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含聚二甲基硅氧烷侧链的丙烯酸酯共聚物的研究 总被引:5,自引:0,他引:5
采用含活性基团的聚二甲基硅氧烷与丙烯酸酯进行自由基共聚合,合成了自聚二甲基硅氧烷侧链的丙烯酸酯共聚物。采用IR,^1H-NMR,GPC等分析方法对共聚物结构和组成进行了表征。通过接触角和X-射线光电子能谱对共聚物的表面性能和表面组成进行了研究,并通过粘接性能和破坏面形貌对共聚物与金属铝材和加成型硅橡胶的粘接性进行了探讨。 相似文献
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四氟乙烯/偏氟乙烯乳液共聚反应的竞聚率测定 总被引:3,自引:0,他引:3
用亨利定律关联了四氟乙烯 (TFE) /偏氟乙烯 (VDF)乳液共聚合体系中的单体气相分压与其对应液相浓度间的关系 ,推导了用气相摩尔分数表示的共聚物组成方程式 .通过气相色谱和19F NMR分别测定了共聚反应前后气相单体组成和共聚物组成 ,用非线性回归法 (RREVM )计算TFE/VDF乳液共聚合反应表观竞聚率分别为γTFE=0 35和γVDF=0 6 3 .将实测的表观竞聚率代入共聚物组成方程计算共聚物组成与由19F NMR测定的结果一致 ,为进一步的工业放大试验提供科学依据 相似文献
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丙烯酸β-羟丙酯与苯乙烯共聚合的研究 总被引:1,自引:0,他引:1
<正> 丙烯酸β-羟丙酯(HPA) 是一种具有多种反应功能的丙烯酸酯类单体,由它制得的大分子同时带有羰基、酯基和羟基,因而可用它制备特定功能的大分子如耐火树脂、涂料、油田助剂及水处理剂等,国内外对HPA的共聚合活性报道很少,CHOW曾研究过HPA与苯乙烯(St)的共聚合,并用Mayo-Lewis方程法计算出它们的竞聚率。本文研究了HPA与St在甲苯溶液中的自由基共聚合,用Mayo-Lewis方程法、FR法、YBR法及K-T法四种方法分别计算出St-HPA共聚合出竞聚率r_1、r_2及HPA的Q、e值,作出了共聚物组成曲线,并由此计算出St-HPA共聚物的平均序列长度及序列长度分布。 相似文献
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具有预期结构的苯乙烯与丙烯酸丁酯接枝共聚物的合成与表征 总被引:10,自引:0,他引:10
通过苯乙烯 (St)与 4 对氯甲基苯乙烯 (CMS)进行氮氧稳定自由基共聚合反应 ,合成了二元共聚物P(St co CMS) ,并以此共聚物引发丙烯酸丁酯进行原子转移自由基聚合 ,成功地合成了结构明晰的以聚苯乙烯为主链、聚丙烯酸丁酯为支链的接枝共聚物 ,研究了共聚合反应动力学 .P(St co CMS)和接枝共聚物的结构通过1 H NMR得到确认 ,并表征了接枝共聚物平均侧链数目和平均侧链长度 相似文献
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两亲性丙烯酸酯共聚物的聚合研究 总被引:1,自引:0,他引:1
利用过氧化苯甲酰为引发剂探讨了甲基丙烯酸β-羟乙酯和丙烯酸长链烷基酯的自由基共聚合。重点讨论了合成条件如溶剂、沉淀剂、引发剂用量、单体配比、反应时间等对共聚反应的影响以及各种聚合条件对该共聚物的组成、结构和性能的影响。并用IR,GPC,^13CNMR等手段对共聚物进行了表征。 相似文献
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采用Matlab GUI工具,以单体组成为中间变量,依据共聚物组成方程及单体组成与转化率关系式,开发出一款用于绘制二元共聚合反应共聚物组成与单体转化率关系曲线的图形用户程序。通过对苯乙烯与甲基丙烯酸甲酯、丙烯腈与醋酸乙烯酯等共聚反应的应用表明:该图形用户程序界面友好,交互性强,适用性广,计算便捷,解决了绘制过程中共聚物组成与单体转化率关系式过于复杂而无法找到直接关系的困难,为预测不同竞聚率、不同投料比时共聚物组成与转化率的变化规律,控制共聚物组成,选择控制方法,验证实验,指导生产提供理论依据。 相似文献
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Shigeru Yabumoto Kiyoshi Ishii Koichiro Arita 《Journal of polymer science. Part A, Polymer chemistry》1969,7(7):1577-1588
Copolymerization of acrylonitrile with styrene spontaneously occurred on addition of zinc chloride without addition of any other radical initiator. The composition of the copolymer approached that of strictly alternating copolymer as zinc chloride added to the copolymerization system increased. The significance of the apparent monomer reactivity ratios of this copolymerization system was studied from a kinetic point of view, and it was shown that the monomer sequence distribution is indicated by the apparent monomer reactivity ratios. Further, equations which represent the relation between the apparent monomer reactivity ratios and Q,e values at a given salt concentration were derived. These equations reasonably accounted for the decrease of the apparent monomer reactivity ratios of the copolymerization of acrylonitrile with styrene in the presence of zinc chloride and the behavior of the other acrylonitrile copolymerization systems in the presence of zinc chloride. The initiation step of the spontaneous radical copolymerization of acrylonitrile with styrene in the presence of zinc chloride was explained by a cross-initiation mechanism. 相似文献
