Particle coagulation at semicontinuous emulstion polymerization. I. Some factors affecting the process

The factors affecting the amount of coagulum appearing during the semicontinuous emulsion polymerization of acrylic monomers were studied. Monomers were added into the polymerization reactor in the form of emulsion. The stability of the polymerization system was greatly affected by the distribution ratio of a constant amount of emulsifier between the initial charge in the polymerization reactor and the monomer emulsion. The amount of arising coagulum was dependent also on the alkyl length of the alkyl acrylate and increased from ethyl acrylate to 2-ethylhexyl acrylate. The amount of appearing coagulum was essentially decreased by copolymerization with acrylic acid and sulfoethyl methacrylate, respectively. In the case of insufficient covering of particle surface by emulsifier, the colloid stability of polymerizing system was greatly increased by the presence of strong as well as weak acid groups chemically bound on the particle surface.     

The effect of carboxylic monomers on surfactant-free emulsion copolymerization

A study was made of the effect of carboxylic monomers on the surfactant-free emulsion polymerization of styrene and styrene–butadiene. Acid monomers, such as acrylic acid, methacrylic acid, and itaconic acid, were shown to play a critical role in particle formation and particle stabilization in such systems. In the emulsion polymerization of styrene, methacrylic acid forms particles more efficiently than acrylic acid. This difference is attributed to the more hydrophobic nature of the methacrylic monomer which allows it to diffuse more rapidly to the particle surface where it acts to prevent agglomeration. The ability of carboxyl groups to orient at the particle–water interface was studied by acid–base and soap titrations of carboxylated styrene–butadiene latices. The polymerization of itaconic acid onto the particle surface of a styrene–butadiene latex produces a surface carboxyl density much higher than is obtainable with classically adsorbed surfactants. This result is used to explain the greater stability of carboxylated versus noncarboxylated emulsion polymers. During the polymerization of styrene–butadiene latices, carboxyl groups dervied from methacrylic acid are shown to be buried more deeply into the particle as compared to carboxyls derived from the more hydrophilic acrylic acid which orient more at the particle–water interface.     

乳液聚合中保护胶体的研究进展

介绍了乳液聚合中保护胶体稳定聚合物乳液的机理,详细综述了保护胶体在乙烯基单体、共轭烯单体和丙烯酸酯类单体乳液聚合中的研究进展。指出了单体在保护胶体上的适量接枝是乳胶粒稳定的必要条件,因此,合理使用保护胶体在乳液聚合中有重要意义。     

Preparation of carboxylated polymer emulsion particles in which carboxyl groups are predominantly localized at surface layer by using the seeded emulsion polymerization technique

It was studied how to localize carboxyl groups at the particle surface in a preparation of styrene (S)/butyl acrylate (BA)/methacrylic acid (MAA) polymer emulsion. The relative distribution of carboxyl groups in the emulsion was determined by conductometric titration method: in serum, at surface, and inside particle. By seeded (two-stage) emulsion polymerization that S–BA–MAA terpolymer emulsion was first prepared at low pH and then second stage polymerization of S–BA was continued at high pH, S/BA/MAA polymer emulsion particles in which carboxyl groups are localized predominantly at the surface could be prepared.     

苯丙乳液碱增稠机理的研究

以苯乙烯、丙烯酸、丙烯酸丁酯和甲基丙烯酸甲酯为单体，采用乳液聚合合成了苯丙乳液。讨论了所用的乳化剂及其用量，并以特定的工艺所引起的苯丙乳液粒子表面羧基富集，着重讨论了其加碱增稠的机理，为苯丙乳液生产工艺的制定提供理论依据。     

Polymerization behavior and distribution of carboxyl groups in preparation of soap-free carboxylated polystyrene latexes

Soap-free carboxylated polystyrene latexes have been prepared by copolymerizing acrylic acid (AA) in a wide range of the degree of neutralization using a slight amount of soap; and the distribution of carboxyl groups was investigated from the determination of carboxyl groups localized on the surface of particles (surface carboxyl groups). It appears that the degree of neutralization of AA or the amount of AA has a considerable effect on the rate of polymerization as well as the stability of the polymerization system. At a degree of neutralization of approximately 0.80, stable latexes are obtained at a sufficient rate of polymerization. It is also clarified that the distribution of carboxyl groups is governed substantially by the degree of neutralization of AA. At a degree of neutralization of 0.80, approximately 30% of the total carboxyl groups are localized on the surface of particles. The amount of AA or the particle diameter seems to have little effect on the distribution of carboxyl groups.     

