反相乳液共聚合制备两性丙烯酰胺共聚物的研究

采用Span80-Tween80复合乳化剂和AIBA引发剂,进行丙烯酸钠(NaAA)/丙烯酰胺(AM)/丙烯酰氧基乙基三甲基氯化铵(DAC)反相乳液共聚合.研究了聚合温度、引发剂用量、单体浓度、共聚单体中DAC和AM含量、乳化剂用量及其HLB值、水/油比和水相pH值等聚合反应工艺条件或参数对聚合反应单体转化率和聚合物特性粘度的影响,聚合物特性粘度随引发剂用量和单体浓度的增大而增大的实验结果证实了该两性丙烯酰胺共聚物反相乳液制备过程中凝胶效应的存在.傅立叶红外光谱组成分析表明了两性丙烯酰胺共聚物的成功合成,扫描电镜观测乳胶粒粒径范围在0.6~8.0μm.     

等离子体引发丙烯酰胺的反相悬浮聚合

通过等离子体引发技术进行了丙烯酰胺的反相悬浮聚合研究,考察了后聚合时间,放电时间,放电功率,单体浓度,分散剂浓度及溶剂极性对聚合物分子量和转化率的影响。结果发现：延长后聚合时间有利于反应的进行,而在聚合反应中存在着一个最佳的单体浓度值,增加溶剂的极性有利于反应进行,降低体系中空气残留量也有利于反应进行。     

紫外光引发丙烯酰胺分散聚合研究

以聚丙烯酸接枝壬基酚聚氧乙烯(PAA -g -NPEO)作分散剂,紫外光(UV)引发丙烯酰胺(AM )在叔丁醇 水(TBA /H2 O)体系中进行了分散聚合.考察了聚合反应特征以及醇水比、初始单体浓度、引发剂浓度、分散剂浓度、表面入射光强、反应温度、液层厚度等参数对聚合产物粒径及分子量的影响.结果表明该聚合体系不存在诱导期,反应速度快,光照4 0min转化率可达到90 % ,产物分子量达6 . 5×10 6 .透射电镜(TEM)观察显示所得聚合物粒子基本为球形,粒径分布较为均匀.     

丙烯酰胺-N-羟甲基丙烯酰胺反相乳液共聚合

：以Ｓｐａｎ ４０ 为乳化剂,过硫酸铵为引发剂,进行了丙烯酰胺 Ｎ 羟甲基丙烯酰胺反相乳液共聚反应,研究了反应温度、单体浓度、引发剂浓度、乳化剂浓度等因素对聚合动力学的影响,并讨论了其聚合机理。     

反相乳液聚合法合成高分子量聚丙烯酸钠

以丙烯酰氧基Span-80为乳化剂,采用反相乳液聚合法合成了高分子量聚丙烯酸钠.研究了乳化剂和中和度对聚合体系稳定性的影响,以及(NH4)2S2O8—甲基丙烯酸-N、N-二甲氨基乙酯(DMAEMA)—NaHSO3引发剂和单体浓度对聚合物分子量的影响.结果表明,最佳的实验条件:中和度为90%;乳化剂用量为3%(油相);引发剂占单体的质量分数分别为(NH4)2S2O80.06%、DMAEMA0.04%、NaHSO30.02%;单体在水相的质量分数为40%(水相).在最佳实验条件下,合成聚合物分子量超过2.6×107,且溶解性能优于溶液聚合所得产品.     

4,4′-偶氮二[4-氰基戊酰(对-二甲基氨基)苯胺]引发丙烯酰胺聚合及其动力学研究

以N,N-二甲基甲酰胺(DMF)为溶剂,研究了4,4′-偶氮二[4-氰基戊酰(对-二甲基氨基)苯胺](ACPDA)为引发剂引发丙烯酰胺(AAM)的聚合行为.考察了聚合反应温度、单体浓度和引发剂浓度对聚合物分子量和聚合反应速率的影响,测定了反应级数和聚合反应的活化能.实验结果表明,ACPDA引发AAM的聚合速率方程为Rp=K[AAM]1.03[ACPDA ]0.48,聚合反应的表观活化能(Ea)为126.44kJ·mol-1.     

FeBr3/Me6TREN催化MMA反向原子转移自由基聚合研究

对FeBr3/Me6TREN催化的反向原子转移自由基聚合进行了研究.在不同的催化剂、引发剂的配比、聚合温度和配体用量等条件下,该催化体系催化的MMA聚合反应动力学为一级反应,聚合物分子量可控,分子量分布很窄,说明该体系催化的聚合反应为活性可控聚合.通过实验计算了反应的活化能,并利用UV光谱对催化剂进行了研究.     

