可聚合乳化剂对St-BA共聚乳液稳定性及羧基分布的影响

以苯乙烯(St)和丙烯酸丁酯(BA)为主单体,以丙烯酸和丙烯酸-2-羟基丙酯为功能单体制备了St-BA共聚乳液,研究了可聚合乳化剂烯丙氧基壬基酚聚氧乙烯(10)醚单磷酸(ANPEO10-P1)对共聚乳液的聚合稳定性、化学稳定性、羧基分布及乳胶膜耐水性、剥离强度等性能的影响。结果表明:与常规乳化剂十二烷基硫酸钠(SDS)相比,使用可聚合乳化剂ANPEO10-P1能有效地改善乳液的性能。通过电导滴定发现,乳化剂对乳液不同区域的羧基分布有较大的影响,因而影响乳胶膜的耐水性和剥离强度。     

可聚合乳化剂的类型及乳液聚合

介绍了一些新型的乳化剂－可聚合乳化剂,分别亲水基类型,可聚合基团类型和可聚合基团在分子中位置等对其进行了分类,综述了各类可聚合乳化剂研究及应用情况,展望了其发展前景。     

一种马来酸酯类可聚合乳化剂

以马来酸酐和十二醇聚氧乙烯醚-15(AEO15)为原料,通过一条绿色合成路线,合成了同时具有阴离子和非离子结构特点的马来酸酯类可聚合乳化剂。将可聚合乳化剂与传统乳化剂十二烷基硫酸钠(SDS)分别应用到醋酸乙烯酯-丙烯酸丁酯-叔碳酸乙烯酯-甲基丙烯酸六氟丁酯的半连续式乳液共聚合时发现,由可聚合乳化剂得到的乳胶液电解质稳定性、贮存稳定性及冻融稳定性要优于传统乳化剂,而且使用可聚合乳化剂所成膜的耐水性也得到提高。     

反应型乳化剂的合成及其在乳液聚合中的应用

合成了2类可聚合乳化剂马来酸酐单酯硫酸钠和马来酸酐单酯磺酸钠，测定了产物的纯度和临界胶束浓度，研究了它们在苯乙烯/丙烯酸丁酯/丙烯酸三元乳液聚合中的转化率。以十二烷基硫酸钠为参照物，用可聚合乳化剂制备的乳液对电解质的稳定性有很大的提高，干胶膜的耐水性和拉伸强度得到了显著改善。     

可聚合乳化剂的合成及其在水性复膜胶中的应用

报道了马来酸酐单酯羧酸钠的合成,从理论上分析马来酸酐单酯羧酸钠作为水性复膜胶乳化剂的可行性,并与工业上可聚合乳化剂SVS、HPMAS、HAPS及常规的复合乳化剂K-12和OP-10进行比较,得出马来酸酐单酯羧酸钠A/B可用于水性复膜胶的制备,且性能优于SVS、HPMAS、HAPS、K-12和OP-10。     

可聚合乳化剂的类型及乳液聚合（续）

介绍了一些新型的乳化剂－可聚合乳化剂,分别按亲水基类型,可聚合基因类型和可聚合基因在分子中位置等对其进行了分类。综述了各类可聚合乳化剂研究及应用情况,展望了其发展前景。     

可聚合乳化剂对丙烯酸乳液性能的影响

用甲基丙烯酸甲酯、丙烯酸丁酯及丙烯酸-2-羟丙酯作主单体，丙烯酸作功能单体合成了水性涂料用纯丙乳液，比较了常规乳化剂和可聚合乳化剂对丙烯酸酯乳液性能（包括聚合稳定性，化学稳定性等）的影响，同时用透射电镜观察了粒子形态。结果表明：使用可聚合乳化剂烯丙氧基壬基酚聚氧乙烯（10）醚硫酸铵（DNS-86），能有效改善乳液的性能。     

不同可聚合乳化剂对丙烯酸酯乳液性能的影响

使用3种可聚合乳化剂制备了水基胶粘剂用丙烯酸酯乳液。考查了可聚合乳化剂与单体间的共聚性能,比较了各乳化剂用量对丙烯酸酯乳液的固含量和单体转化率、乳液稳定性(聚合稳定性、贮存稳定性、冻融稳定性)以及乳胶膜的耐水性等性能的影响。结果表明,乳化剂1-烯丙氧基-3-(4-壬基苯氧基)-2-丙醇聚氧乙烯(10)醚(ANPEO10)、烯丙氧基壬基酚聚氧乙烯(10)醚双磷酸(ANPEO10-P2)和烯丙氧基壬基酚聚氧乙烯(10)醚硫酸铵(DNS-86)均成功地聚合到丙烯酸酯聚合物中。用3种乳化剂制备的乳液性能各有特点。使用DNS-86以及ANPEO10-P2制得的乳液的贮存稳定性好;用ANPEO10制得乳液的冻融稳定性最好;使用DNS-86制得的乳胶膜的耐水性最好。3种乳化剂用量均为2.0%时,制得的乳液综合性能最好。     

