功能材料
功能材料
공능재료
JOURNAL OF FUNCTIONAL MATERIALS
2012年
16期
2187-2190,2195
,共5页
王华林%殷德飞%颜世民%李胜水
王華林%慇德飛%顏世民%李勝水
왕화림%은덕비%안세민%리성수
聚对苯撑乙烯%超支化聚合物%Gilch聚合%反应机理
聚對苯撐乙烯%超支化聚閤物%Gilch聚閤%反應機理
취대분탱을희%초지화취합물%Gilch취합%반응궤리
poly(p-phenylenevinylene)%hyperbranched polymer%Gilch polymerization%reaction mechanism
在以Gilch路线合成了一系列含烷氧基超支化聚对苯撑乙烯(HPPV)共聚物的基础上,对其聚合反应的过程及机理进行了初步研究。通常,PPV的聚合是按照自由基机理进行,即反应物单体在分子内脱去卤化氢(HX)后形成一种对醌二甲烷单体,再通过自由基链增长达到聚合的目的。通过DFT(B3LYP/6-311G(d))方法对反应单体1,3,5-三氯甲基-2,4,6-三甲氧基苯(TCMTMOB)在分子内脱去HCl后的结构进行了优化,发现此单体同样可以形成稳定的间二醌结构,易于与对醌二甲烷单体共聚生成超支化共聚物,这与实验结果相吻合。
在以Gilch路線閤成瞭一繫列含烷氧基超支化聚對苯撐乙烯(HPPV)共聚物的基礎上,對其聚閤反應的過程及機理進行瞭初步研究。通常,PPV的聚閤是按照自由基機理進行,即反應物單體在分子內脫去滷化氫(HX)後形成一種對醌二甲烷單體,再通過自由基鏈增長達到聚閤的目的。通過DFT(B3LYP/6-311G(d))方法對反應單體1,3,5-三氯甲基-2,4,6-三甲氧基苯(TCMTMOB)在分子內脫去HCl後的結構進行瞭優化,髮現此單體同樣可以形成穩定的間二醌結構,易于與對醌二甲烷單體共聚生成超支化共聚物,這與實驗結果相吻閤。
재이Gilch로선합성료일계렬함완양기초지화취대분탱을희(HPPV)공취물적기출상,대기취합반응적과정급궤리진행료초보연구。통상,PPV적취합시안조자유기궤리진행,즉반응물단체재분자내탈거서화경(HX)후형성일충대곤이갑완단체,재통과자유기련증장체도취합적목적。통과DFT(B3LYP/6-311G(d))방법대반응단체1,3,5-삼록갑기-2,4,6-삼갑양기분(TCMTMOB)재분자내탈거HCl후적결구진행료우화,발현차단체동양가이형성은정적간이곤결구,역우여대곤이갑완단체공취생성초지화공취물,저여실험결과상문합。
Based on the synthesis of a series of hyperbranched PPVs via Gilch polymerxzatlon, the polymermauon mechanism was discussed. It is a broad consensus that in Gilch polymerizations the 1,4-bis(halomethylene)ben- zene starting material first changes into an α-halo-p-quinodimethane intermediate which then acts as the real ac- tive monomer in the subsequent radical chain polymerization. In this copolymerization reaction, the branched unit cannot be eliminated to form a p-quinodimethane intermediate. The plausible route is a trigonal trianion acting as initiator for an anionic polymerization, If the copolymerization reaction is processed in radical mecha- nism, it is the key step to form a stable a-halo-m-quinodimethane in the copolymerization. In order to verify the existence and stability of α-halo-m-quinodimethane intermediate, the molecular geometry of 1,3,5- trichlorom- ethyl -2,4,6- trimethyloxybenzene (TCMTMOB) were optimized by DFT methods (B3LYP/6-311G(d)). The results show that the monomer TCMTMOB can eliminate HC1 to give a stable α-halo-m-quinodimethane struc- ture; the negative charges on quinodimethane are increased because of the electron-donating effect of the alkoxy groups in the ring, which is in favor of the stability of the corresponding exocyclic double bonds. The interme- diate represent the initiators of subsequent bilateral radical chain growth via 1,6-type addition of further p- quinodimethane monomers to form a hyperbranched copolymer. So, the theoretical analysis agrees well with experiment result.