含氧光敏引发体系的研究——Ⅵ.二苯酮/三乙胺体系引发光聚合过程中的再次引发效应

过去,作者曾发表了多种光敏引发体系引发烯类单体光聚合的工作,在研究2,2-二甲氧基苯乙酮在氧存在下引发甲基丙烯酸甲酯光聚合时,结合在聚合物链端的引发剂碎片具有光化学活性,在光聚合反应中产生高分子自由基,发生再次聚合,出现高分子量     

链转移剂单体存在下苯乙烯乳液聚合反应研究

以α-甲基丙烯酸-3-巯基己酯(MHM)为链转移剂单体,过硫酸钾(KPS)为引发剂,十二烷基苯磺酸钠(LAS)为乳化剂,通过乳液聚合合成支化聚苯乙烯(BPSt).采用1H-NMR和三检测体积排除色谱(TD-SEC)对聚合反应过程和合成的聚合物进行了表征分析.结果表明,在合适的乳化剂用量、引发剂用量和聚合反应温度等条件下,反应初期生成的初级链可以完全转化成支化聚合物,在高单体转化率下不发生交联得到较窄分子量分布的高分子量支化聚苯乙烯(Mn,SEC1.4×105,Mw,MALLS2.0×106,PDI4.5),而且所得聚合物表现出很高的支化程度(g'=0.5~0.6).     

超声波辅助合成低分子量聚丙烯酸钠

以过硫酸铵为引发剂,在超声波辅助下引发丙烯酸单体聚合。研究了单体浓度、引发剂用量、反应温度等对单体转化率和聚丙烯酸钠分子量的影响。结果表明:在超声作用下,能够加快聚合反应速度,提高转化率,但对产物聚合度影响很小;控制单体浓度30-40%、引发剂用量1.0%、反应温度50-70℃,在超声波作用下,制得聚丙烯酸钠的相对分子量在2,000-5,000之间。     

二甲基二烯丙基氯化铵反相乳液聚合动力学及机理的研究

研究以异构烷烃混合物为连续相,以丁二酸二(2-乙基)己酯磺酸钠(Sodium-di-2-ethylhexylsulfosuccinate,CH~3CH~2CH~2CH~2CH(C~2H~5)CH~2OCOCH(SO~3Na)CH~2COOCH~2CH(C~2H~5)-CH~2CH~2CH~2CH~3,AOT)和山梨糖醇单油酸酯(SMO)为乳化剂,以偶氮二异庚腈(ADVN)为引发剂的二甲基二烯丙基氯化铵的反相乳液聚合,得到了R~P~,~0=kc^0^.^4~Ⅰ~,~0c^0^.^5~A~O~Tc^-^0^.^4~S~M~Oc^3^.^0~M~,~0的表观动力学表达式。首次提出并研究了反相乳液聚合中单体在单体液滴和胶束中的分配系数对聚合动力学的影响,成功地解释了初始聚合反应速度和单体浓度三次方成正比的原因。通过对胶粒(latex)直径、单体在油相中的溶解度、聚合反应速度与AOT浓度及搅拌速度间的关系的测定,证明聚合反应是通过胶束(micelle)成核机理而进行的。通过对不同单体浓度下的^1H NMR盐效应的研究,证明溶液聚合的速度和单体浓度二次方成正比不是由于生成双分子π配合物,而是由静电屏蔽效应和粘度的改变引起的。     

PHOTOINITIATED INVERSE EMULSION POLYMERIZATION OF SODIUM ACRYLATE

Photoinitiated inverse emulsion polymerization of sodium acrylate (AANa) in kerosene was carded out at room or lower temperature, using 2,2-dimethoxy-2-phenylacetophenone (DMPA) as the initiator. Kinetic investigations indicated that the polymerization could be completed in about 30 min and produce polymer with high molecular weight (10^6-10^7). It was found that monomer droplets are the main sites for the polymerization (nucleation). With the increase of DMPA concentration, polymerization rate (Rp) reaches a maximum value while molecular weight of the produced polymer has an adverse result, but the dependence of Rp on incident light intensity is similar. Influences of other parameters such as monomer concentration, emulsifier content and reaction temperature, etc. were also studied. At lower pH values of water phase, Rp depends strongly on the pH due to the electrostatic interaction between the ionized radicals and the monomer. At higher pH, Rp shows a slight dependence on pH.     