丙烯酸高级酯共聚物组成与其无皂乳液稳定性研究

制备了不同分子结构的丙烯酸高级酯共聚物无皂乳液,测定了丙烯酸和甲基丙烯酸十六酯的竟聚率,考察了共聚物的组成对无皂乳液电解质稳定性、机械稳定性和pH值稳定性的影响。结果显示,丙烯酸竟聚率为2.32,甲基丙烯酸十六酯竟聚率为0.59,随共聚物中丙烯酸组分含量增加,乳液粒子表面羧基含量增大,乳液机械稳定性和pH值稳定性提高,乳液适合在偏碱性条件下使用。     

Seeded emulsion polymerization of styrene: Incorporation of acrylic acid in latex products

Seeded batch emulsion polymerization of styrene and acrylic acid was studied. The influence of pH and acrylic acid content on the polymerization rate and the amount of carboxylic acid groups incorporated in the final latex products was investigated. The distribution of the functional groups over the aqueous phase, the latex particle surface, and the interior of the latex particle was determined using aqueous conductometric titration and nonaqueous potentiometric titration at intermediate and complete overall conversions. Combined with kinetic results, the carboxylic acid group distribution history provided valuable information about the process of incorporation of acrylic acid in latex products. Two‐step processes in which a shot of acrylic acid was performed in the last stage of the emulsion polymerization reaction were investigated as a strategy to increase the surface incorporation efficiency. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 875–885, 2000     

一种分散稳定剂的合成及应用

文章合成了一种阴离子型分散聚合稳定剂;特性粘数2～4dL/g,浓度20%,表观粘度200～300mPa·s该稳定剂兼有高分子和表面活性剂的特点,具有优异的分散稳定作用;使用该稳定剂合成的聚丙烯酸分散液,分散粒子总比表面积0.28m2/g,表面积平均粒径19.33μm,体积平均粒径为228.82μm。稳定期大于半年。     

Seeded emulsion polymerization of styrene: influence of acrylic acid on the particle growth process

The seeded batch emulsion copolymerization of styrene and acrylic acid was studied. The polymerization rate was investigated with pH as the main parameter. Some attempts were made to evaluate the average number of growing chains per particle during Stage II of the emulsion polymerization process. The final latex products were characterized by means of conductometric aqueous titration and potentiometric titration in an organic solvent mixture. The distribution of the acid groups over the aqueous phase, the particle surface, and the interior of the particles together with the kinetic results provided insight into important features governing the incorporation of acrylic acid. The results indicate that pH is the dominating parameter for the incorporation process. An optimal incorporation on the surface of the particles is observed for a low value of pH. In that case, all the acid groups are protonated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1186–1196, 2000     

Preparation of small-sized carboxylated latexes by emulsion polymerization using alkali-soluble random copolymer

Alkali-soluble random copolymer (ASR), poly(styrene/α-methylstyrene/acrylic acid) [M_n: 4,300; acid number: 190], was used as a polymeric emulsifier in the emulsion polymerization of styrene and methyl methacrylate, respectively. ASR containing a large number of carboxyl groups could form aggregates like micelles, and the solubilization ability of the aggregates was dependent on the neutralization degree of ASR. The polystyrene latexes prepared using ASR showed the small particle size (ca. 40 nm) and monodispersed particle size distribution. On the other hand, the particle size distribution of poly(methyl methacrylate) latexes became broader as the neutralization of ASR increased. This could be explained by the effects of water solubility of the monomer and the neutralization degree of ASR on particle formation. Thin layer chromatography/flame ionization detector analysis confirmed that the grafting reaction of polystyrene to ASR occurred during emulsion polymerization. The ζ potentials of final latexes showed high values due to ASR that was adsorbed and grafted on the surface of the latex particle. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 543–550, 1998     

