A kinetic study of the emulsion polymerization of vinyl acetate

The emulsion polymerization of vinyl acetate was studied at 50°C. It was found that the rate of polymerization was proportional to the 0.5 power of the initiator concentration and the 0.25 power of the number of particles. The number of particles was proportional to the power 0.5 ± 0.05 of the emulsifier concentration, but independent of the initiator concentration. The limiting viscosity number of the polymers produced was independent of the initiator concentration and number of polymer particles. It is suggested that the mechanism of vinyl acetate emulsion polymerization is similar to that of vinyl chloride. The linearity of the conversion-versus-time curve is explained as being due partly to a decrease in the desorption rate of radicals from the polymer particles and partly to a decrease in the termination rate constant.     

低聚合度、低醇解度聚乙烯醇的合成与性能研究——I.低聚合度聚醋酸乙烯酯的合成

以甲醇为溶剂,偶氮二异丁腈(AIBN)为引发剂,采用自由基聚合方法合成了低聚合度聚醋酸乙烯酯,并对其结构进行了表征。讨论了聚合时间、引发剂用量、物料配比、聚合温度等因素对聚合率的影响,获得了相对较佳的工艺参数。     

Semicontinuous miniemulsion terpolymerization: Effect of the operation conditions

The effect of solids content, initiator concentration, feed-flow rate, and amount of cosurfactant on the kinetics of the high solids content, semicontinuous miniemulsion terpolymerization of butyl acrylate, methyl methacrylate, and vinyl acetate was studied. In addition, the effect of the operation variables on the feasibility of obtaining a 65 wt% solids content latex with low amount of coagulum was investigated. The operation variables studied were: (1) partition of the monomer between the initial charge and the feed, (2) type and concentration of emulsifier; (3) feed-flow rate; and (4) sonication. © 1993 John Wiley & Sons, Inc.     

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     

微悬浮聚合法合成聚醋酸乙烯酯的动力学研究

采用微悬浮法合成聚醋酸乙烯酯,对其聚合反应的动力学进行了研究。考察了引发剂浓度、乳化剂浓度、单体浓度以及温度对聚合反应速率的影响。结果表明,聚合反应速率对引发剂浓度、乳化剂浓度和单体浓度的反应级数分别为0．45,0．28,1．90,单体浓度对聚合反应速率的影响最大,反应体系的表观活化能为105．96 kJ/mol。     

RADICAL DESORPTION IN EMULSION POLYMERIZATION OF VINYL ACETATE

In the present paper a model equation for calculating the radical desorption rate constant,k_0,in the emulsion polymerization of vinyl acetate was suggested and the various parameters forevaluating k_0 were determined.Effects of reaction temperature,emulsifier concentration,initiator con-centration,monomer conversion and phase ratio on k_0 were studied.It indicates that the desorptionof radicals from latex particles to aqueous phase must be taken into account in the modelling ofemulsion polymerization for the monomers with higher hydrophilicity such as vinyl acetate.     

提高聚醋酸乙烯酯乳液性能的实验研究

目的:提高聚醋酸乙烯酯乳液的稳定性和耐水性.方法:采用醋酸乙烯酯为聚合单体、聚乙烯醇为胶体保护剂及乳化剂壬基酚聚氧乙烯醚的聚合反应,制备聚醋酸乙烯酯乳液.再利用单组实验法研究聚乙烯醇、乳化剂、引发剂、加料方式及反应温度等对制备稳定性和耐水性好的聚醋酸乙烯酯乳液的影响规律.结果:制备粘接强度、稳定性和耐水性良好的聚醋酸乙...     

丙烯酸改性聚醋酸乙烯酯乳液聚合的研究

通过丙烯酸与聚乙二醇共聚合成了具有反应活性的丙烯酸聚氧乙烯酯（简称大单体）,将大单体作为表面活性剂对醋酸乙烯酯乳液聚合的动力学进行了研究;同时在性能上与普通的乳液聚合体系进行了比较。实验结果表明聚合速率随亲水链长度、乳化剂浓度、引发剂浓度、温度的增大而增大,pH值的减小而加快,乳液性能也有了很大的改善．     

Photo‐induced emulsion polymerization of vinyl acetate in the presence of poly(oxyethylene) nonyl phenyl ether,a nonionic emulsifier (II)

Synthesis of high molecular weight poly(vinyl acetate) having less branched structure via photo‐induced emulsion polymerization of vinyl acetate in the presence of poly(oxyethylene)₂₀ nonyl phenyl ether, a nonionic emulsifier, was attempted at 0°C or even below 0°C in the presence of methanol. It was found that 100% conversion is always achieved in all runs and poly(vinyl acetate) having the number‐average degree of polymerization of 9000 with less branched structure (degree of branch < 0.5) can be obtained from this photo‐induced emulsion polymerization system. Mechanisms of the polymerization were also discussed on the basis of the kinetic results. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2153–2158, 2002     

Continuous emulsion polymerization of vinyl acetate. I. Operation in a single continuous stirred tank reactor using sodium lauryl sulfate as emulsifier

