单官能团单体C存在下A_2-B_2型缩聚产物的分子量分布

分别以概率统计方法和Monte Carlo模拟获得了单官能团单体C存在下A_2-B_2型线型缩聚产物的分子量分布。Monte Carlo方法与统计计算得出一致的结果,表明建立的Monte Carlo模型是合理的。研究了单官能团单体C的反应活性对缩聚产物分子量分布的影响,对反应体系中存在的各种不同的分子类型的消长情况分别进行了动态模拟。     

线型缩聚聚合度和体型缩聚凝胶点公式中反应程度p的物理意义剖析

反应程度p影响线型缩聚聚合度以及体型缩聚凝胶点,因此缩聚反应中涉及到反应程度p的计算公式特别多。因缩聚反应是A和B两个官能团之间的反应,聚合体系中有A官能团的反应程度p_A,B官能团的反应程度p_B,以及体系总反应程度p_S三种不同物理意义的反应程度。本文从公式推导过程出发,明确和比较了线型缩聚聚合度求算和体型缩聚凝胶点预测5个常用公式中涉及到的反应程度p的物理意义。通过对教材中两个练习题的改动,主动暴露学生薄弱知识点,有助于加深学生对反应程度的理解。     

基于格子链的缩聚反应的动态Monte Carlo模拟

采用描述自回避格子链的键长涨落模型, 以动态Monte Carlo方法对AB型单体的线型缩聚反应动力学过程进行了模拟. 通过该方法可以得到反应过程中链的瞬时构象, 还可以得到反应程度、聚合度、分子量分布及其随时间的演化. 模拟得到了合理的结果, 同时验证了无规线团尺寸与平均链长的标度关系, 表明该方法用于研究逐步聚合反应过程是可行的, 并且与一般的研究聚合反应的Monte Carlo方法相比, 还能够同时得到构象等空间信息. 还比较了不同大小的模拟体系所得到的分子量和多分散系数的异同, 讨论了有限元胞效应.     

ABg型单体缩聚反应的动力学分析

研究了AB_g型单体缩聚反应的动力学,导出了分子量分布函数以及数均和重均分子量.一些结果与Flory用统计方法得到的一致.数值计算结果表明,单体上B官能团越多,反应所得的超支化聚合物的分子量分布越宽;多分散性随着A基团转化率的增加而增加,且当反应接近完成时迅速增加,这个结论与Turner等的实验数据定性地一致.     

关于统计方法处理分子量分布问题的探讨

用统计方法研究高聚物分子量的分布,首先是由Flory提出的。在考察了Flory对缩聚反应分子量分布的统计理论以后,本文作者提出新的概念,用不同的统计方法,简化了对AA,BB型缩聚分子量分布的推导。为了便于说明,首先提出作者对AB型缩聚分子量     

缩聚平衡常数与聚合度

根据官能团等活性理论,推导出封闭体系和敞开体系中,缩聚平衡常数、数均聚合度及原料配比数三者之间的关系式。 1.封闭体系聚合反应在密闭容器中进行,反应过程中无物质损失。设有反应     

缩聚反应中的一个基本关系式

在缩聚反应中,缩聚物的分子量与体系的组成及官能团的反应程度存在一定的依赖关系.这种关系的表达式目前很多,但没有一个通用公式,一般均随反应条件的变化而变化.本文介绍一种在缩聚反应中能通用的基本关系式. 1.公式的导出设一聚合体系,有i种单体组成,N_i、f_i分别代表i单体的初始摩尔数及官能度.N_j、f_j分别代表官能团摩尔总数较少的j单体的初始摩尔数及官能度,P代表该官能团的反应程度.若官能团等摩尔混合,N_j、f_j、P分别代表体系中某一种官能团的单体摩尔数、官能度及反     

从反应步数推导缩聚反应聚合度计算公式

聚合度计算是缩聚反应学习的重要内容之一.本文从聚合度的定义出发,根据反应步数与聚合物分子数之间的关系,简易地推导了线型缩聚2-2型单体体系a-A-a+b-B-6、2-2+1型单体体系a-A-a+b-B-b+C-b以及2+1型单体体系a-A-b+C-6达到一定反应程度时统一形式的数均聚合度计算公式:n=(1+r)/(1+...     

