共查询到18条相似文献,搜索用时 93 毫秒
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研究了聚丙烯基聚肟偕氮合铜(Ⅱ)(PPAO—Cu)—亚硫酸钠体系引发甲基丙烯酸甲酯(MMA)水溶液聚合。表观聚合速度(Rp)是 Rp=9.7×10~(12)e~(88.8kJ/RT) c(MMA)~(0.88) c(Na_2SO_3)~(0.50) 聚合诱导期(τ)与亚硫酸钠浓度成反比,与PPAO—Cu用量和单体浓度无关。可表示为 1/τ=1.2×10~(12)e~(-55.3KJ/R) c(Na_2SO_3)=K_τ·R_ 聚合是由PPAO—Cu/Na_2SO_3氧化还原反应产生的初级自由基所引发。 相似文献
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研究了笼形聚羧酸钒(PV)-硫脲(TU)体系在硝酸溶液中引发丙烯腈(AN)聚合动力学。表观聚合速度(R_p)是 R_p=9.7×10~5e~(-10500)/RT[AN]~1.0[PV]~0.50[TU]~0.76[HNO_3]~1.5聚合诱导期(τ)随反应条件而变化,聚合温度越高,引发种浓度越大,聚合诱导期越短,但与单体浓度的变化无关。 1/τ=4.6×10~(12)e~(-13500)/RT[AN]~0[PV][TU]~(-3/2)[HNO_3]~3=K_τ·R_i聚合物分子量随单体浓度增大而提高,但随聚合温度及引发种浓度增大而下降,即 笼形聚羧酸钒—硫脲体系引发丙烯腈聚合的动力学参数和引发机理与杨梅型聚羧酸钒—硫脲体系在相同的条件下引发聚合的行为有明显的区别,认为是和两种树脂大分子链的空间结构所引起的传质阻力有关。 相似文献
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Cu~(2+)-Na_2SO_3体系引发甲基丙烯酸甲酯聚合动力学 总被引:3,自引:1,他引:3
研究了Gu~(2+)-Na_2SO_3氧化还原体系在静置的密闭空气气氛下引发甲基丙烯酸甲酯水溶液聚合。表观聚合速度(R_p)是 R_p=1.86×10~(15)e~(-24,200/RT)[MMA]~(1·0)[Cu~(2+)]~0[Na_2SO_]~(0·50)覆盖气氛对聚合有显著影响。氧抑制聚合反应,但可使Gu~(2+)离子氧化再生。表现为低的表观聚合速度和高的碰撞频率因子与表现聚合活化能。 本文讨论了引发聚合机理。 相似文献
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研究了笼形聚肟偕亚氨二乙酸钒(CPV)-硫脲(TU)体系在硝酸溶液中引发丙烯腈(AN)聚合反应.表观聚合速度(R_P)是 R_P=1.0×10~8e~(-10.500/RT)[AN]~(1.0)[CPV]~(1.0)[TU]~(1.5)[HNO_3]~(3.0) 聚合诱导期(τ)随反应温度和物料浓度发生变化,可表示为 1/τ=5.2×10~9e~(-12.800/RT)[AN]~1.0[CPV]~1.0[TU]~1.5[HNO_3]~3.0实验结果表明,聚合反应以单基终止为特征,可能是和高分子载体较大的空间位阻有关. 相似文献
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研究了亚硝酸钠引发硝酸溶液中丙烯腈的聚合反应。测得表现聚合速度 Rp=Ae~(-10,800/RT)[AN]~2.2[NaNO_2]~(0.17-1.0)[HNO_3]~(1.0-0.67 丙烯腈-丙烯酸甲酯共聚合反应中竞聚率分别是γ_An=0.96,γ_MA=1.17,表明聚合反应是按自由基机理进行。 根据聚合动力学和红外光谱分析,认为以亚硝酸钠引发硝酸溶液中丙烯腈的聚合反应与电解或金属溶蚀过程中的次级引发相同。 相似文献
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研究了硝酸溶液中聚丙烯基聚偕氨肟(PPAO)—硫脲(TU)络合物引发丙烯腈(AN)聚合动力学。在[TU]/[PPAO]<0.5摩尔比的条件下,表观聚合速度(R_p)是R_p=9.1×10~4e~(-45.2k J/RT)[AN]~(2.0)[HNO_3]~(1.5)[TU]~(1.0)聚合物分子量随聚合温度升高而下降,并与硝酸浓度的1.5次方和硫脲浓度的1.0次方成反比,与丙烯腈浓度和 PPAO 浓度无关。可表示为_m=K·1/T·(1/[HNO_3]~(1.5)[TU]~(1.0))=K_M·1/T·(R_p/R_t)根据实验结果,提出了“络合—质子转移”引发机理。 相似文献
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研究了金属镁在硝酸溶液中引发丙烯腈的聚合反应。实验结果表明,聚合速度与金属镁的用量无关,并且当[HNO_3]>[AN]时服从下列关系式: R_p=1.91×10~5e~(-15000/RT)[Mg]~0[AN]~(2.2)[HNO_3]~(0.45) 丙烯腈-丙烯酸甲酯的共聚试验证明,聚合反应是按自由基机理进行。 相似文献
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A. B. Moustafa M. A. Abd El-Ghaffar A. S. Badran A. M. Rabie 《Journal of polymer science. Part A, Polymer chemistry》1981,19(3):719-727
The aqueous polymerization of methyl methacrylate (MMA) with sodium bisulfite as initiator was carried out in a nitrogen atmosphere with and without inorganic substances like copper metal, cupric and cuprous oxides, and cupric sulfide. It was also done in the presence of organocopper compounds like copper phthalocyanine and copper biphthalocyanine. The catalytic effect of these compounds was studied. Mildly heated cupric sulfide proved to have a small catalytic effect on the polymerization process that may be attributed to the retarding effect of the released elementary sulfur. The catalytic effect of the different copper compounds and the copper metal equivalent contained in them was studied. The polymerization process revealed that cuprous and cupric oxides possess the highest catalytic influence. An attempt was made to investigate the role of the different anions on the polymerization process. It was found that an increase on the concentration of the copper compounds leads to a corresponding increase in the catalytic effect. It was also observed that the behavior of insoluble copper catalysts is different from that of the soluble. The effect of these catalysts on the average molecular weight of the poly(methyl methacrylate) (PMMA) produced was also examined. 相似文献
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Polymerization of methyl methacrylate with cupric laurate-N,N-dimethyl formamide as initiator system
Prabir Kumar Pal Ajit Kumar Chaudhuri 《Journal of polymer science. Part A, Polymer chemistry》1990,28(11):3123-3135
