水解对乙烯—乙酸乙烯共聚物乳液复合的影响

乙烯－乙酸乙烯共聚物（ＥＶＡ）乳液在ＮａＯＨ作用下进行表面水解处理后,加入甲基丙烯酸甲酯（ＭＭＡ）,在过硫酸铵引发下进行复合反应。对复合乳胶粒的凝胶质量分数的测定、热分析及动态粘弹性的表征表明,随ＥＶＡ乳胶粒表面水解度的增大,ＭＭＡ在其表面的接枝率增大,体系的交联程度随之增大,两相相容性得到改善。此外还探讨了复合配比及加入少量丙烯酸对复合体系的影响。     

乙酸乙烯酯的微波加热聚合

对乙酸乙烯酯甲醇溶液在微波加热条件下的聚合反应进行了研究,讨论了微波聚合条件、引发剂浓度、溶剂浓度和种类对聚合产物的转化率和分子量的影响。聚合物可以在较短时间内获得。且在同样的实验条件下,用不同的溶剂获得的聚合物的分子量不同。     

新型引发剂引发乙酸乙烯酯乳液聚合动力学

以十二烷基硫酸钠为乳化剂,采用偶氮二异(N-胺乙基)丁脒引发乙酸乙烯酯低温乳液聚合。考察了引发剂浓度、单体浓度、乳化剂浓度及反应温度对聚合反应速率的影响,测定了反应级数和聚合表观活化能。得到乙酸乙烯酯乳液聚合动力学关系式,该式与经典的乳液聚合动力学模型有较大偏差,聚合表观活化能为56.8 kJ/mol。     

抗水性和抗冻性聚乙酸乙烯酯乳液胶黏剂的制备

用乙烯-乙酸乙烯酯共聚乳液作为种子进行聚合，制备了抗水性和抗冻性的聚乙酸乙烯酯乳液胶黏剂。研究了乙烯-乙酸乙烯酯共聚物乳液的用量对改进型PVAC乳液的抗冻性、抗水性及表面张力的影响。     

复合引发剂用量估算

介绍了复合引发剂的理论用量计算方法,提出了引发剂初级游离基消耗量计算的观点。     

国产复合引发剂在聚氯乙烯树脂生产中的应用

文章从悬浮聚合引发剂的选择、分析，介绍了105m3聚合釜使用国产TX23／TX36复合引发剂替代EHP单一引发剂生产PVCSG-7型树脂的情况。采用国产复合引发剂不但解决了悬浮聚合反应后期的超温超压现象，还提高了聚合釜的生产能力，降低了树脂成本，提高了产品在市场上的竞争力。     

乙酸乙烯酯无乳化剂乳液聚合的影响因素探讨

采用乙酸乙烯酯(VAc)在水中以过硫酸钾(KPS)和亚硫酸氢钠氧化还原体系作为引发剂进行无乳化剂乳液聚合,探讨了引发剂浓度、聚合温度、单体浓度和搅拌速度对聚合速率及转化率的影响。结果表明:当VAc质量分数为30%,KPS:VAc摩尔比为1:2 000,聚合温度10℃,反应时间10 h,搅拌速度80 r/min,时聚合产物聚乙酸乙烯的聚合度达到10 848;当VAc质量分数为35%时,聚合转化率可达到96%,聚合速率与引发剂浓度的0.944次方成正比;当搅拌速度达到200 r/min以上时,搅拌速度对聚合速率以及转化率影的响可以忽略。     

复合引发剂存在下的氯乙烯聚合动力学

Kinetic models for the rate constants of vinyl chloride polymerization in the presence of initiator mixtures were proposed. They may be used to design the initiator recipes for the vinyl chloride polymerization with uniform rate at different temperatures at which various grades of poly(vinyl chloride) will be prepared.     

乙烯-乙酸乙烯酯共聚物中乙酸乙烯酯的红外光谱法测定

利用ATR技术测量样品的红外光谱,采用偏最小二乘法对所测光谱进行分析,建立了一种快速分析方法;对乙烯-乙酸乙烯酯共聚物中乙酸乙烯酯进行测定。结果表明：标准曲线线性关系良好,相关系数为0．99985,方法简单快速,结果可靠。     

水解对乙烯－乙酸乙烯共聚物乳液复合的影响Ⅲ.复合乳液的性能

对水解处理后的乙烯－乙酸乙烯共聚物（ＥＶＡ）乳液与丙烯酸丁酯、甲基丙烯酸丁酯的复合乳液的性能进行了表征。结果表明,复合单体的水解处理后的ＥＶＡ乳胶粒表面的接枝状况对复合乳液的稳定性及其胶膜的而水性和力学性能有较大影响,热处理对胶膜性能的影响与复合单体的ＥＶＡ乳胶粒表面的接枝状况有关。     

Synthesis of high-molecular weight poly(vinyl alcohol) by low-temperature emulsifier-free emulsion polymerization of vinyl acetate and saponification

High-molecular weight (HMW) poly(vinyl alcohol) (PVA) was prepared via an emulsifier-free emulsion polymerization of vinyl acetate (VAc) using a redox initiation system in low temperatures, and the subsequent saponification with potassium hydroxide in methanol. The effect of the polymerization conditions on the conversion, molecular weight, and branching degree was investigated. PVA with maximum viscosity-average degree of polymerization (DP) of 8270 could be prepared by saponification of poly(vinyl acetate) (PVAc), with DP of 10,660 obtained at temperature of 10°C, monomer concentration of 30%, potassium persulfate molar ratio to monomer of 1/2000, agitation speed of 160 rpm. The conversion was above 90%. From the emulsifier-free emulsion polymerization of VAc in low temperature, PVAc with HMW and high linearity was effectively prepared, which might be useful for the preparation of high-strength and high-modulus PVA fiber. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Graft polymerization of vinyl acetate onto silica