AB分批投入的AB,B型缩聚产物的分子量分布

本文用统计方法和动力学方法同时获得了AB单体分批投入的AB,B线型缩聚产物的分子量分布函数。所得的分子量分布远比Flory分布窄。计算结果与Monte Carlo模拟的结果完全相符合。     

在四官能团引发剂存在下的自缩合乙烯基聚合反应制备丙烯酸酯类超支化共聚物

超支化聚合物具有特殊的结构和性能 ,可通过一步法聚合直接制得 ,具有大规模工业应用前景 .近年来 ,超支化聚合物的研究已成为高分子科学的热门课题之一[1～ 3 ] .超支化聚合物的一个主要缺点是它的分子量分布比较宽 .Ｍ櫣ｌｌｅｒ[4] 等通过理论计算指出 ,在聚合体系中加入ｆ个功能基团的分子Ｂｆ[对自缩合乙烯基聚合反应 (ＳＣＶＰ) ,Ｂｆ为ｆ个引发基的引发剂 ;对ＡＢｘ 型单体的缩聚反应 ,为有ｆ个Ｂ官能团的分子 ],可以降低超支化聚合物的分子量分布 ,这一结果已被实验证实[5～ 7] .我们用ＭｏｎｔｅＣａｒｌｏ方法模拟了在多官能团引…     

Distributions in nonself-condensing polycondensations: A kinetic approach

The size distributions of a number of different polycondensations with nonself-condensing monomers were calculated by a kinetic method. The results of linear polycondensations with and without reversibility or stoichiometry and of multifunctional polycondensations are exactly the same as those obtained by Flory with probability methods and do not differ, when comparable, from the size distributions produced by the polycondensation of self-condensing monomers. Size distributions were also obtained for reactions in which the order of reaction changes with conditions or during reaction. These results clearly show that a Flory distribution is obtained as long as the principle of equal reactivity applies at any given instant, although this reactivity may vary in the course of the reaction.     

SYNTHESIS OF MACROPOROUS TERPOLYMERS OF TRIALLYL ISOCYANURATE，DIVINYLBENZENE AND VINYL ACETATE

The reactivity ratios of the trinary system of triallyl isocyanurate,divinylbenzene and vinyl acetate wrere calculated from the Q and e values determined by other investigators.According to these ratios,the terpolymerization of these monomers was predicted possible and the polymerization was carried out by suspension polymerization with toluene and gasoline as extenders,forming spherical macroporous terpolymers.The influences of the amount of the extenders and the crosslinking degree on the pore propertities were studied.The result showed that under adequate reaction conditions,this polymerization system could produce macroporous copolymers with very high surface area(>1000m^2/g) which have never been obtained in other polymerization system using silimar polymerization technique.This was most probably caused by the formation of some linear or branched poly(vinyl acetate) during the polymerization process because of the poor copolymerizing ability of vinyl acetate.This linear or branched polymer acted as an extender and formed a trinary pore porducing reagent with toluene and gasoline.     

“One-pot” synthesis of poly(amide-imide)s derived from trimellitic acid monoesters and multiring aromatic diamines

Aromatic processable poly(amide-imide)s have been prepared according to the Yamazaki and Higashi phosphorylation reaction from flexible aromatic diamines and a mixture of isomeric 1,2,4-benzenetricarboxylic acid monoethylesters following a novel “one-pot” procedure. The polymerization was performed in 1-methyl-2-pyrrolidone/LiCl solutions using triphenylphosphite and pyridine as condensing agents to form amide bonds. Cyclization of the intermediate poly(amide-amic ethylester) occurred by eliminating ethanol under the polymerization conditions used, thus leading to the formation of imide rings. The influence of several parameters which regulate the degree of polymerization and the formation of the imide rings, such as reaction temperature, triphenylphosphite/monomers molar ratio, and pyridine concentration was carefully investigated. In particular, the catalytic activity of pyridine in the imidization reaction has been demonstrated. ¹³C-NMR spectroscopy has been used to show the absence of constitutional regularity in the prepared PAIs thus indicating equal reactivity toward polycondensation of the two different carboxyl groups of the 1,2,4-benzenetricarboxylic acid monoethylesters. © 1996 John Wiley & Sons, Inc.     