The polymerization of methyl methacrylate with cupric laurate in combination with N,N-dimethyl formamide as initiator was studied in carbon tetrachloride medium at 60°C. The rate of polymerization was found to be proportional to the 3/2th power of the monomer concentrations and to the square root of both cupric laurate and DMF concentrations. Spectroscopic investigations indicated a ternary complex formation involving cupric ion, methyl methacrylate, and DMF. A reaction scheme is suggested on the basis of these results and various kinetic constants have been evaluated. 相似文献
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Prabir Kumar Pal Dipa Nandi Ajit Kumar Chaudhuri 《Journal of polymer science. Part A, Polymer chemistry》1989,27(5):1687-1699
The polymerization of methyl methacrylate initiated by cupric laurate in combination with benzoin has been investigated in carbon tetrachloride medium at 60°C. The rate of polymerization was found to be proportional to the square root of both cupric ion and benzoin concentrations, and to the 1.5th power of the monomer concentration. Spectral studies indicated that there is a complex formation between cupric ion and the monomer methyl methacrylate. A reaction scheme, based on initial formation of the complex and its subsequent reaction with benzoin to produce the free radicals responsible for initiation has been postulated to explain the observed results. 相似文献
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The cupric sulfate–hydrazine system has been used to initiate the aqueous solution polymerization of methyl methacrylate at pH 9.25 in the absence of oxygen. There is no decomposition of hydrazine on the surface of the reduced cupric hydroxide until a flocculant precipitate is formed (cupric sulfate concentration of about 10?3 mole/1). Below this concentration, the initiating reaction occurs solely in solution, the rate of polymerization decreasing when the reaction mixture becomes depleted in cupric ions. When a suitable surface area of the precipitated polymer is attained, adsorption and decomposition of hydrazine occurs on its surface, causing further initiation of polymerization. 相似文献
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消除甲基丙烯酸酯类单体阴离子聚合副反应的几种主要方法 总被引:1,自引:0,他引:1
本文论述了甲基丙烯酸酯类单体阴离子聚合过程中主要副反应的机理,重点讨论了三类主要的化合物(金属烷氧基化合物,金属卤化物和冠醚类化合物)对于甲基丙烯酸酯类单体阴离子活性中心的稳定作用。 相似文献
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The cupric sulfate–hydrazine system has been used to initiate the aqueous solution polymerization of methyl methacrylate at pH 9.25 in the presence of oxygen. At cupric sulfate concentrations greater than the saturation solubility of cupric hydroxide, hydrazine is adsorbed on, and decomposes on, the surface of the hydroxide. The kinetics of the decomposition are zero-order both in the absence and the presence of monomer. The initiation of the polymerization occurs both at the surface of the cupric hydroxide on to which some monomer is adsorbed and also in solution. Below the saturation solubility of cupric hydroxide, the initiation reaction between cupric ions and hydrazine occurs in solution. 相似文献
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K. Takemoto T. Takata Y. Inaki 《Journal of polymer science. Part A, Polymer chemistry》1972,10(4):1061-1068
Polymerization of methyl methacrylate and other vinyl monomers was studied in the presence of oligoamide (?-aminocaproic acid, its dimer, trimer, tetramer, and pentamer) and cupric ion in aqueous media. The polymerization was found to be of free-radical character and selective for the type of vinyl monomer. Carbon tetrachloride can accelerate the polymerization. The initiation mechanism of the polymerization is discussed. Spectroscopic measurements were indicative of formation of 1:1 complex between oligoamides and cupric ion in aqueous NaClO4 solution. Some chemical and physical properties of the resulting polymers were measured. 相似文献