The free‐radical graft polymerization of vinyl acetate onto nonporous silica particles was studied experimentally. The grafting procedure consisted of surface activation with vinyltrimethoxysilane, followed by free‐radical graft polymerization of vinyl acetate in ethyl acetate with 2,2′‐azobis(2,4‐dimethylpentanenitrile) initiator. Initial monomer concentration was varied from 10 to 40% by volume and the reaction was spanned from 50 to 70°C. The resulting grafted polymer, which was stable over a wide range of pH levels, consisted of polymer chains that are terminally and covalently bonded to the silica substrate. The experimental polymerization rate order, with respect to monomer concentration, ranged from 1.61 to 2.00, consistent with the kinetic order for the high polymerization regime. The corresponding rate order for polymer grafting varied from 1.24 to 1.43. The polymer graft yield increased with both initial monomer concentration and reaction temperature, and the polymer‐grafted surface became more hydrophobic with increasing polymer graft yield. The present study suggests that a denser grafted polymer phase of shorter chains was created upon increasing temperature. On the other hand, both polymer chain length and polymer graft density increased with initial monomer concentration. Atomic force microscopy–determined topology of the polymer‐grafted surface revealed a distribution of surface clusters and surface elevations consistent with the expected broad molecular‐weight distribution for free‐radical polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 300–310, 2003     

氯乙烯聚合用引发剂的研究

在研究单一引发剂分解动力学的基础上,提出复合引发剂分解动力学模型,并结合ＶＣＭ聚合动力学,为恒速聚合的复合引发体系的配方设计提供指导。     

乳液聚合法合成高相对分子质量聚醋酸乙烯酯的研究

采用过硫酸铵/亚硫酸氢钠氧化还原体系低温引发醋酸乙烯酯乳液聚合,合成出分子量为1.07×106、分子量分布为2.75的聚醋酸乙烯酯。讨论了聚合温度、单体用量、十二烷基硫酸钠(SDS)用量、过硫酸铵用量、亚硫酸氢钠用量等因素对聚醋酸乙烯酯黏均分子量的影响,并用GPC法对其进行表征。     

Semicontinuous emulsion polymerization of vinyl acetate: Effect of ethoxylation degree of nonionic emulsifiers

Poly(vinyl acetate) latices were prepared in the presence of an ammonium persulfate initiator, 10–50 mol of an ethoxylated nonylphenol nonionic emulsifier, and a poly(vinyl alcohol) colloid stabilizer by applying semicontinuous emulsion polymerization (delayed monomer and initiator addition process) in a laboratory scale similar to industrial practice. Two approaches were applied: the molar concentration of the nonionic emulsifier was kept constant and the weight ratios in the polymerization recipe varied or the weight ratios were kept constant. The effects of the change in the ethoxylation degree of the emulsifier to the final latex viscosity, average polymer molecular weight, polymer grafting degree, surface tension of the latex, and the surface free energy of the dried films were investigated. It was determined that the resultant latex viscosity decreases and the viscosity‐average polymer molecular weight increases with increase of the nonionic emulsifier ethoxylation degree. The increase of the ethoxylation degree does not seriously affect the surface tension of the resultant latex or the surface free energy of the dried poly(vinyl acetate) films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 844–851, 2002     

Seeded emulsion polymerization of vinyl acetate: order of reaction with respect to initiator

The emulsion polymerization of vinyl acetate has been studied using carefully prepared seed lattices. Experiments were carried out in which temperature, particle size and the monomer-polymer ratio could be varied independently. In all cases the polymerization rate was proportional to the initiator concentration raised to the 0.7 power. No new particles were formed. The importance of polymerization in the aqueous phase and changes in the propagation rate coefficient are discussed.     

氯乙烯悬浮(本体)聚合用过氧化物引发剂

介绍了氯乙烯(VC)悬浮(本体)聚合常用过氧化引发剂的合成方法，着重阐述引发剂与聚合动力学的关系以及聚合动力学的检测方法。研究了单一和复合引发剂条件下的VC聚合动力学，为优化引发剂体系、缩短聚合时间、提高聚合釜的生产能力提供理论基础。     

Controlled synthesis of poly(vinyl acetate) by traditional radical emulsion polymerization

A new redox initiation system, potassium persulfate/N,N‐dimethylethanolamine, was used to initiate traditional radical emulsion polymerization of vinyl acetate at low temperature. Polymers were characterized using gel permeation chromatography, scanning electron microscopy and dynamic light scattering. The results showed that poly(vinyl acetate) with high molar mass and small dispersity (?) was successfully synthesized. © 2016 Society of Chemical Industry     

新型过氧化物引发剂引发氯乙烯悬浮聚合动力学

研究了新型过氧化物引发剂过氧化新癸酸 1,1 二甲基-3-羟基丁基酯(Lup 610)在51.3与56.8℃以及过氧化新庚酸叔丁酯(Lup 701)和过氧化新戊酸叔己酯(HPV)在61.8℃单一引发剂引发氯乙烯悬浮聚合动力学,并采用模型计算结果绘制转化率 时间曲线,取与实验数据符合最好的f值作为引发剂的引发效率,求得引发剂Lup 610在51.3与56.8℃的引发效率分别为0.80与0.75,引发剂Lup 701和HPV在61.8℃下的引发效率分别为0.55和0.50。研究了上述引发剂与过氧化二碳酸二(2-乙基己酯)、过氧化新癸酸叔丁酯在各温度下复合引发剂引发氯乙烯悬浮聚合的动力学,与模型值相比较,发现两者能很好吻合。