Self-Reguiating Poiycondensations. II. A Study of the Order Present in Polyamide-Hydrazides Derived from Terephthaloyl Chloride and p-Aminobenzhydrazide

The problem of chemical order of polyamide-hydrazides prepared from terephthaloyl chloride with an unsymmetrical monomer, p-aminobenzhydrazide, is discussed. An NMR method for identifying the molecular structure of species formed in the early stages of poly condensation has enabled the course of a polymerization to be followed during this time and the final degree of order to be predicted qualitatively. These studies have provided a demonstration that the structure of these polymers can be controlled to a significant degree by appropriate variations in experimental conditions. But even under the most adverse conditions usually employed, poly amide-hydrazides are found to be at least “partially ordered” copolymers. The techniques developed for this study may find application in the study of other polymer forming reactions with monomers having two functional groups with dissimilar reactivities.     

Mechanistic and Synthetic Aspects of Atom Transfer Radical Polymerization

Abstract

Mechanistic and synthetic aspects of atom transfer radical polymerization (ATRP) are reviewed. This controlled/“living” system polymerizes many monomers including styrenes, (meth)acrylates, acrylonitrile and dienes. The halogen end groups can be converted to other functional groups such as amines and azides. In addition to producing well-defined linear homopolymers, statistical copolymers, block copolymers, and gradient copolymers, ATRP can be used to synthesize graft and hyperbranched copolymers through copolymerization with functionalized monomers. Selection of appropriate conditions for ATRP depends on targeted molecular weight and degree of polymer chain end-functionality and includes considering the monomer(s) to be polymerized, initiator structure/reactivity, amount of catalyst/deactivator used, halogen end-group used, and temperature.     

Sol-gel polycondensation of methyltrimethoxysilane in ethanol studied by <Superscript>29</Superscript>Si NMR spectroscopy using a two-step acid/base procedure

Sol-gel polymerization of methyltrimethoxysilane (MTMS) in ethanol using a two-step acid/base catalyzed procedure (B2) is followed by ²⁹Si NMR spectroscopy. Analysis of the structural evolution of the B2 system shows that esterification of monomeric and end silicon species is rate-limited while that of linear and cyclic species is able to reach pseudoequilibrium in the second basic step. Condensation reactivity is reduced with increasing network connectivity, however, to a much less degree under B2 conditions than MTMS polymerization under acidic conditions. Steric effects as well as many other factors are attributed to this trend. The concentration of cyclic and polycyclic species of the B2 system is nearly 3 times lower compared to the acid-catalyzed system. The empirical degree of condensation at the gel point is determined to be 0.88. The effects of cyclization and phase separation on MTMS gelation are discussed for both B2 and acid-catalyzed systems. Based on these results it is believed that MTMS-based gels form for B2 and not acid-catalyzed conditions due to reduced cyclization, rapid hydrolysis and condensation, effective use of functional groups, and effective contribution of branched and polycyclic species as crosslinking points to connect polymeric chains in the B2 system.     

