丁二烯与丙烯腈共低聚反应中共聚物组成的控制

在二元共聚反应中,为了制备具有均匀组成的共聚物,对于分批聚合,在反应过程中须补加消耗较快的单体以保持单体的浓度比为常数。本工作提出了为控制共聚物组成在反应过程中补加单体的计算方法,它不仅适用于丁二烯与丙烯腈的共低聚反应,也适合于其它二元共聚反应。用这种方法制备了具有均匀组成的丁二烯与丙烯腈共低聚物。     

基于Matlab的二元共聚物组成与转化率关系曲线的绘制及应用

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。     

二元共聚物的分子量与链段分布(Ⅰ)——活性共聚体系

本文用几率与动力学相结合的方法处理二元共聚反应,得到了能够同时表征活性二元共聚物分子量分布与任意长度链段分布的统一分布函数.利用流体力学体积加和性得到了活性二元共聚物的理论GPC谱图计算公式.     

偏氟乙烯和四氟乙烯共聚反应

本文用过氧化二碳酸二异丙酯为引发剂,丙酮为分子量调节剂,对偏氟乙烯-四氟乙烯共聚反应进行了研究,并制得了不同组成,不同分子量的样品,用色谱分析方法分析在共聚反应过程中单体组成的变化,方便地确定了偏氟乙烯-四氟乙烯共聚反应中的“恒比”组成范围,并能控制共聚物组成的均匀性,丙酮有效地调节了共聚物的分子量,对共聚物的性能测定表明,它们有很好的机械性能和热稳定性,在“恒比”组成范围的共聚物的热电系数有一个极大值,它对应于熔点的极小值。     

二元共聚反应的蒙特卡罗模拟(Ⅰ)——末端模型与共聚物的序列分布

本文根据蒙特卡罗方法的原理,编写了微机用BASIC程序,供模拟末端模型二元共聚反应使用。形成的共聚物分子链中两单元的各种段的数目,是跟模拟一道统计的。用该程序获得的结果,与用一级马尔可夫链算出者极其接近,该程序可用来研究由末端模型形成的二元共聚物的序列分布。     

二元共聚物宏、微观组成讲授方法的一种新尝试

对二元共聚物宏、微观组成的讲授方法进行了一种新的尝试，并提出了二元共聚物组成与相关参数间关系的图解方法。     

不伴随解聚的二元共聚反应的计算机模拟

用计算机模拟化学反应是一项饶有兴趣的研究课题。本文主要讨论不伴随解聚的二元共聚反应的计算机模拟问题。通过模拟,希望能获得如下两方面信息:(1)给出任意的某一原料单体组成下所对应的共聚体的组成。(2)给出共聚体中单体单元的序列分布。我们知道,高分子具有多分散性的特点,对共聚体而言,除分子量的多分散性以外,还须研究共聚物组成     

端羟基丁二烯/丙烯腈共低聚物的合成及其力学性能I.控制组成的计算方法

通过分批聚合，制备具有均匀组成的共聚物。提出了为控制共聚物组成在反应过程中补加单体的计算方法。它不仅适用于丁二烯与丙烯腈的共低聚反应，也适用于其它二元共低聚反应     

BF_3,络合的丙烯酸乙酯与丙烯的共聚机理

BF_3络合的丙烯酸乙酯(EA)与丙烯(P)在25℃进行自由基共聚。聚合速率和引发剂浓度的平方根成直线关系。链转移剂CCl_4可显著影响共聚物的[η];溶剂的介电常数越小,共聚反应速率越大;两种单体浓度相等时共聚反应速率最大。~1H-NMR和 _13C-NMR表明,当[EA·BF_3]/[EA·BF_3]+[P]>O.5时所得共聚物为富于EA的无规共聚物。实验数据表明,共聚反应按三元络合物与二元络合物的无规共聚机理进行,当[EA·BF_3]/[EA·BF_3]+[P]<0.5时,得到交替共聚物,共聚反应按三元络合物均聚机理进行。UV光谱测得了戊烯-1(丙烯的同系物)与EA·BF_3三元络合物的存在,这对三元络合物的均聚机理是有力的证据。     

