Effects of Reaction Conditions on the Structure of Plasma-Polymerized Ethylene

Liquid and solid polymeric products were derived from a low-pressure glow discharge of ethylene. Polymerization pressure, discharge power, and monomer flow rate were systematically varied. Products were analyzed by infrared spectroscopy to determine the concentrations of characteristic functional groups in each. Polymer form, apparent crosslink density, and deposition rate were also reported. Structural variations and the form of the polymerization products can be explained in terms of the prevailing discharge conditions and the deposition rate, both of which are functions of the reactor operating parameters. It was found that the degree of crosslinking in rigid films of plasma polymerized ethylene is in the range of 6 to 16 chain carbons between crosslinks.     

新型镍催化剂催化乙烯聚合的阳离子机理

含氮氧配位原子的镍催化剂是一类新型催化剂.文章以配体为[NH=CH－CH=CH－O]的镍催化剂为模型,用密度泛函方法（DFT）在B3LYP/LANL2MB水平上研究了该类乙烯聚合催化的反应机理.计算结果表明,催化的反应过程中,中心原子镍最先形成带空位的四边形阳离子配合物,乙烯以垂直于催化剂平面的方式占据空位,然后旋转到催化剂平面内以利于插入反应的进行；插入反应发生后,在催化剂中Ni和β-C之间形成一种氢桥键,协助新空位的形成,实现链的增长.     

Surface-Initiated Polymerization on Self-Assembled Monolayers: Effect of Reaction Conditions

Self-assembled monolayers of 4′-nitro-4-mercaptobiphenyl were modified by electron beam irradiation and diazotization to create a surface-bond asymmetric azo initiator for the surface-initiated polymerization (SIP). The effect of different reaction conditions upon the thermally and photochemical initiated SIP was investigated.     

Positional Electronic Effects in Iminopyridine-N-oxide Nickel Catalyzed Ethylene Polymerization

Main observation and conclusionA series of dibenzhydryl-based iminopyridine-N-oxide ligands bearing a range of electron-donating or-withdrawing substituents(OM...     

反应物浓度对硅铝酸盐聚合反应的影响

研究硅铝酸盐聚合反应是探讨沸石分子筛形成机理的关键问题之一,同时对于改善现有沸石晶化导向剂的性能和发现新型沸石晶化导向剂具有指导意义。关于单纯的硅酸及其盐或单纯的铝酸盐的聚合反应研究报道较多,但是对于硅铝酸盐的聚合反应研究报道较少,至于高浓度和高硅铝比条件下硅铝酸盐的聚合反应研究尚未见报道。本文以沸石分子筛液相成核和沸石晶化导向剂为应用背景,研究了高浓度高硅铝比条件下反应物浓度对硅铝酸盐聚合反应的影响。     

Reversible Addition-Fragmentation Chain Transfer Polymerization of Methyl Methacrylate in Microemulsion: The Influence of Reaction Conditions on Polymerization

The reversible addition-fragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) using cetyltrimethylammonium bromide (CTAB) as surfactant and a difunctional RAFT agent S,S′-bis (α, α′-dimethylacetic acid) trithiocarbonate (BDAT) as chain transfer were conducted in microemulsion. The influence of polymerization temperature and concentration of RAFT agent on the polymerization were investigated, respectively. The results showed that the molecular weight of products increased linearly with conversion, the polydispersity indexes remained low value, and the polymerization processes were totally under control with increasing concentration of RAFT agent, the polymerization behavior exhibited living polymerization characters. In addition, the influence of RAFT concentration on the particle size was investigated by TEM. The results indicated that the particles were highly monodispersed and the particle size increased with increasing concentration of RAFT agent.     