Bulk atom transfer radical polymerization of allyl methacrylate

A detailed investigation of the polymerization of allyl methacrylate, a typical unsymmetrical divinyl compound containing two types of vinyl groups, methacryloyl and allyl, with quite different reactivities, was performed with atom transfer radical polymerization (ATRP). Homopolymerizations were carried out in bulk, with ethyl‐2‐bromoisobutyrate as the initiator and with copper halide (CuX, where X is Cl or Br) with N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalyst system. Kinetic studies demonstrated that during the early stages of the polymerization, the ATRP process proceeded in a living manner with a low and constant radical concentration. However, as the reaction continued, the increased diffusion resistance restricted the mobility of the catalyst system and interrupted the equilibrium between the growing radicals and dormant species. The obtained poly(allyl methacrylate)s (PAMAs) were characterized with Fourier transform infrared, ¹H NMR, and size exclusion chromatography techniques. The dependence of both the gel point conversion and molecular characteristics of the PAMA prepolymers on different experimental parameters, such as the initiator concentration, polymerization temperature, and type of halide used as the catalyst, was analyzed. These real gel points were compared with the ones calculated according to Gordon's equation under the tentative assumption of equal reactivity for the two types of vinyl groups. Moreover, the microstructure of the prepolymers was the same as that exhibited by those homopolymers prepared by conventional free‐radical polymerization; the fraction of syndiotactic arrangements increased as the reaction temperature was lowered. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2395–2406, 2005     

Synthesis and cationic photopolymerization of epoxy‐functional siloxane monomers and oligomers

A series of difunctional silicon‐containing monomers were prepared with a novel method consisting of the monohydrosilation of an α,ω‐difunctional Si? H‐terminated siloxane with a vinyl‐functional epoxide or oxetane followed by the dehydrodimerization of the resulting Si? H‐functional intermediate. This method used simple, readily available starting materials and could be conducted as a streamlined one‐pot, two‐step synthesis. This novel method was also applied to the synthesis of several epoxy–silicone oligomers. The reactivities of these new monomers and oligomers were examined with Fourier transform real‐time infrared spectroscopy and optical pyrometry. Those monomers containing epoxycyclohexyl groups displayed excellent reactivity in cationic ring‐opening polymerization in the presence of lipophilic onium salt photoinitiators. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3056–3073, 2003     

Monte Carlo simulation on kinetic behavior of one-pot hyperbranched polymerization based on AA*+CB2

Monte Carlo simulation was applied to investigate the kinetic behavior of AA*+CB₂ system. The algorithm consisted of two procedures to simulate the in-situ synthesis of AB₂-like intermediate and the subsequent polymerization, respectively. In order to improve the accuracy of the prediction, the mobility distinction between different scale molecules in polymerization was taken into account by relating the reaction rate constants to the collision possibility of each pair of species. The feed ratio of initial monomers and the activity difference between the two functional groups within AA* were studied systematically to catch the essential features of the reaction. Simulation results have revealed that the achievable maximum conversion primarily depends on the extent of the reactivity difference between A and A*-groups, and it is suggested that A*-group should be at least 10 times more active than A-group to achieve high number-average degree of polymerization.     

Synthesis and characterization of novel optically active poly(amide-imide)s and poly(ester-imide)s containing calix[4]arene and amino acid units with binding ability towards alkali metal and toxic heavy metal cations

<正>A novel calix[4]arene derivative 2 with amino functional groups at the lower rim was first prepared via introduction of nitro functional groups and amination of the dinitro derivative of calix[4]arene.The optically active monomers were synthesized by dehydration of L-leucine(and L-isoleucine) and 3,3',4,4'-benzophenonetetracarboxylic- 3,3',4,4'-dianhydride(3) followed by reaction with thionyl chloride to form 5a and 5b.Two methods,polymerization under microwave irradiation and solution polymerization in CH_2Cl_2/TEA,were then employed to carry out the condensation polymerization of 2 with the optically active monomers 5a and 5b,respectively.The polymerization conditions affected the kind of resulting polymers,poly(amide-imide)s(PAIs) 6a and 6b and poly(ester-imide)s(PEIs) 6a' and 6b' were obtained selectively in good yields and moderate inherent viscosities.Sorption-extraction experiments were carried out using cram picrate extraction method and verified good binding ability of the resulting calixarene-based polymers towards silver,alkali metal and toxic heavy metal cations.Also thermogravimetric analysis indicated that the resulting PAIs and PEIs were thermally stable.