N-丙烯酰吩噻嗪氧化物敏化的甲基丙烯酸甲酯的光聚合

研究了N -丙烯酰吩噻嗪氧化物 (APTO)敏化甲基丙烯酸甲酯 (MMA)的光聚合 ,得到了APTO敏化MMA光聚合的速率方程和表观活化能并探讨了其引发机理     

8-丙烯酰氧喹啉及其聚合物增感的丙烯腈光聚合

<正> 我们曾研究过电子给体基团和电子受体基团共存于同一分子中的一类功能性单体,如甲基丙烯酸-4-(N,N)-二甲氨基苄酯(DMABMA)、N-(4-N′,N′-二甲氨基苄基)丙烯酰胺(DMAPAA)、8-丙烯酰氧喹啉(AQ)。N-丙烯酸-N′=苯基哌嗪(APP)等     

N-丙烯酰-2-氯吩噻嗪、N-丙烯酰-2-乙酰基吩噻嗪单体和聚合物的合成以及荧光行为的研究

Two N-acrylic monomers having phenothiazine moieties , N-acrylyl-2-chlorophe-nothiazine ( I ) , N-acrylyl-2-acetylphenothiazine ( I ) were synthesized and their polymers were obtained by free radical polymerization . The fluorescence study showed that at the same molar concentration of the chromophores, the fluorescence intensities of the polymers were much stronger than that of the monomers. This would be explained by what we called "Structural Self-quenching Effect. " The Stern-Volmer constants of the polmers quenched by several electron defecient vinyl monomers were obtained. The results indicated that their quenching efficiencies were relevant to the degree of the electron deficiency of the double bond.     

8-丙烯酰氧喹啉及其聚合物与四溴化碳双组分体系敏化的丙烯腈光聚合

我们曾报道过8-丙烯酰氧喹啉本身在光照下可以聚合;8-丙烯酰氧喹啉(AQ)及其聚合物(PAQ)的喹啉环上的氮原子可以和双键缺电子单体如丙烯腈(AN)在紫外光下能形成激基复合物引发AN的光聚合,并且通过荧光分析证明AQ或PAQ还参与AN聚合物链中,含有氮杂环的烯类单体如N-乙烯基咔唑等不仅和缺电子化合物,和一些卤代烷如CCl_4、CBr_4等在激发下也可以形成激基复合物,进而可以引发烯类单体聚     

N-丙烯酰吩噻嗪异构体的量子化学研究

用量子化学从头算方法 ,在RHF/ 6_31G 的水平上 ,对N_丙烯酰吩噻嗪分子两种异构体进行了理论计算 ,优化得到了它们的平衡几何构型 ,并计算了它们的谐振动频率 .结果表明 :N_丙烯酰吩噻嗪分子两种异构体的稳定性不同 .用PM3/CIS和AM1/CIS方法计算了它们的电子光谱 ,得到了由基态到各激发态的垂直跃迁能和相应的振子强度 .这些结果对探讨N_丙烯酰吩噻嗪引发丙烯腈聚合的机理是有益的     

含吩噻嗪氧化物的N-丙烯酰基吩噻嗪氧化物的合成及其荧光行为

含吩噻嗪氧化物的Ｎ 丙烯酰基吩噻嗪氧化物的合成及其荧光行为刘向前杜福胜李子臣李福绵（北京大学化学与分子工程学院北京１００８７１）关键词Ｎ 丙烯酰基吩噻嗪氧化物，荧光光谱，荧光结构自猝灭我们曾报道过含给电子性生色基团的丙烯酰类单体及其聚合物的荧光行为...     

N-丙烯酰-2-氯吩噻嗪、N-丙烯酰-2-乙酰基吩噻嗪单体和聚合物的合成以及荧光行为的研究

含芳杂环的丙烯酰类功能性单体及其聚合物的合成一直吸引人们的兴趣,原因之一是由于这类单体可用一般的自由基引发剂引发聚合,这类聚合物所表现出的光化学、电化学性质甚被瞩目。如含吩噻嗪的丙烯酰类衍生物可以和缺电子的化合物形成电荷转移     

N-甲基丙烯酰-N′-嘧啶基哌嗪及其聚合物敏化的丙烯腈光聚合

The photopolymerization of acrylonitrile (AN) sensitized by N-methacrylyl-N'-pyrimidi-nopiperazine (MPMP) and its polymer, P(MPMP) was studied kinetically. It was found that the photopolymerization rate of AN sensitized by monomeric MPMP is proportional to 0.35th power of MPMP concentration and 0.85th power of AN concentration, respectively. In the case sensitized by Polymeric MPMP, P(MPMP) is proportional to 0.30th power of P(MP-MP) concentration and 1.0 power of AN concentration, respectively. The overall activation energies for photopolymerization sensitized with MPMP and P(MPMP) were determined to be 4.71Kcal/mol and 4.58Kcal/mol,respectively.From the fluorescence analysis for P(AN) senstitized by either MPMP or P(MPMP),it was confirmed that MPMP and P(MPMP) not only sensitized the photopolymerization of AN but also entered into the P(AN) chains.     

