GAD室温自交联乳液的合成及其涂膜性能

合成了含有缩水甘油基、羧基和胺基的多层核壳型室温自交联乳液，研究了聚合温度、乳化剂用量和加料速率对所得乳液性能及其涂膜性能的影响。研究表明，聚合温度升高使乳胶膜的交联密度降低，而涂膜耐水性和乳液贮存稳定性在50℃呈现最佳值。在乳化剂含量为2%时，涂膜的交联密度最大且耐水性最佳，而乳液的贮存稳定性能随乳化剂量的增加而增大。加大乳化单体滴加速率，乳液贮存稳定性降低，乳胶膜的交联密度增大。     

自交联型丙烯酸酯共聚物乳液的研究

以羟甲基丙烯酰胺、丙烯酸作为活性单体，采用种子乳液聚合法制得四元体系自交联型丙烯酸酯共聚物乳液。用透射电镜观察了乳胶粒的微观形态，并对共聚物乳液的流变性，稳定性等进行了测试，考察了羟甲基丙烯酰胺和丙烯酸的含量、聚合方式对共聚物乳液性能的影响。     

含氨基、羟基丙烯酸乳液聚合的稳定性

采用间歇及半连续乳液聚合方式,以过硫酸铵/亚硫酸钠为引发体系,合成了甲基丙烯酸甲酯/丙烯酸丁酯/甲基丙烯酸羟乙酯/甲基丙烯酸二氨基乙酯四元共聚物胶乳.系统研究了乳化剂种类和浓度、聚合温度、乳化单体进料方式及进料速率对聚合过程稳定性的影响.聚合温度降低,乳化单体进料速度减慢有利于聚合过程的稳定,采用种子半连续聚合方式比间歇聚合过程更稳定,乳化剂浓度的增加有利于聚合稳定性的提高和乳胶粒子的均匀化.     

室温交联型硅丙微胶乳的合成研究Ⅲ.聚合工艺对聚合稳定性及胶膜性能的影响

采用两种聚合工艺(种子微乳液聚合法和单体预乳化法)分别合成了室温交联型有机硅改性丙烯酸酯聚合物微胶乳，研完了不同工艺条件对聚合稳定性、乳胶粒径和胶膜的结构性能的影响．     

改性丙烯酸乳液合成及性能研究

通过核壳乳液聚合法合成了烷基丙烯酸酯磷酸酯改性的丙烯酸乳液,讨论了聚合温度、乳化剂、磷酸酯的加入方式和用量、pH值等因素对乳液合成以及涂膜性能的影响。结果表明:聚合温度控制在75～80℃之间较为合适,使用了烷基丙烯酸酯磷酸酯进行改性的乳液,单体转化率和固含量提高,凝胶率以及涂膜吸水率明显下降,乳液的稳定性得到提升。当聚合温度为78℃,磷酸酯占单体总质量0.5%(wt)、反应体系pH值在5左右以及采用延后滴加磷酸酯单体的方式时,能够提高乳液耐水等性能以及涂膜的交联度,合成性能优异的磷酸酯改性丙烯酸乳液。     

含吡咯烷酮基丙烯酸酯类单体的合成及聚合

轻度交联的聚甲基丙烯酸2-羟乙酯(HEMA)是众所周知的医用水凝胶,即所谓的“Hvdron”。但其吸水率一般在59%(EWC为37%),并不尽人意。近年来,为了提高这类水凝胶的亲水性及生物相容性,常用一些亲水性的烯类单体进行表面改性或通过共聚以达到此目的,N-乙烯基吡咯烷酮是较为常用的这类单体之一。本文合成了含吡咯烷酮基丙烯酸酯类的单体,即丙烯酸2-N-吡咯烷酮基乙酯(PyEA),甲基丙烯酸2-N-吡咯烷酮基乙醋(PyEMA),并研究了这两种单体在甲基丙烯酸二甲氨乙酯(DMAEMA)与过硫酸钾(KPS)所组成的氧化还原引发体系下的聚合。     