可聚合乳化剂合成含氟丙烯酸酯无皂乳液及其性能

以甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）、甲基丙烯酸六氟丁酯（HFMA）等为主要原料,采用预乳化种子乳液聚合法合成了含氟丙烯酸酯无皂乳液,考察了可聚合乳化剂烯丙氧基壬基酚聚氧乙烯（10）醚硫酸铵（DNS-86）和HFMA的用量对无皂乳液的电解质稳定性和涂膜耐水性的影响。利用傅里叶红外光谱、差示量热扫描仪及热重分析对氟丙乳液涂膜进行了表征。结果表明：与传统乳液聚合得到的乳液及相应的涂膜相比,无皂乳液的耐电解质性能和涂膜的耐水性都有一定的提高,含氟单体有效地参与了聚合,涂膜的疏水性大大增强,耐热性显著提高。     

新型可聚合乳化剂及其在乳液聚合中应用

综述了可聚合乳化剂的分类、性能与应用,比较了可聚合乳化剂与传统乳化剂在乳液聚合中的优缺点,讨论了可聚合乳化剂的溶液性能,指出了可聚合乳化剂的发展趋势。     

聚氨酯预聚体——可聚合乳化剂用于MMA乳液聚合动力学及聚合稳定性研究

将合成的聚氨酯预聚体可聚合乳化剂（APUA）用于甲基丙烯酸甲酯（MMA）乳液聚合体系中，研究了不同引发剂体系和乳化剂对聚合体系的聚合稳定性和动力学影响，并与SDS乳化剂进行了对照。结果显示，用油溶性引发剂（AIBN）和水溶性引发剂（K2S2O8）都能引发该体系的聚合反应，而且聚合速率和转化率都相当高。用AIBN作引发剂时，APUA和SDS两种乳化所对应的动力学曲线不同，但APUA比SDS的聚合速率大得多，其分别类似于微乳液聚合（miniemulsion)和微悬浮聚合（microsuspention)，且聚合过程中会产生一定的凝胶。当乳化剂APUA用量适合时，凝胶量极少，聚合体系是稳定的；而当用K2S2O8作引发剂时，两乳化剂对应动力学曲线相似，聚合过程不产生凝胶。但当引发剂用量较大并以APUA作乳化剂时，在聚合过程中会出现全部粒子突然粗化现象，而以SDS作乳化剂没有出现这一现象。     

可聚合乳化剂DNS-6对丙烯酸酯乳液稳定性的影响

使用可聚合乳化剂烯丙氧基壬基酚丙醇聚氧乙烯（10）醚硫酸铵（DNS-86）,通过半连续聚合工艺制备了水基丙烯酸酯乳液。考查了DNS-86对乳液的固含量、转化率、乳胶粒的大小及形态、Zeta电位以及各种稳定性（聚合稳定性、化学稳定性及冻融稳定性）的影响。与常规乳化剂十二烷基硫酸钠（SDS）制备的丙烯酸酯乳液性能进行了对比。结果表明,DNS－86因反应活性大,能与丙烯酸酯单体进行共聚,制得的乳胶粒大小均一,形态规整,乳液的稳定性得到改善。     

Preparation of planar and oblate particles from emulsion polymerization using polymerizable comb-like branched emulsifiers

This paper presents a method for preparation of planar polymeric microstructures by emulsion polymerization using polymerizable branched emulsifier. Planar, oblate and spherical particles can be prepared by changing the volume and functionality of the hydrophobic tail of the comb-like polymerizable emulsifier, together with altering the monomers. Emulsifiers with bulky tails favored the formation of planar microstructure. The polymerizable emulsifiers were immobilized on the latex particles. Hindered desorption of the emulsifier from the latex improved the latexes' stability and facilitate the formation of planar and oblate particles. The polymerization conversion also depends on the molecular characteristics of the emulsifiers and monomers.     