Carboxyl-stabilized emulsion polymers

An emulsion polymerization process is reported for the production of high-solids, surfactant-free styrene/butadiene latices. With this procedure latices require no surfactants, for stabilization is built into the emulsion particles by means of copolymerized acid monomers. This “pH variable” method is a two-step, batch-on-batch polymerization. In the first step, all the ingredients are present in the reaction mixture; however, only enough styrene and butadiene is added to reach a low solids content. This step, carried out at low pH, produces a carboxylated seed latex. On raising the pH of this low-solids emulsion, the copolymerized carboxyl groups ionize, and the now highly charged latex particles provide an expedient locus for the generation of stable, highsolids latices. Neutralizing the carboxyl groups of the seed latex before adding the remaining monomers induces the highly hydrophilic carboxyl anions to remain on the surface of the latex particle, nearer to the aqueous environment of the surrounding media. Hence, the maximum stabilization capacity of the acid monomers is utilized. The process was evaluated to ascertain the effects of the following variables: the particle size and solids content of the first step, the nature of the base used to raise the pH, the pH of the dispersion prior to the second step, and the effect of the acid monomer on the latex stability.     

无皂乳液聚合制备增稠剂及其性能研究

以聚乙烯醇为胶体保护剂、N,N′-亚甲基双丙烯酰胺为交联剂,用过硫酸钾-亚硫酸钠引发丙烯酸、丙烯酰胺、丙烯酸丁酯进行无皂乳液聚合,以制备高性能的涂料印花增稠剂,所得产品稳定性好、增稠效果优良。并研究了交联剂、引发剂、胶体保护剂的用量等聚合条件对增稠剂性能的影响。引发剂用量增加,增稠剂黏度下降,黏度指数上升。交联剂用量增加可使增稠剂的黏度出现极大值,但黏度保留率下降。采用PVA作为胶体保护剂,产品增稠能力强,稳定性好,耐电解质等综合性能均较好。     

以聚乙烯醇为保护胶体的乳液与部分官能团的接枝反应研究

主要研究了在以聚乙烯醇为保护胶体的醋酸乙烯乳液聚合中,乳液与环氧丙烯酸酯、聚氨酯、硅烷等官能团的接枝反应.在以过硫酸铵为引发剂、以聚乙烯醇为保护胶体的醋酸乙烯乳液聚合中,乳液与上述各类官能团间发生的接枝反应直接影响乳液的黏度、固体含量、剪切强度等宏观性质.研究发现官能单体脂肪醇聚氧乙烯醚、丙烯酸异辛酯(2-EHA)等单体和丙烯酸(AA)与乙烯基三乙氧基硅烷共同作用时对乳液的宏观性质影响显著.     

甲基丙烯酸甲酯的乳液聚合

以甲基丙烯酸甲酯为主要原料,过硫酸铵为引发剂,OP-10和十二烷基苯磺酸钠(1∶1)为混合乳化剂,聚乙烯醇为分散剂,用乳液聚合的方法合成了聚甲基丙烯酸甲酯乳液.考察了产品的转化率、粒径、红外光谱、粘度及其热稳定性并进行了表征.与传统的聚合方法相比,该聚合方法具有乳液粒径小且分布均匀、聚合速度快、所获得的聚合物纯度较高以及合成的聚乳液可以直接应用等优点.     

