新型螺环单体的合成和自由基聚合反应的研究

新型螺环单体的合成和自由基聚合反应的研究王宏鲁剑涛冯品珍（中国科学技术大学研究生院化学部北京１０００３９）关键词自由基聚合，新单体合成，螺环单体，自由基共聚虽然离子型开环聚合早已为人熟知，但是自由基开环聚合反应的研究和应用开发还刚刚起步．...     

等离子体聚合膜的电学性质研究——Ⅱ.腈类单体结构的影响

等离子体聚合膜多为具有高电阻的绝缘体。但是,近年来的研究结果表明,选择合适的单体及采取一些措施,可使等离子体聚合膜从绝缘体至半导体乃至导体的宽范围变化。本文将一些具有不同化学结构的腈类单体进行了等离子体聚合,研究了单体化学结构对所得聚合膜结构及电学性质的影响。聚合方法等同前报。     

大分子单体及其规整接枝共聚物

论述了通过活性阴离子聚合、活性阳离子聚合、基团转移聚合、自由基聚合、缩聚等途径合成各种大分子单体,论讨了大分子单体的表征,并结合自己的工作综合介绍近年来大分子单体共聚的进展及其规整接枝共聚物的纯化和特性。     

大分子单体的制备方法

最常见的大分子单体是末端含碳—碳双键的烯类大分子单体，除此以外还有可开环聚合、可氧化偶联和可开环易位聚合的大分子单体等。本文介绍了大分子单体常用的制备方法。     

GC—MS方法测定等离子体引发丙烯酸酯聚合引发活性种

在等离子体引发的液态丙烯酸酯类单体聚合体系中加入大量链转移剂乙硫醇,得到了端基带有引发活性种的低聚物,利用气相色谱-质谱的多离子检测手段,测定了活性种的结构,结果表明:引发活性种是单体在等离子体区裂解生成的酯基碎片[-C—O—R].进而解释了丙烯酸酯类单体可以由等离子体引发聚合,而苯乙烯不能引发聚合的问题.     

聚合色素的研究：（Ⅴ）PPP—MO在偶氮型可聚合色素单体中的应用

应用自洽场分子轨道理论对１２个可聚合色素单体的λｍａｘ进行了计算，并将其与实测值进行了比较，二者拟合程度较好。关于吡啶酮类色素的ＰＰＰ－ＭＯ的计算结果，理论上证明了吡啶酮型色素单体是以崇体结构存在。文中的参数选取及计算结果为今后偶氮型聚合色单体的分子设计奠定了基础。     

全息用光致聚合物中双单体组分对材料性能的影响

本文研究了薄膜型光致聚合物材料中双单体(2-苯氧基乙基丙烯酸酯和N-乙烯基咔唑)的不同配比对材料聚合效率的影响.用红外光谱测定了双组分单体在固体薄膜中光反应条件下的竟聚率,分析了双组分单体在全息记录过程中的聚合情况.针对同一点多角度复用的大容量存储要求,提出了双单体薄膜型光致聚合物的理想模型.初步测定了不同摩尔配比条件下材料的全息存储性能,分析了其中的影响因素.     

活性阴离子聚合及其单体的研究进展

适用于活性阴离子聚合的单体拓展研究是有关活性阴离子聚合的一项重要的研究工作.本文重点介绍了近十年在活性阴离子聚合领域出现的新型单体的结构设计、合成及其聚合过程的研究进展.文中涉及到的新型单体主要包括非(弱)极性类单体、极性单体及其它单体.进一步细分,非(弱)极性类单体分为苯乙烯衍生物类单体和丁二烯衍生物类单体,极性单体中含有丙烯酸酯类单体、丙烯酰胺类单体、氯乙烯以及N-乙烯基咔唑,其它单体包括异氰酸酯类、烯酮类以及杂环类单体.最后本文对上述这些新型单体中的一些单体用于复杂大分子拓扑结构的设计合成情况也作了简要介绍.     

等离子体引发聚合的机理初探

等离子体引发聚合与常规自由基聚合存在许多不同之处。本文从等离子体引发聚合物一些现象,如较强的溶剂效应、极高的单体选择性、主成超高分子量聚合物等方面,系统介绍了等离子体引发聚合的机理研究成果,并提出了自己的看法。     

等离子体挥发性产物引发甲基丙烯酸甲酯聚合反应动力学

本文发现甲基丙烯酸甲酯等离子体挥发性产物能够有效地引发单体聚合,获得超高分子量聚合物。其聚合过程属于瞬时引发、向单体链转移的活性自由基聚合机理。     

A STUDY OF THE POLYMERIZATION MECHANISM OF ACETONITRILE IN GLOW DISCHARGE

Plasma polymerization of acetonitrile was carried out by a capacitively coupled RF plasma apparatus with external electrodes under some different reaction conditions such as discharge power. By investigating the informations provided by the polymer deposition regularities, IR spectra and elementary analysis results, the polymerization mechanism of acetonitrile in glow discharge have been investigated. The results show that acetonitrile polymerized in glow discharge mainly through hydrogen detachment for initiation at lower energy levels and the role that opening C≡N triple bond played in polymerization became more important at higher energy levels.     

Glow Discharge Induced Graft Polymerization of Nonvolatile Monomers on Wool

Nonvolatile monomers were grafted to wool by exposure to rf glow discharge under vacuum. The amount of grafting was limited to an average of 2 to 5% weight uptake. With increasing impregnation the amount of graft decreased, and mostly extractable homopolymers formed. Increasing the intensity of the glow discharge above a certain level is also detrimental because at this point the rate of degradation exceeds the rate of polymerization.     