Microemulsion polymerization of styrene in the presence of a cationic emulsifier

The principal subject discussed in the current paper is the radical polymerization of styrene in the three- and four component microemulsions stabilized by a cationic emulsifier. Polymerization in the o/w microemulsion is a new polymerization technique which allows to prepare the polymer latexes with the very high particle interface area and narrow particle size distribution. Polymers formed are very large with a very broad molecular weight distribution. In emulsion and microemulsion polymerizations, the reaction takes place in a large number of isolated loci dispersed in the continuous aqueous phase. However, in spite of the similarities between emulsion and microemulsion polymerization, there are large differences caused by the much larger amount of emulsifier in the latter process. In the emulsion polymerization there are three rate intervals. In the microemulsion polymerization only two reaction rate intervals are commonly detected: first, the polymerization rate increases rapidly with the reaction time and then decreases steadily. Essential features of microemulsion polymerization are as follows: (1) polymerization proceeds under non-stationary state conditions; (2) size and particle concentration increases throughout the course of polymerization; (3) chain-transfer to monomer/exit of transferred monomeric radical/radical re-entry events are operative; and (4) molecular weight is independent of conversion and distribution of resulting polymer is very broad. The number of microdroplets or monomer-starved micelles at higher conversion is high and they persist throughout the reaction. The high emulsifier/water ratio ensures that the emulsifier is undissociated and can penetrate into the microdroplets. The presence of a large amount of emulsifier strongly influences the reaction kinetics and the particle nucleation. The mixed mode particle nucleation is assumed to govern the polymerization process. At low emulsifier concentration the micellar nucleation is dominant while at a high emulsifier concentration the interaction-like homogeneous nucleation is operative. Furthermore, the paper is focused on the initiation and nucleation mechanisms, location of initiation locus, and growth and deactivation of latex particles. Furthermore, the relationship between kinetic and molecular weight parameters of the microemulsion polymerization process and colloidal (water/particle interface) parameters is discussed. In particular, we follow the effect of initiator and emulsifier type and concentration on the polymerization process. Besides, the effects of monomer concentration and additives are also evaluated.     

Kinetic study of the polymerization of acrylamide in inverse microemulsion

The polymerization of acrylamide in inverse microemulsions stabilized by Aerosol OT emulsifier and initiated with azobisisobutyronitrile (AIBN) or potassium persulfate (K₂S₂O₈) has been investigated. The inverse polyacrylamide latexes formed are clear and highly stable. A dilatometric technique was used to follow the conversion of monomer at T = 45°C. The rate of polymerization is first order with respect to initial monomer concentration in the presence of AIBN, and is 1.5 order with K₂S₂O₈. An inverse relationship between molecular weight and emulsifier concentration is found which suggests participation of the emulsifier in the initiation reaction. This is confirmed by the independence of the molecular weight of polyacrylamide on the concentration of the initiators. High values of the rate of polymerization are obtained combined with high molecular weights (up to 10⁷). An important and novel feature of this microemulsion process is that each final latex particle consists of one single molecule of polyacrylamide in a collapsed state. This suggests kinetics which do not follow the Smith and Ewart theory but are characterized by continuous particle nucleation.     

INVERSE EMULSION POLYMERIZATION OF ACRYLAMIDE: POLYMERIZATION KINETICS AND PROCESS DEVELOPMENT

Inverse emulsion polymerization confers the benefits of emulsion polymerization kinetics — rapid polymerization rates combined with high polymer molecular weights — on water-soluble polymers, particularly polyacrylamide and its copolymers and derivatives, and allows easy dissolution of the polymer in water by inversion of the latex. The mechanism and kinetics of the inverse emulsion polymerization of acrylamide in o-xylene containing Tetronic 1102 emulslfier and benzoyl peroxide initiator are described, particularly the formation of 10-200nm multiple emulsion droplets resulting from the particulate emulsifier, and their effect on the polymerization process     

Use of block copolymer surfactants in the inverse-suspension polymerization of acrylamide

A comprehensive experimental investigation of the inverse microsuspension polymerization of acrylamide using an oil-soluble initiator and a block copolymeric surfactant whose hydrophobic miety is poly(12-hydroxystearic acid) and whose hydrophilic moeity is polyethylene oxide was carried out. It was found that the initial polymerization rate was first order with respect to molar monomer concentration, first order with respect to molar initiator concentration and zeroth order with respect to molar emulsifier concentration. Based on these experimental findings, a mechanism was proposed which includes initiation, propagation transfer to monomer and termination. It also includes transfer to impurities which are believed to be found in the surfactant. The kinetic model developed from the proposed mechanism is found to be in good agreement with the experimental conversion and weight-average molecular weight data. Comparing with sorbitan esters of fatty acids, the copolymeric surfactant provides higher polymerization rate and very high and linear molecular weight comparable to those obtained by solution polymerization.     

