产生了一定程度的规整排列,限制了磷酰杂菲基团的转动,降低了其非辐射能量转移,从而相对于MED,使PED在THF溶液中荧光强度得到了明显增强.由于PED在沉淀聚集过程中受到THF和沉淀剂(水或正己烷)的共同影响,在沉淀剂含量达到70%之前,侧基之间难以形成规整排列,其分子链内转动很大程度引起非辐射能量转移,所以随着沉淀剂含量的增加,荧光强度不断降低;然而当沉淀剂含量达到70%以上时,由于水分子能够与两个相互靠近的侧基共同形成基于氢键作用的复合超分子结构,这不仅抑制了磷酰杂菲基团的转动能力,增强了荧光强度,在一定程度上表现出AIEE特性,而且会在450nm处出现新的肩峰,以显示该结构有别于侧基自身的密聚集;但以正己烷为沉淀剂时,因不能形成氢键超分子结构,PED分子链只是无序密聚集,所以表现为只是随着正己烷加入荧光强度不断降低,没有出现荧光红移的现象。
(2-oxo-6-oxo-diphenyl (c, e) <1,2> oxaphosphoyl) -1,4-dihydroxybenzene (ODOPB) In the esterification reaction, 4-vinylbenzoyl and 4-pentyloxybenzoyl groups were introduced into the esterification reaction, which were used as monomer of styrene derivative (MED). Under AIBN polymerization, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide (abbreviated as phosphoryl phenanthroline, DOPO) group due to the strong interaction between the side chains and the poly Styrene backbone rigid and easy to form aggregates, the molecular weight beyond the GPC detection range; also showed good thermal stability, MED and PED 5% weight loss when the corresponding temperature was 339 ° C and 345 ° C These two kinds of effects exist at the same time and restrict each other, and there is a certain degree of regular arrangement between the side groups, which limits the rotation of the phosphoryl phenanthrene group and reduces the non-radiative energy transfer, so that relative to the MED, the PED Fluorescence intensity was significantly enhanced in THF solution.Due to the common influence of PED and precipitation agent (water or n-hexane) during the precipitation and aggregation process, it is difficult for the side groups to be formed before the content of precipitant reaches 70% Forming a regular arrangement, the molecular chain rotation caused a large extent non-radiative energy transfer, so as the precipitant content increases, the fluorescence intensity continues to decrease; however, when the precipitant content reaches 70% or more, due to the water molecules with two The adjacent side groups together form a composite supramolecular structure based on hydrogen bonding which not only inhibits the phosphaphenanthrene group’s ability to rotate, enhances the fluorescence intensity, to some extent, exhibits AIEE properties, and at 450 nm A new shoulder peak appears to show that the structure is different from the dense aggregation of side groups; however, when n-hexane is used as the precipitating agent, the hydrogen bonding supramolecular structure can not be formed and the PED molecular chain is only a disorderly dense aggregation, Only with the addition of n-hexane fluorescence intensity decreased, there is no red fluorescence shift phenomenon.