Continuous emulsion polymerizations of vinyl acetate were carried out at 50 °C in a single continuous stirred‐tank reactor using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator. It was found that (1) the so‐called limit cycles could take place in monomer conversion, the number of polymer particles and the molecular weight of polymers produced under certain operating conditions, (2) the time‐average steady‐state monomer conversion was proportional to the 0.31 power of the emulsifier concentration in the feed, to the 0.50 power of the initiator concentration, to the ?1.0 power of the monomer concentration, and to the 0.90 power of the mean residence time, and (3) the time‐average steady‐state number of polymer particles produced was proportional to the 2.1 power of the emulsifier concentration in the feed, to the ?0.80 power of the initiator concentration, to the 0 power of the monomer concentration, and to the ?0.92 power of mean residence time. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2748–2754, 2002     

PVAc Microspheres via Semicontinuous Emulsion Polymerization: Synthesis,Characterization, Kinetic,and Surface Morphology Studies

Poly (vinyl acetate) (PVAc) latexes are economically important products with many desirable features. They are used as adhesives for porous materials in various processing stages of industries. Synthesis parameters have an important role on the physico-chemical properties of PVAc latexes such as: viscosity, average molecular weight, degree of polymerization, and surface morphology. In this work, PVAc was prepared via semicontinous emulsion polymerization (delayed monomer and initiator addition process) in the presence of ammonium persulfate (APS) as conventional anionic initiator, poly (vinyl alcohol) (PVA) as stabilizer, and sodium lauryl sulfate (SLS) as anionic emulsifier. The surface morphology of PVAc microspheres was, examined using a scanning electron microscope (SEM) and atomic force microscope (AFM). It is evident from the SEM photographs that all the particles became microspheres and are uniform in shape. The use of AFM for imaging of polyvinyl acetate confirms a typical sphere polymer. The effect of changes in the different parameters such as concentration of emulsifier, initiator concentration, and presence or absence of buffer on the vinyl acetate (VAc) conversion, the steady state polymerization rate, the viscosity-average molecular weight, and the final latex viscosity of synthesized PVAc were investigated. The effects of anionic emulsifier on the synthesized PVAc are also compared with those obtained by the nonionic emulsifier. The comparison indicated that the VAc monomer conversion and the final latex viscosity of the anionic system were higher than for the nonionic system but the viscosity-average polymer molecular weight of the anionic system was lower than that of the nonionic system. The adhesive strength of the synthesized PVAc latex was examined and the load and deflection data were reported.     

Preparation of polystyrene/poly(vinyl acetate) nanocomposites with a core–shell structure via emulsifier‐free emulsion polymerization

Polystyrene/poly(vinyl acetate) latex nanoparticles with a core–shell morphology in an emulsifier‐free emulsion polymerization system were prepared with purified styrene and vinyl acetate (VAc) as monomers and 2,2′‐azo bis(2‐amino propane) dihydrochloride (ABA,2HCl) as the initiator and emulsifier. The optimized conditions of polymerization of VAc, on top of the already‐formed polystyrene as a core polymer, with a core–shell morphology were obtained using various parameters such as volume ratio of the first and second stages, type of process, and reaction time. The morphologic structure of the nanoparticles was studied by scanning electron microscopy and transmission electron microscopy. The latex nanoparticles and polymers were characterized by differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2409–2414, 2006     

Photo‐induced emulsion polymerization of vinyl acetate in the presence of poly(oxyethylene)10 nonyl phenyl ether ammonium sulfate,an anionic emulsifier (I)

Poly(vinyl alcohol) (PVA) having a number‐average degree of polymerization of 7000 was obtained from the poly(vinyl acetate) (PVAc) having a number‐average degree of polymerization 9000, a product of photo‐induced emulsion polymerization of vinyl acetate (VAc), carried out at 0°C, using poly(oxyethylene)₁₀ nonyl phenyl ether ammonium sulfate as an anionic emulsifier. It was found that 100% conversion is always attained in the whole range of the investigation and the emulsifier plays an important role in the initiation process. The applicability of the photo‐induced emulsion polymerization system to a relatively large‐scale production was tested by using an apparatus equipped with an internal high‐pressure Hg lamp with a capacity of several hundred grams per batch under nitrogen atmosphere. It was found that both the rate of polymerization and the degree of polymerization of resulting polymers are slightly lower than those obtained from corresponding small‐scale polymerizations prepared on a high vacuum system because of the presence of oxygen. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2425–2431, 2002     

Microemulsion Radical Polymerization of Alkyl Acrylates

The oil/water microemulsion polymerizations of alkyl (methyl (MA), ethyl (EA), butyl (BA), hexyl (HA) and 2-ethylhexyl (EHA)) acrylates initiated by a water-soluble (ammonium peroxodisulphate (APS)) initiator were investigated. The rate of polymerization versus conversion curve shows two inconstant intervals. The maximum rate of polymerization of MA, EA, BA and EHA is found to be proportional to the 0·53, 0·17, 0·46 and 0·59 powers of the APS concentration and to the first power of the monomer (MA, BA and EHA) concentration. Homogeneous (solution) radical polymerization is operative in the MA, BA and EHA systems. The strong rate dependence on the EA monomer concentration is assumed to be caused by both the polymerization within the micelle core and the gel effect. The particle size was observed to increase with conversion in the EA and BA runs and to decrease in the EHA and HA runs. The number of particles increased with conversion during the whole polymerization. The polymer particles grow by recruiting monomer and emulsifier from the free monomer-swollen micelles and dead particles. © 1997 SCI.     