8-丙烯酰氧喹啉及其聚合物与四溴化碳双组分体系敏化的丙烯腈光聚合

Photopolymerization of acrylonitrile (AN) sensitized by binary component initiators consisting of 8-acryloyloxyquinoline (AQ) and its polymer (PAQ) with carbon tetrabromide (CTB) are investigated kinetically. It is found that the polymerization rates are proportional to 0.19th power of AQ concentration, 0.35th power of CTB concentration and 0.62th power of AN concentration for AQ-CTB system initiation system; proportional to 0.24th power of PAQ concentration, 0.22th power of CTB concentration and 1.0th power of AN concentration initia-ted by above systems are obtained to be 5.26Kcal/mol and 6.34Kcal/mol respectively. It is also found that the polymerization rates sensitized by addition of CTB to AQ or PAQ are much higher than that ofAQ or PAQ alone. Forom the fluorescence analysis of AN polymers,it is confirmed that AQ or PAQ joints into the AN polymer chains. The molecular weight of PAN sensitized by the binary initiatorsystems is lower than that of AQ or PAQ sensitized.     

N-甲基丙烯酰-N′-嘧啶基哌嗪及其聚合物敏化的丙烯腈光聚合

我们曾报道过同一分子中含有给电子生色基团和电子受体基团的一类功能性单体,如甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA),N-(4-N′,N′-二甲氨基苯基代丙烯酰胺,N-(4-N′、N′)-二甲氨基苯基代甲基丙烯酰胺(DMAPMA),8-丙烯酰氧喹啉(AQ),N-丙烯酰-N′-苯基哌嗪(APP)的合成、聚合以及单独或与过氧化二酰构成氧化还原体系以引发烯类单体的聚合研究。N-甲基丙烯酰-N′-嘧啶基哌嗪(MPMP)     

N-甲基-N-(2-甲基丙烯酰氧乙基)苯胺敏化的丙烯腈光聚合

含有芳香叔胺基的烯类单体如N,N-二甲氨基苯乙烯,N-4-N',N'-二甲氨基苯基代丙烯酰胺(DMAPAA),N-4-N',N'-二甲氨基苯基代甲基丙烯酰胺(DMAPMA),甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA),8-丙烯酰氧喹啉(AQ)等不仅与过氧化物构成氧化还原引发体系以引发其它烯类单体的光聚合还可以作为光敏剂引发烯类单体的光聚合。由于这类功能性单体在同一分子中既含有缺电子双键基团又含有供电子生     

可聚合的二苯酮-脂肪叔胺光氧化还原体系敏化的丙烯腈光聚合

<正> 关于二苯甲酮-三级胺体系引发烯类单体光聚合的研究已有许多报道。其引发机理研究得也比较透彻。此类引发体系之所以引人注目,除其本身具有良好的引发效果外,还有重要的一点在于氧气对于此体系不但无阻聚作用,而且在一定条件下能够加速其聚合反应。甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA)是可聚合的脂肪叔胺。有关芳香酮类如二苯甲酮。芴酮与DMAEMA构成的引发体系的研究已有城田等人和张举贤     

芴酮-甲基丙烯酸N,N-二甲氨基乙酯引发丙烯腈光聚合的研究

二苯酮(BP)-脂肪叔胺体系作为光氧化还原引发体系引发烯类单体的光聚合已有许多研究。甲基丙烯酸N,N-二甲氨基乙酯(DMAEM)是含有脂肪叔胺基的丙烯酸酯类。由于含有叔胺基,它不仅能参与和芳香酮类构成的光氧化还原引发体系,其本身还参与聚合反应。 三川等报道了DMAEM在BP存在下的本体光聚合,并指出氧对此聚合体系有加     

N-(4-苯甲酰苯基)衣康酰亚胺与甲基丙烯酸-N,N-二甲氨基乙酯组成的可聚合光氧化还原体系引发的丙烯腈光聚合

Ｎ （４ 苯甲酰苯基）衣康酰亚胺与甲基丙烯酸 Ｎ，Ｎ 二甲氨基乙酯组成的可聚合光氧化还原体系引发的丙烯腈光聚合高青雨杨更须崔元臣张福莲张举贤（河南大学化学化工学院开封４７５００１）李福绵（北京大学化学系北京１００８７１）关键词Ｎ （４ 苯甲酰苯基）...     

一种水溶性可聚合敏化剂N－甲基丙烯酰－N＇－嘧啶哌嗪敏化的丙烯酰胺光聚合

一种水溶性可聚合敏化剂Ｎ－甲基丙烯酰－Ｎ＇－嘧啶哌嗪敏化的丙烯酰胺光聚合高青雨，杨更须，张福莲，张举贤，李福绵（河南大学化学化工系开封４７５００１）（北京大学化学系北京１００８７１）关键词Ｎ－甲基丙烯酰－Ｎ＇－嘧啶哌嗪，丙烯酰胺，水溶性光敏剂，光聚合...     

N-甲基-N-(2-甲基丙烯酰氧乙基)苯胺敏化的丙烯腈光聚合

The photopolymerization of acrylonitrile sensitized by N-methyl-N-(2-methacryloyloxye-thyl)aniline (MEMA) was studied kinetically. The photopolymerization rate of AN in DMF by using MEMA as sensitizer is proportional to 0.32 th power of MEMA concentration and 1.20 th power of AN concentration. The overall activation energy for the polymerization was found to be 4.82 Kcal/Mol. From the fluorescence analysis of obtained polyacrylonitrile sensitized by MEMA, it was confirmed that MEMA not only joined the inition but also entered into the polyacrylonitrile chains. The initiation mechanism was proposed tentatively.