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The present report introduces a simple and novel strategy for producing an ordered porous copolymer film material by using its side reaction product, homopolymer, in free radical copolymerization as template. In general, homopolymers are side products in free radical copolymerization, but herein we try to make good use of them (e.g. PMMA). In this paper, we optimized the graft copolymerization of gelatin and MMA via traditional free radical initiation. PMMA is a side product and act as a template to create ordered nanoporous structure. Furthermore, this approach has been successfully extended to chitosan-g-PMMA and gelatin-g-PS systems. The present novel approach provides a new opportunity by using the side product in copolymerization to fabricate ordered porous structure film materials. The porous gelatin-g-PMMA film is especially suitable as surfaces for cell growth due to its good biocompatibility, mechanical properties and multilayer structure. 相似文献
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针对自由基聚合歧化终止和偶合终止两类机理生成的线型高聚物,应用统计物理的基本原理,对其分子量分布重新进行了理论推导,其方法简洁清晰,无须任何附加假定,导出FlorySchulz分布.结果有助于从另一方面理解FlorySchulz分布的物理学基础. 相似文献
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<正> 偶联接枝反应,例如阴离子活性聚合物与聚对卤代甲基苯乙烯的接枝反应,以及阳离子活性聚四氢呋喃与聚乙烯基吡啶的接枝反应,近年常见报道。本工作对上述反应进行动力学分析,求得了分子量分布函数、平均分子量、接枝分布、接枝度和接枝率等公式。然后,又将所得公式作适当修正,使之进一步适用于其它类型的接枝反应。 相似文献
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The combination of MALDI-ToF-MS and pulsed laser polymerization has been used to study the propagation rate coefficients for the copolymer system styrene-methyl methacrylate. For the first time, complete information regarding mode of termination, reactivity of photoinitiator-derived radicals, copolymer molecular mass, chemical composition, and copolymerization rates is obtained interrelated. The polymerizations were carried out in bulk with varying styrene concentrations at a temperature of 15.2 degrees C by an excimer pulsed laser with varying frequencies. Both chemical composition distributions and molecular weight distributions were determined by MALDI-ToF-MS. The data were fitted to the implicit penultimate unit model and have resulted in new point estimates of the monomer and radical reactivity ratios for the copolymer system styrene-methyl methacrylate: r(St) = 0.517, r(MMA) = 0.420, s(St) = 0.296, s(MMA) = 0.262. Comparison between Monte Carlo simulations and the obtained results further confirmed the very successful combination of pulsed laser copolymerization experiments with MALDI-ToF-MS. The obtained results are believed to be the most accurate and complete set of copolymerization parameters to date. 相似文献
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E. Merz T. Alfrey G. Goldfinger 《Journal of polymer science. Part A, Polymer chemistry》1996,34(1):5-12
The Flory-Wall expressions for the fraction of substituents remaining of a vinyl copolymer, when substituents are removed of random from adjacent 1.3 positions, are extended to the case of nonrandam copolymerization. A copolymer composition equation is desired for the case in which the type of monomer preceding the active free radical chain and affects the propagation reaction. The distribution of lengths of sequences in copolymers is discussed. 相似文献
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Abstract The penultimate effect in the radical copolymerization of vinyl chloride (C) and vinylidene chloride (V), described in a previous paper, is interpreted in terms of head-to-head addition of a V molecule to a C-ended radical. The later is estimated from NMR analysis of the copolymer. It occurs about three times faster than the corresponding head-to-tail addition. It is shown that both the penultimate effect model and the “head-to-head assumption” lead to the same values for either the copolymer composition or several functions of the sequence distribution. It is further suggested that the head-to-head addition is possible owing to the propagation-depropagation equilibrium for the V-ended radical and to the very high reactivity of the tail radical produced. 相似文献