环氧乙烷均聚反应机理的理论研究

借助量子化学理论计算方法对环氧乙烷均聚反应历程进行了理论探讨．采用DFT中的B3LYP方法在6-311G^**基组下对环氧乙烷基态和激发态以及亲核试剂和亲电试剂进攻环氧乙烷反应产物进行几何构型全优化,确定了各物种的电子结构、电荷分布和键长等参数．运用前线轨道理论从微观电子结构层次上对环氧乙烷的各种均聚反应机理进行了分析,探讨了阳离子均聚和阴离子均聚机理的合理性．由于受到前线轨道对称性和能级差的限制,环氧乙烷的基态分子不能发生均聚,同样也不能发生自由基均聚;而当环氧乙烷基态分子被亲电试剂或亲核试剂进攻时,可以进一步生成新的亲电或亲核试剂从而引发环氧乙烷均聚．计算结果很好地阐明了实验事实．     

反应介质对N，N－二乙基二硫代氨基甲酸苄酯引发丙烯酰胺聚合反应的影响

反应介质对Ｎ，Ｎ－二乙基二硫代氨基甲酸苄酯引发丙烯酰胺聚合反应的影响杨文君，沈家骢（青岛化工学院橡塑工程研究所，青岛，２６６０４２）（吉林大学化学系）关键词聚丙烯酰胺，溶剂效应，自由基聚合，引发－转移－终止剂近年来，具有结构的有机硫化物以其优良的Ｉｎ...     

反应介质对N,N-二乙基二硫代氨基甲酸苄酯引发丙烯酰胺聚合反应的影响

The effects of reaction medium (alcohol, dioxane, dioxane/alcohol)on the heterogenous polymerization of acrylamide initiated by BDC (benzyl diethyldiothiocarbate)were studied. The results showed that herterogenous polymerization differed from homogeneous solution polymerization initiated by BDCand did not have the character of living radical polymerization. The polarity of reaction medium affected the enolization of acrylamide obviously, and made the yield of polymer and molecular weight different from each other, behaving obvious solvent effects.The UVspectra of products and polymerization of acrylamide initiated by products, show that iniferter functional groups remained in products.     

Plasma Polymerization on Metals

An ellipsometric technique is described for accurately measuring the film thickness of plasma-polymerized polymers on metallic substrates. The index of refraction n and absorption index Kof the plasma polymer film can also be studied by ellipsometry. Films of plasma polystyrene and polyepichlorohydrin were deposited on evaporated aluminum substrates and their thickness and optical constants determined. Plasma polystyrene films from 20 to 1600 Å thick have optical constants n = 1.63 and K =0 independent of film thickness. Plasma polyepichlorohydrin films over the same range of thickness give n ? 1.70 and K? 0.01. By utilizing the ellipsometric method the effect of plasma polymer film thickness on surface energy properties was determined. Advancing contact angle measurements and surface energy analysis detail the polar γSV^P dispersion γSV^Pcontributions to the solid-vapor surface tension γSV = γSV^d + γSV^P Polystyrene and polyepichlorohydrin films on etched aluminum. For thin plasma polystyrene films (600 Å), anomalies in the calculated surface energy are discussed and related to possible surface nonuniformity caused by film growth. Thicker films of plasma polystyrene are shown to have normal surface energy properties as does plasma poly-epichlorohydrin over the entire range of film thickness measured. The adhesive and cohesive properties of plasma polystyrene and polyepichlorohydrin films are discussed as estimated from a lap-shear bond strength study. Etched aluminum coated with various thicknesses of these two polymers and bonded with an epoxy-phenolic adhesive shows a decreasing shear strength with increasing plasma film thickness but begins to level off at ～1600 psi for films >1600 Å thick.     