乳液聚合中单体醋酸乙烯酯与保护胶体聚乙烯醇的接枝反应研究

研究了以聚乙烯醇为保护胶体的醋酸乙烯乳液聚合中,聚乙烯醇与单体的接枝反应。探讨了引发剂用量、聚合反应温度、保护胶体聚合度等因素对接枝反应的影响。     

淀粉接枝丙烯酸异辛酯-醋酸乙烯共聚反应的研究

采用乳液聚合的方法,以硝酸铈铵为引发剂,十二烷基硫酸钠为乳化剂,重点考察了淀粉与醋酸乙烯／丙烯酸异辛酯的接枝共聚反应中引发剂浓度、单体浓度、反应温度、反应时间等条件对接枝率、接枝效率以及接枝反应速率的影响,得到了较为理想的产物。结果表明,接枝率最高可达248.9％,接枝效率可达72.1％,单体转化率可达94.3％。     

有机硅氧烷改性醋酸乙烯酯-丙烯酸酯乳液的合成与性能

采用种子乳液聚合,引入乙烯基三甲氧基硅烷(A-171),以十二烷基苯磺酸钠(DSB)和壬基酚聚氧乙烯(20)醚(OP-10)作复合乳化剂,以过硫酸钾(KPS)为引发剂,在反应温度为78±2℃条件下,合成了A-171改性醋酸乙烯酯(VAc)-丙烯酸酯共聚乳液。实验采用单体滴加工艺,考察了配方中丙烯酸丁酯(BA)、甲基丙烯酸(MAA)和A-171用量对共聚物性能和乳液聚合过程的影响,并用红外光谱仪(FTIR)、粒度仪和差示量热扫描仪(DSC)对共聚物的结构及性能进行了表征。结果表明,引入w(BA)=10%~15%(相对于配方中单体总质量,下同)、w(MAA)=4%、w(A-171)=1%到VAc-丙烯酸酯共聚物乳液中,共聚物乳液涂膜的吸水率<5.0%,耐寒性通过10个循环,60℃加速贮存稳定性>100 d。     

Kinetics of vinyl chloride and vinyl acetate emulsion polymerization

The kinetics of vinyl chloride and vinyl acetate emulsion polymerization are reexamined. The validity of Ugelstad's model for systems with high desorption rate is confirmed by simulating conversion histories for both systems at different initiator concentrations and particle numbers. On the basis of the model, it is shown that at ordinary initiation rates, termination reactions are unimportant with respect to molecular weight development in both systems, and as a consequence, molecular weight development is independent of number and size distribution of polymer particles and of initiator and emulsifier level. Based on this conclusion, it is shown that in accordance with experimental facts, the molecular weight distribution obtained in vinyl chloride emulsion polymerization is the most probable distribution, and it is concluded that the number of long-chain branch points per repetition unit is less than 2 × 10^?4 at high conversions. In vinyl acetate emulsion polymerization, an almost logarithmic normal distribution is obtained. The distribution is strongly broadened by branching reactions with the number of long-chain branch points increasing rapidly with monomer conversion. The increase of M_n with increasing conversion is due to terminal double-bond polymerization, while the increase in M_w is due mainly to transfer to polymer.     

环氧乳液聚合的实验研究

采用烯酯类单体通过乳液聚合法对环氧树脂进行改性,分别考察了反应物配比、乳化剂用量、种子乳液用量、引发剂用量、反应时间与反应温度对环氧乳液聚合反应的影响。结果表明,在反应物配比m环氧树脂∶m乙酸乙烯酯=1∶1,复合型乳化剂质量分数8%、复合型乳化剂配比mOP-10∶mT-80∶mSDS=12∶3∶1,种子乳液的质量分数30%,引发剂质量分数2%,反应时间4h及反应温度65℃的最佳乳液聚合条件下,可得到由乙酸乙烯酯改性的,白色、均匀、稳定性良好的环氧乳液。     

无毒高相对分子质量PVA的合成与结构分析研究

以甲醇为溶剂,以环氧树脂为引发剂,乙酸乙烯酯与甲醇的质量比为25∶3.96,反应温度为(65±2)℃,引发剂用量为0.080 2 g,反应4.5 h,以溶液聚合法制备粘均相对分子质量为1.95×105的聚醋酸乙烯酯,经醇解得到无毒的聚乙烯醇,产品经UV,FTIR,1H NMR谱进行确认和结构分析。讨论了反应温度、反应时间、引发剂用量、原料质量比对醋酸乙烯酯相对分子质量的影响。