Copolymerization of toluene with tetrafluoromethane or octafluorocyclobutane by plasma technique

Plasma copolymerization of toluene with tetrafluoromethane or octafluorocyclobutane was carried out in a capacitively coupled tubular reactor with external electrodes. The polymer structure was characterized by means of XPS, IR, and pyrolysis/GC/MS and the condensates of the gases in the plasma reaction chamber were measured by GC–MS. It is observed that the monomers undergo a plasma states polymerization in a glow discharge and only those monomer fragments with sufficient reactivity join the copolymerization. The types of fluorine-containing groups in the polymer structure are related to the chemical structure of the flurocarbons. The fluorine content depends upon the discharge power, the system pressure, and the fraction of fluorocarbons in the monomers     

Distribution of polymer deposition in plasma polymerization. III. Effect of discharge power

Distribution of polymer deposition in an inductively coupled rf discharge system is studied as a function of level of discharge power with acetylene and styrene as monomers. When a fixed flow rate is used, the discharge power has a relatively small effect on the pattern of distribution of polymer deposition as long as values of W/FM, where W is discharge wattage, F is flow rate, and M is molecular weight of monomer, are maintained above a critical level to maintain full glow in the reaction tube. It has been shown that plasma polymerization of two monomers which have different molecular weights can be compared in a fair manner by selecting conditions to yield similar value of W/FM.     

Comparisons of glow-discharge polymerizations among tetramethylsilane,dimethyldimethoxysilane, and tetramethoxysilane

Glow-discharge polymerizations among tetramethylsilane, dimethyldimethoxysilane, and tetramethoxysilane were compared by elemental analyses and infrared spectroscopy. The elemental composition of the polymers prepared from the three monomers depended strongly on the operational conditions necessary to sustain a glow discharge, i.e., the W/FM parameter, where W is the rf power, F is the flow rate of the monomer, and M is the molecular weight of the monomer. Methoxy groups were more susceptible to glow discharge than methyl groups. Differences in chemical structure among these monomers appeared in the polymer structures formed when the glow-discharge polymerization was carried out at a low value of the W/FM parameter, while the differences disappeared at high values of the W/FM parameter, for analogous polymers. Substitution with methoxy groups was favorable for the formation of polymers of low carbon content only when the glow-discharge polymerization was performed at low values of W/FM.     

Glow characterization in direct current plasma polymerization of trimethylsilane

Plasma polymerization of trimethylsilane (TMS) was carried out in a direct current (dc) glow discharge and was investigated by optical photography and plasma diagnostic techniques including optical emission spectroscopy and residual gas analysis. The nature of the glow formed in TMS discharge, which deposited plasma polymers, was significantly different from that of a simple gas such as Ar. In an Ar discharge, the dominant glow was the well known negative glow, which developed at a distinctive distance from the cathode, whereas the cathode surface remained in the dark space. In strong contrast to this situation, in TMS dc discharge the dominant or primary glow was the cathode glow, which appeared at the cathode surface. At a similar location where the Ar negative glow appeared, a very feeble glow as a secondary glow was also observed in TMS glow discharge. The deposition results and plasma diagnosis data evidently indicated that in TMS glow discharge, the cathode glow resulted from the low‐energy electron‐impact dissociation of TMS molecules that creates polymerizable species, but the negative glow was related to nonpolymerizable species such as hydrogen atoms and molecules. In this article, the cathode glow formed in glow discharges of organic compounds was designated as the dissociation glow according to its underlying plasma reactions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1042–1052, 2004     

甲苯二异氰酸酯的低温等离子聚合

辉光放电等离子聚合技术已逐步得到发展和应用,Harada报导,TDI的等离子聚合薄膜具有极为优良的耐磨性能。本工作报道不同进气和电感位置对TDI等离子聚合的影响,并结合红外光谱和元素分析对聚合产物进行了结构分析。     

Wachstum dünner Fluorkohlenstoffschichten auf der Anode einer Glühkathodenentladung

The polymerization of tetrafluorethylene on the anode of a hot glow discharge has been investigated. Rates of polymer deposition have been measured as a function of monomer pressure, discharge current density, and electrode surface temperature. A mechanism of polymer formation is suggested. The results are different from those obtained by polymerization of the same monomer in a glow discharge. It is concluded that negative ions have a great influence on mechanism of polymer formation. Additionally, monomer molecules adsorbed at the electrode are polymerized by electron bombardment.     

丙醛的等离子体聚合以及聚合物的结构与性质初探

应用外部电容耦合式等离子体聚合方法,制得了丙醛聚合物,研究了不同的等离子体条件对丙醛的聚合行为的影响。通过元素分析、红外光谱分析、色谱-质谱联合分析、X-射线衍射、润湿性测定等手段研完发现,聚合物为无定形交联结构,表面能为41—45达因/厘米。     

A Mechanisms and Kinetics Study of Polymeric Thin-Film Deposition in Glow Discharge

Polymeric thin-film deposition in a capacitively coupled rf glow discharge of styrene has been investigated. A kinetic scheme for the polymerization was proposed in which initiation of monomers by electron impact was followed by propagation and termination as in conventional polymerization, the initiation rate constant being a function of electron temperature alone. Four mechanism models were examined, depending on where each reaction step takes place: in the gas phase or on the substrate. Free-radical polymerization was assumed. Experiments were carried out at pressures ranging from 0.25 to 1.05 Torr and at voltages and currents that yielded cold and stable discharges. Substrate temperature was controlled. Deposition rate was determined by weighing. A regression program was used in addition to experimental tests in which substrate temperature was varied. The best approximation to the plasma polymer deposition process was found to be the following model: monomers are activated in the gas phase by electron bombardment and subsequently diffuse to the substrate where they propagate and terminate, adsorption of monomers on the substrate playing an important role. A rate expression relating polymer film deposition rate to the experimental variables is presented.