等离子体聚合法

扼要介绍等离子体聚合的原理、设备和方法,对其应用也作了叙述。     

新型的乙烯聚合催化剂

简要介绍了新型的烯烃聚合催化剂－Ｎｉ（Ⅱ）、Ｐｄ（Ⅱ）、Ｆｅ（Ⅱ）、Ｃｏ（Ⅱ）类后过渡金属催化剂的发展,特点及催化乙烯聚合机理,并就它们的组成结构、聚合条件和配体体积对聚合产物结构,分子量等的影响根据配体不同分类进行了讨论。     

碳酸乙烯酯溶剂中丙烯腈的聚合行为

以碳酸乙烯酯为溶剂,偶氮二异丁腈（AIBN）为引发剂,采用溶液自由基聚合的方法对丙烯腈(AN)均聚合、丙烯腈/衣康酸(AN/IA)二元共聚及丙烯腈/衣康酸/丙烯酸甲酯(AN/IA/MA)三元共聚合进行了研究。 考察了反应温度对丙烯腈均聚合,以及聚合单体浓度对丙烯腈共聚合的影响,在60 ℃合成了相对分子质量高于4.5×105、单体转化率高于85%的丙烯腈均聚物及共聚物。 采用正十二烷基硫醇（DDT）和甲酰基哌啶（FP）作为链转移剂,对AN均聚物、AN/IA及AN/IA/MA共聚物的相对分子质量进行调控,考察了链转移剂浓度对聚合物相对分子质量和单体转化率的影响。 结果表明,w(DDT)为0.25%时（以单体质量计）,聚合物相对分子质量可有效调节到1×105,而单体转化率保持在80%以上。     

等离子体聚合及其聚合物的应用

本文着重综述了烃,含氮、氧的有机化合物,碳氟化合物以及有机硅化合物的等离子体聚合。同时还系统地介绍了等离子体聚合物在制备反渗透膜、分离膜、材料表面的涂层等方面的国内外的最新研究成果。     

烯烃聚合催化剂和聚合反应

简要叙述了传统齐格勒－－纳塔催化剂的发展和演变,介绍了茂金属催化睡聚烯烃工业的新发展,并对新一代后过渡金属烯烃聚合催化剂的研究进展作了综合评述。     

六甲基二硅胺烷的等离子体聚合

在室温和无添加气体条件下,完成了六甲基二硅胺烷较低功率密度的等寒子体聚合。研究了聚合膜的沉积规律和过程。给出了聚合物膜的结构和性质。得到经验式为 C_(1.42)H_(2.65)N_(0.2)O_(0.15)Si的新聚合物。     

Fundamentals of Plasma Polymerization

The plasma polymerization of ethylene is used as an example through which to discuss the elementary steps involved in forming a polymer in an electric discharge. The relationship of the experimentally controlled variables to the rate of formation of first generation active species is discussed. These species are related, in turn, to the overall rate of polymerization through a simple model. Two asymptotic conditions are discussed which correspond to minimal and total conversion of monomer to polymer. The dependence of polymer deposition rate on monomer flow rate predicted by the model is found to correspond very closely to that observed experimentally. The predicted effect of gas pressure on polymer deposition rate also agrees with that found experimentally.     

乙烯气相配位聚合综合实验的设计

利用合成的α-二亚胺钯配合物作为催化剂，在四（3，5-二（三氟甲基）苯基）硼酸钠活化下催化乙烯气相配位聚合，并对所得聚合物样品进行力学性能测试。本实验涵盖了有机配体合成、金属催化剂合成、高分子材料合成和力学性能测试等4方面的内容，并且能观察到"气体变材料"的有趣现象，在激发学生学习兴趣的同时能够全面提高学生的实验技能。     

茂金属催化乙烯聚合反应动力学

以茂金属化合物[(CH3)2C(η－C5H3）（η－C9H6）]ZrCl2为主催化剂，甲基铝氧烷MAO为助催化剂催化乙烯聚合，对不同的反应条件下（如温度，铝锆摩尔比）聚合反应的动力学进行了研究，并根据此聚合反应体系的动力学特点及考虑到活性中心的再活化，在分析和研究以往的动力学模型的基础上，对烯烃均相聚合动力学反应作了一些假定，建立了动力学模型，用模型对实验数据进行了拟合，结果表明与实验数据相吻合，可以认为，在该聚合反应体系中，确实存在铝氧烷的再活化作用，根据模拟拟合得到了聚合反应的动力学参数。