Inverse emulsion polymerization of acrylamide. I. Contribution to the study of some mechanistic aspects

The inverse emulsion polymerization of aqueous solution of acrylamide in toluene has been studied at 40°C using a blend of surfactants as emulsifying system and oil soluble azo initiators. The azo compound partition between the phases has been measured and the effects of their nature and concentration on the polymerization kinetics have been investigated. The influence of other parameters on the kinetics and particle size of the inverse latex have also been investigated: the nature and amount of the emulsifier system, the stirring rate, and the presence of oil-soluble inhibitor. The particle-size analysis using electron microscopy or dynamic light-scattering methods showed the presence of two populations of particles in the initial monomer emulsion and in the final inverse latex: one with very tiny particles (20 nm diam) and the other with larger particles (80–400 nm diam) which is highly polydispersed. The average size of these large particles undergoes a sharp decrease at a certain percent conversion depending upon the stirring rate. The evolution of the particle size distribution may result from a balance between coalescence and dispersion of the emulsion droplets under the effect of prevailing shear rate due to agitation. Concerning the initiation process, the very low solubility of the azo compound in the aqueous solution, together with the effect of the stirring rate and the presence of an oil-soluble inhibitor on the polymerization kinetics lead to the conclusion that most of the initiaton originates from the capture of radicals or oligomeric radicals produced in the oil phase or in the interfacial layer.     

Preparation of Fluorine-Containing Polyacrylate Emulsion by a UV-initiated Polymerization

A fluorine-containing polyacrylate emulsion was synthesized by a UV-initiated emulsion polymerization from methyl methacrylate (MMA) and hexafluorobutly methacrylate (HFMA) in the presence of 2-hydroxy-4-(2-hydroxyethoxy)-2-methyl-propiophenone (Irgacure 2959) as a hydrophilic photoinitiator at room temperature. The latex and films were characterized by Fourier transformed infrared (FT-IR) spectrometry, nuclear magnetic resonance (¹H-NMR, ¹⁹F-NMR) spectrometry, transmission electron microscopy (TEM), recycling gel permeation chromatography (GPC), dynamic light scattering (DLS), and contact angle (CA) analysis, respectively. The effects of photoinitiator and emulsifier concentration on the polymerization were discussed. Compared to the corresponding thermal polymerization, UV-initiated polymerization of the MMA/HFMA emulsion could be accomplished at a much higher speed. The polymerization conversion in UV-initiated polymerization reached 95% within 10 min at an emulsifier concentration of 0.6 wt%, photoinitiator concentration of 0.4 wt%, and monomer concentration of 10 wt%.     

Sterically stabilized emulsion polymerization of styrene: Pseudo‐semicontinuous approach

The sterically stabilized emulsion polymerization of styrene initiated by a water‐soluble initiator at different temperatures has been investigated. The rate of polymerization (R_p) versus conversion curve shows the two non‐stationary‐rate intervals typical for the polymerization proceeding under non‐stationary‐state conditions. The shape of the R_p versus conversion curve results from two opposite effects—the increased number of particles and the decreased monomer concentration at reaction loci as the polymerization advances. At elevated temperatures the monomer emulsion equilibrates to a two‐phase or three‐phase system. The upper phase is transparent (monomer), and the lower one is blue colored, typical for microemulsion. After stirring such a multiphase system and initiation of polymerization, the initial coarse polymer emulsion was formed. The average size of monomer/polymer particles strongly decreased up to about 40% conversion and then leveled off. The initial large particles are assumed to be highly monomer‐swollen particles formed by the heteroagglomeration of unstable polymer particles and monomer droplets. The size of the “highly monomer” swollen particles continuously decreases with conversion, and they merge with the growing particles at about 40–50% conversion. The monomer droplets and/or large highly monomer‐swollen polymer particles also serve as a reservoir of monomer and emulsifier. The continuous release of nonionic (hydrophobic) emulsifier from the monomer phase increases the colloidal stability of primary particles and the number of polymer particles, that is, the particle nucleation is shifted to the higher conversion region. Variations of the square and cube of the mean droplet radius with aging time indicate that neither the coalescence nor the Ostwald ripening is the main driving force for the droplet instability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 804–820, 2003     

Polymerization of acrylamide in nonionic microemulsions: Characterization of the microlatices and polymers formed

Free radical polymerization of acrylamide was carried out in nonionic microemulsions of water, an isoparaffinic oil, Isopar M and a blend of nonionic emulsifiers: a sorbitan sesquioleate and a polyoxyethylene sorbitol hexaoleate (HLB of the mixture: 9.3). The size and the stability of the latex particles formed after polymerization were studied as a function of monomer, emulsifier and electrolyte concentration. High emulsifier and high monomer contents favor obtaining high molecular weight polyacrylamides. It is shown that both the number of polymer chains contained in each latex particle and the size of the particles are essentially controlled by the acrylamide/emulsifier weight ratio.