Stability of carboxylated poly(butyl acrylate) latices during semibatch emulsion polymerization

The stability of latex particles in the semibatch emulsion polymerization of butyl acrylate (BA) in the presence of 0–10% acrylic acid (AA) was investigated. The amount of coagulum (i.e., large flocs caused by intensive coagulation) can be greatly reduced by an increase in the concentration of sodium lauryl sulfate (SLS) in the monomer emulsion feed. On the other hand, increasing the concentration of SLS in the initial reactor charge can result in an increase in the percentage of the particle volume change (i.e., a measure of the degree of limited flocculation) later in the process. Both the scrap and percentage of the particle volume change increase with an increase in the electrolyte concentration. Both the coagulation and secondary nucleation process can result in a significant deviation from the Novak model. Experimental data also show that latex particles comprising pure BA can lose their stability rapidly at higher total solids content because of the crowding effect. Incorporation of only 5% AA into the emulsion polymers greatly improves the latex stability. © 1996 John Wiley & Sons, Inc.     

VAc-BA-AA三元乳液共聚合研究

用 (NH4) 2 S2 O8-Na2 SO3氧化还原体系引发醋酸乙烯 (VAc) -丙烯酸丁酯 (BA) -丙烯酸 (AA)三元乳液共聚合 ,研究了引发剂、乳化剂、聚合反应条件对聚合转化率 ,乳液粘度和乳液稳定性的影响。实验结果表明体系动力学与经典 Smith-Ewart的乳液合理论不一致。反应速率 (Rp)随着乳化剂浓度的增加而增大 ,乳液的稳定性受乳化剂浓度的影响。聚合温度、引发剂浓度、丙烯酸的浓度对三元共聚乳液的稳定性也有影响     

STUDIES ON SYNTHESIS OF SILICA SOL-ORGANIC POLYMER COMPOSITE EMULSION

An emulsion of polystyrene/poly (butylacrylate-methyl methacrylate acrylic acid) core/shell latex particles (PS/P (BA-MMA-AA)) has been prepared by use of three synthetic methods. The effects of synthetic methods on the distribution of carboxyl groups in latex particles were studied. The results show that the seed emulsion polymerization in which the pre-emulsified monomers were added by dropping method to the second stage is the best technique for obtaining the optimum distribution of carboxyl groups on the surface of the latex particles. Furthermore, by using PS/P (BA-MMA-AA), a type of novel composite emulsion of silica sol-PS/P (BA-MMA-AA) was synthesized with the above method. By observation through transmission EM, the morphology of the latex particles obtained shows that a composite structure has been formed between silica sol particles and organic polymer particles.     

含磷丙烯酸酯乳液的制备及性能研究

以甲基丙烯酸酯基烷氧基磷酸酯（PAM-100）、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸等为单体,采用预乳化半连续乳液聚合法制备了含磷丙烯酸酯共聚乳液。研究了PAM-100用量对单体转化率、乳液稳定性和乳胶粒粒径及分布的影响,并通过红外光谱（FT-IR）和微型燃烧量热分析（MCC）对乳胶膜的结构及性能进行表征。结果表明：PAM-100的加入有利于提高乳液聚合的稳定性及乳胶膜阻燃性能。与纯丙乳液相比,当PAM-100用量为10wt%时,含磷丙烯酸酯共聚乳液的乳胶粒表面Zeta电位绝对值由34.6mV提高至41.3mV,粒径由169nm下降至132nm;同时,含磷丙烯酸酯乳胶膜热释放速率峰值（pHRR）由391.1W/g下降至333.3W/g,到达pHRR的时间由264s推迟至300s。     

丙烯酸乳液胶粘剂的研究

采用半连续乳液聚合工艺,以MMA、BA、AA等为主要单体,加入乳化剂、引发剂、交联剂,经共聚反应,合成自交联型丙烯酸酯乳液胶粘剂。讨论了聚合机理,考查了固含量、离子稳定性、离心稳定性、剥离强度、拉伸强度、粒径、黏度等多项性能;根据综合的性能测试,分析了单体种类及配比、共聚物的玻璃化温度、丙烯酸用量、乳化剂用量及配比、引发剂用量、温度等因素对乳液型胶粘剂性能的影响,得出了最适宜的反应条件和胶粘剂最佳配方。通过性能对比,表明自交联型丙烯酸酯乳液胶黏剂性能更为优异。