端羟基丁二烯／丙烯腈共低聚物的合成及其力学性能：Ⅰ.控制？…

通过分批聚合,制备具有均匀组成的共聚物,提出了为控制共聚物组成在反应过程中补加单体的计算方法。它不仅适用于二烯与丙烯腈的共低聚反应,也适用于其它二元共低聚反应。     

端羟基丁二烯丙烯腈共低聚物的合成及其力学性能Ⅱ.均匀组成的液体共聚物的合成

根据共聚物组成的计算方法,合成了组成均匀的端羟基丁二烯与丙烯腈液体共聚物并用ＮＭＲ观察和计算了该液体聚合物的序列分布,测定了力学性能     

Reversible addition–fragmentation transfer (RAFT) copolymerization of methyl methacrylate and styrene in miniemulsion

In the reversible addition–fragmentation transfer (RAFT) copolymerization of two monomers, even with the simple terminal model, there are two kinds of macroradical and two kinds of polymeric RAFT agent with different R groups. Because the structure of the R group could exert a significant influence on the RAFT process, RAFT copolymerization may behave differently from RAFT homopolymerization. The RAFT copolymerization of methyl methacrylate (MMA) and styrene (St) in miniemulsion was investigated. The performance of the RAFT copolymerization of MMA/St in miniemulsion was found to be dependent on the feed monomer compositions. When St is dominant in the feed monomer composition, RAFT copolymerization is well controlled in the whole range of monomer conversion. However, when MMA is dominant, RAFT copolymerization may be, in some cases, out of control in the late stage of copolymerization, and characterized by a fast increase in the polydispersity index (PDI). The RAFT process was found to have little influence on composition evolution during copolymerization. The synthesis of the well‐defined gradient copolymers and poly[St‐b‐(St‐co‐MMA)] block copolymer by RAFT miniemulsion copolymerization was also demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6248–6258, 2004     

全氟甲基乙烯基醚和其它含氟单体乳液共聚合的竞聚率测定

分别通过气相色谱法测定了全氟甲基乙烯基醚 (PMVE)与偏氟乙烯 (VDF)以及PMVE与四氟乙烯(TFE)二元乳液共聚反应中的气相单体组成和共聚物组成 ,然后用非线性回归法 (RREVM )计算得TFE PMVE及VDF PMVE乳液共聚合反应的表观竞聚率分别为γTFE =3 89和γPMVE =0 0 5以及γVDF =1 0 6和γPMVE =0 11.结合已经测定的TFE VDF二元乳液共聚的表观竞聚率 ,计算了由VDF TFE PMVE三元乳液共聚合反应合成的共聚物组成 ,后者与由1 9F NMR实测的共聚物组成吻合     

Grafting copolymerization of styrene and maleic anhydride binary monomer systems induced by UV irradiation

Photografting copolymerization of maleic anhydride (MAH) and styrene (St) onto LDPE film was investigated by using a one-step method, and further thermally induced grafting copolymerization of them was carried out by using a two-step method. Regarding the photografting copolymerization of MAH/St binary monomer system, both conversion percentage (CP) and grafting efficiency (GE) increased with raising the content of MAH in the monomer feed. In addition, the content of MAH in the grafted copolymers also increased with increasing the fraction of MAH in the monomer feed. The formation of LDPE-g-P(MAH-co-St) grafted film was identified by FTIR and ESCA spectroscopy. In the case of grafting copolymerization of MAH/St by the two-step method, grafting copolymerization proceeded slowly compared with the non-grafting copolymerization. The apparent activation energy (E_a) for the non-grafting copolymerization in the solution and the grafting copolymerization on LDPE film was 24 and 82 kJ/mol, respectively, which were noticeably lower than those of MAH/vinyl acetate (MAH/VAC) binary monomer system under the similar grafting conditions. These data of E_a explained why the grafting copolymerization of styrene/MAH took place faster than that of MAH/VAC binary monomer system. The composition of the grafted copolymer chains was largely affected by the composition of the monomer feeds; however, the composition of the non-grafted copolymers nearly remained at 1/1 even in systems with largely different MAH/styrene ratios in monomer feeds. It is indicated that the non-grafting copolymerization proceeded predominantly following alternating copolymerization, but the grafting copolymerization performed random copolymerization.     

