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甲基丙烯酸2-(N-吖啶酮基)乙酯的合成及其敏化的烯类单体光聚合 总被引:2,自引:0,他引:2
我们曾报道过4-甲基丙烯酰氧基二苯甲酮(MABP)与甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA)构成的氧化还原引发体系敏化丙烯腈的光聚合。由于MABP及DMAEMA是可聚合的二芳基酮和脂肪叔胺,因而既能参与引发又能参与聚合而进入聚合物链中。一般二苯甲酮要同三级胺,如三乙胺等一起在紫外光照条件下形成光氧化还原引发体系才能有较好的引发效果。同一分子中既含二苯甲酮基又含三级胺基的光敏剂, 相似文献
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我们曾报道了含芳香叔胺基功能性单体的合成及其聚合的研究,这些单体都是既参与引发反应又参与聚合的“引发剂单体”。本文报道了一种含有芳香叔胺基的新单体——N-丙烯酰-N′-苯基哌嗪(APP)和N-甲基丙烯酰-N′-苯基哌嗪(MPP)的合成及其光聚合。由于APP或MPP含有芳香叔胺基,它们和过氧化苯甲酰(BPO)配合, 相似文献
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<正> 前文我们报告了含有芳香叔胺基的丙烯酸酯、甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA)在过氧化二月桂酰(LPO)引发下的聚合动力学。从所得的聚合速度方程式及低的聚合活化能,认为DMABMA与LPO形成氧化还原体系而使DMABMA聚合,在本文第Ⅳ报中报道了DMABMA不仅能引发甲基丙烯酸甲酯的聚合,还参与聚甲基丙烯酸甲酯的链中,因此称这种既能参与引发聚合反应,又参与聚合物链中的引发“引发剂单体(initiatomer)”。这种含有可聚合胺引发体系的优点是,用于丙烯酸酯类医用 相似文献
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<正> 前文报道了含芳香叔胺基丙烯酸酯-甲基丙烯酸4-N,N-二甲氨基苄酯(DMABMA)的合成和聚合。这种在分子中既含有二甲氨基苯基,又含有双键的单体为“可聚合芳香叔胺”,在过氧化二酰如过氧化苯甲酰(BPO),过氧化月桂酰(LPO)引发下,芳香叔胺残基参与氧化还原引发体系,进而双键发生聚合反应。本文报道了二甲氨基苯基取代丙烯酰胺,即N-(4-N,N‘-二甲氨基苯基)丙烯酰胺(DMAPAA)和N-(4-N,N-二甲氨基苯基)甲基丙烯酰胺(DMAPMA)的合成及聚合。 相似文献
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<正> 一些含有吗啉基的高聚物,作为含脂肪叔胺基的医用高分子材料而被瞩目。我们曾报道了N-(N′-次甲基吗啉)取代丙烯酰胺的合成,及其在过氧化二月桂酰引发下的聚合动力学。它的聚合规律和我们以往所报道的含脂肪叔胺基单体的聚合一样。本文合成了在同—分子中既含吗啉基,又含有羟基的丙烯酸脂,即甲基丙烯酸-2-羟基-3-吗啉基丙酯(HMPMA),研究了在过氧化二月桂酰(LPO)引发下的热聚合,以及在芳香酮作增感剂下的光聚合。关于HMPMA的合成,虽有所报道,但关于其表征,在过氧化 相似文献
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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. 相似文献
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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 总被引:1,自引:2,他引:1
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. 相似文献
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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 总被引:1,自引:0,他引:1
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. 相似文献
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我们发现芳香叔胺是丙烯腈聚合极有效的光引发剂。芳香叔胺苯环上氢被正性基取代时,引发能力增加,被负性基取代时,引发能力下降。下列胺的活性次序是:N,N-二甲基对甲苯胺(DMT)>N,N-二羟乙基对甲苯胺(DHET)>N,N-二甲基苯胺(DMA)>N,N-二甲胺基苯甲醛(DMB)>N,N-二甲基对硝基苯胺(DNA)。芳香叔胺引发丙烯腈光聚合属自由基机构,聚合速度与叔胺浓度的0.66次方成正比。在叔胺浓度为10~(-2)—10~(-4)M范围内,聚合物平均聚合度的倒数与叔胺浓度的0.5次方成正比。初步认为在紫外光激发下,芳香叔胺与丙烯腈分子生成激发态电子转移络合物,再分解产生自由基,引发丙烯腈聚合。 相似文献
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Shigeo Tazuke Seizo Okamura 《Journal of polymer science. Part A, Polymer chemistry》1969,7(2):715-724
Photopolymerization of acrylonitrile (AN), an acceptor monomer, was found to be accelerated in the presence of isobutyl vinyl ether (IBVE), a donor monomer. The propagation is completed by a radical mechanism as judged by copolymer compositions; in contrast to the N-vinylcarbazole–AN system studied previously. This photopolymerization system is entirely stable if kept in the dark. The comparison of the relation between Rp and [IBVE]/[AN] ratio in the monomer feed found for the spontaneous photopolymerization with that for radical polymerization initiated by azobisisobutylonitrile in the dark leads to the conclusion that the rate of photoinitiation is enhanced by the interaction between AN and IBVE, whereas the propagation step by a radical mechanism is retarded by increasing concentration of IBVE. The contact charge-transfer complex between IBVE and AN was confirmed by electronic spectroscopy of the polymerization system, which showed photosensitization by charge-transfer interaction. The spectroscopic study of other weak donor–weak acceptor systems is also discussed. 相似文献