Semibatch emulsion polymerization of butyl acrylate. II. Effects of emulsifier distribution

The effects of emulsifier distribution ratio between the initial charge and the feed on particle formation and kinetics of butyl acrylate emulsion polymerization, using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator, were investigated. The number of particles increased with initial emulsifier concentration in the reactor charge. It was shown that traditional ranking, in terms of number of particles produced, of semibatch emulsion polymerization with monomer emulsion feed is not always justified and a semibatch emulsion polymerization can produce far more particles than a conventional batch emulsion polymerization. The number of polymer particles was found to be practically independent of the emulsifier distribution ratio between the charge and the feed for a high overall emulsifier concentration, while for a low overall emulsifier concentration, the number of particles increased with initial loading of the emulsifier. The polydispersity index (PDI) of the final latexes showed a minimum with emulsifier distribution. A bimodal particle size distribution, and a latex with a large PDI, was obtained when there was no emulsifier in the charge. As the initial emulsifier charge increased, a unimodal PSD with a smaller PDI was obtained. With higher proportions of emulsifier in the initial charge, the PDI rose again due to particle nucleation at monomer‐starved conditions, and a skewed unimodal PSD was obtained. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 582–597, 2001     

用可聚合乳化剂制备氟化丙烯酸酯无皂乳液

以丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸三氟乙酯为基本原料,用可聚合乳化剂,通过连续滴定方法制备氟化丙烯酸酯无皂乳液。讨论了不同乳化剂和用量以及乳液预乳化稳定性等对转化率的影响。结果表明,在相同的乳液聚合体系中,采用可聚合乳化剂制得的无皂乳液,其胶膜表面能比使用一般乳化剂体系的为低。     

Semi-continuous emulsion copolymerization of butyl methacrylate with polymerizable anionic surfactants

Two polymerizable anionic surfactants sodium 4-(ω-acryloyloxyalkyl)oxy benzene sulfonate (SABS-n, n=8 or 10) have been successfully used in the semi-continuous emulsion copolymerization with butyl methacrylate (BMA). After generating seeding particles in an emulsion consisting SABS-8 or SABS-10 and small amount of BMA using a redox initiator ammonium persulfate (APS)/tetramethylethylenediamine (TMEDA) at room temperature, most of BMA was added drop-wise to the polymerizing emulsion system during a period of 4-8 h. These emulsion copolymerizations produced nanosized latexes with high polymer/surfactant weight ratios up to about 12/1 and nearly monodisperse particles ranging from 18 to 33 nm in diameter. X-ray photoelectron spectroscopy results showed that SABS-n was significantly enriched on the surface of latex particles. The effects of concentrations of SABS-n, BMA, and APS/TMEDA and the latex characteristics during the continuous addition of monomer were studied. A possible polymerization mechanism was proposed.     

Effect of polyoxyethylene emulsifier composition on the course of emulsion polymerization of vinyl acetate

Three different emulsifier types from vinyl acetate monomer and methoxypolyoxyethylene (35: 65, 27: 73 and 19: 81wt: wt%) were prepared in the presence of benzoyl peroxide using a macroradical initiator technique. Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance were carried out to confirm the structure of the copolymers obtained (emulsifiers). The emulsion polymerization of vinyl acetate initiated by sodium persulphate as an initiator in the presence of non-ionic (polyoxyethylene (POE) type) emulsifier has been kinetically investigated. The rate of polymerization was found to be proportional to the 0·33, 0·40 and 0·44 power of the emulsifier concentration and to the 0·71, 0·79 and 0·87 power of the initiator concentration. The apparent activation energy was found to be 135, 56·5 and 38kJmol^-1 for 65wt%, 73wt% and 81wt% POE, respectively. The particle size was observed to increase with increasing initiator concentration and to decrease with increasing emulsifier concentration. The reaction order with respect to the emulsifier concentration (number of particles versus emulsifier concentration) was found to be 0·10, 2·05 and 0·89 for 65wt%, 73wt% and 81wt% POE, respectively. ©1997 SCI     

可聚合型离子液体乳化剂的性能及在SAN合成中的应用

甲基丙烯酸二甲氨基乙酯与溴代烷烃反应合成可聚合离子液体——甲基丙烯酸二甲氨基乙酯丁基溴盐([DMC4]Br)、甲基丙烯酸二甲氨基乙酯癸基溴盐([DMC10]Br)、双甲基丙烯酸二甲氨基乙酯丁基溴盐([DM-C4-DM]Br2)和双甲基丙烯酸二甲氨基乙酯癸基溴盐([DM-C10-DM]Br2)。采用1HNMR和FTIR对其结构进行了表征。用电导率法测得其临界胶束浓度分别为16.20、11.20、25.61和16.13 mmol/L。分别以[DMC10]Br、[DM-C10-DM]Br2和十二烷基磺酸钠(SDS)为乳化剂制备了苯乙烯-丙烯腈共聚物(SAN);当[DM-C10-DM]Br2添加量(以单体总质量计,下同)为4%时,所制备的SAN单体转化率为90.2%;粒径为320.3 nm;SAN主链热分解起始温度为353℃;制备后废水的化学需氧量(COD)为937mg/L。该乳化剂制备的SAN的主链热分解温度比SDS制备的SAN提高了22℃,废水COD降低了1512 mg/L。