Emulsion copolymerization of tribromophenyl maleimide with styrene

Emulsion copolymerization of Tribromophenyl Maleimide (TBPMI) and styrene was conducted by semi-batch and batch processes. The effects of monomer composition and copolymerization method on copolymerization rate, molecular weight and molecular weight distribution, latex particle size and size distribution, glass transition temperature (T_g), thermal stability and mechanical properties were investigated. A kinetic study has shown that the rate of copolymerization in the batch process increased with increasing TBPMI content in the monomer feed. For the semi-batch polymerized samples, molecular weight decreased and molecular weight distribution increased with increasing TBPMI content in the monomer feed. For the batch polymerized samples, molecular weight also decreased but no obvious tendency was observed for the molecular weight distribution when TBPMI content increased. Compared with the batch copolymers, the semi-batch copolymers have a higher molecular weight at the same initial monomer mixture composition. Latex particle size decreased, while particle size distribution slightly increased with increasing TBPMI content in both semi-batch and batch latices. The semi-batch samples exhibit only a single T_g, the value of which increses linearly with increasing TBPMI content. For the batch copolymers, two T_gs were found, reflecting a mixture of styrene-rich and TBPMI-rich copolymer chains. TGA results indicate that the thermal stability of the semi-batch copolymers increased with increasing TBPMI concentration. Young's and flexural moduli increased, while tensile and flexural strengths decreased by increasing the TBPMI content for both the semi-batch and batch specimens. The semi-batch specimens have higher tensile and flexural strenghts than the batch ones.     

Composition equation for matrix copolymerization

A mechanism of matrix copolymerization in which a monomer (or macroradical) is complexed by matrix was considered. For this case a composition equation was formulated. It was shown that in general case reactivity ratios are dependent on the matrix concentration. The influence of the critical length of a complexed radical on the process of copolymerization is also discussed. A series of copolymerizations of methacrylic acid and styrene were carried out using various compositions of initial monomer mixtures. The process was performed in benzene in the presence of poly(ethylene glycol) as a matrix. The copolymerization were carried out at various ratios of the monomer being complexed (methacrylic acid) to the matrix. Compositions of the complexes prepared were determined by the NMR method. Reactivity coefficients for both monomers were found and the results are discussed on the basis of the derived equation.     

Kinetics of copolymerization—X: Investigation of the copolymerizations acrylonitrile with the sodium and ammonium salts of allyl sulphonic acid in dimethyl formamide solution

Sodium and ammonium salt of allyl sulphonic acid have the same characteristics in radical copolymerizations with acrylonitrile in dimethyl formamide solution. In these cases, the copolymer composition equation does not adequately describe the copolymerization process; this is manifested in the fact that the reactivity ratios change with the initial monomer ratio.     

丙烯酸甲酯/4-丙烯酰胺基-2,2,6,6-四甲基哌啶光共聚合体系的竞聚率和序列分布研究

以丙烯酸甲酯(MA,M1)和4-丙烯酰胺基-2,2,6,6-四甲基哌啶(AATP,M2)溶液光共聚合体系为研究对象,采用1H-NMR手段测定了MA/AATP共聚物的组成,用Mayo-Lewis积分法和扩展Kelen-Tüdos方法计算的竞聚率分别为0.88相似文献