种子乳液聚合的研究进展

种子乳液聚合法因具有乳液稳定性更好、粒径分布窄、易控制等优点,在乳胶粒子设计及制备各种功能性胶乳方面具有重要作用,是制备高固含量乳液及具有核壳结构乳液的最常见最简便的方法.本文综述了近年来种子乳液的聚合工艺、聚合机理, 包括接枝机理、互穿聚合物网络机理、聚合物沉积机理、种子表面聚合机理和离子键合机理等,以及种子乳液聚合在乳胶粒子设计方面的应用研究进展,并讨论了影响种子乳液聚合的各种因素.     

双连续相微乳液辐射聚合制备多孔材料的研究

利用6 0 Co γ射线在室温下辐照双连续相微乳液体系以制备多孔聚合物材料 ,试图在控制多孔材料的微孔结构形态和减少微乳液聚合过程中的相分离方面做一些探索 .通过电导率的测量分析微乳液的结构类型 ,并确定微乳液的双连续相区域范围 .微乳液聚合后所得的样品的孔结构和聚合前的微乳液结构类型有关 ,扫描电镜和热重分析的结果表明双连续相微乳液在聚合时容易发生相分离 ,未必能够得到开孔结构的聚合物 .但适当控制聚合前微乳液的组成 ,如选择合适的水油比例、交联剂的用量和加入一些功能性单体 (如甲基丙烯酸或丙烯酸钠 ) ,可以有效地抑制相分离 ,调节所得聚合物的结构形态 .     

丙烯酸酯纳米乳液的制备与表征

将甲基丙烯酸羟乙酯(HEMA)与甲基丙烯酸(MAA)或丙烯酸(AA)用作甲基丙烯酸甲酯(MMA)／丙烯酸丁酯(BA)乳液聚合体系的反应性助乳化剂，采用一种改进的微乳液聚合方法，合成了高单体／乳化剂比例(大于40：1)的聚丙烯酸酯纳米乳液．讨论了引发剂、乳化剂、助乳化别对乳胶粒大小和胶膜吸水率的影响，并对乳液的流体力学行为，共聚物的拉伸行为及耐水性等进行了研究．     

含羧基/环氧树脂的丙烯酸酯共聚物乳液的制备与交联(Ⅳ)——混合乳液的制备及其中温交联

研究了含羧基丙烯酸酯乳液和含环氧树脂乳液的混合和交联反应。实验结果表明,混合乳液具有较高的机械稳定性,在室温下可以稳定贮存5个月以上,证实了在叔胺促进剂作用下,交联固化机理为单酯化反应,混合乳液可在中温(<100℃)下固化,涂膜具有优良的物理性能。     

聚(甲基丙烯酸N,N-二甲氨基乙酯)的温度和pH敏感性及其对乳液稳定性的影响

甲基丙烯酸N,N-二甲氨基乙酯的均聚物(PDMAEMA)在水中的溶解性具有温敏性,即低温溶解、高温不溶,而且其低临界溶液温度(LCST)与pH密切相关.本文重点考察了PDMAEMA水溶液在不同温度、pH值、溶液离子强度时的相转变特性,并研究了水溶液中乳化剂对PDMAEMA的疏水相互作用和增溶稳定作用.将PDMAEMA的温敏相转变行为同有关乳液的稳定性相关联,揭示了改善乳液稳定性的内在机制.     

Microgel formation in emulsion copolymerization: II. Seeded polymerization

Microgel formation in seeded emulsion copolymerization of methyl methacrylate and ethylene glycol dimethacrylate is investigated both experimentally and theoretically. By introducing seed latex, the network structure development can be changed significantly. Even when the crosslinking density development takes a similar pattern as the crosslinking copolymerization in homogeneous media, the molecular weight development shows both types of behavior that is characteristic of emulsion polymerization without seed latex and of homogeneous polymerization, depending on the primary polymer chain length and the mole fraction of the divinyl monomer used. Once the microgels are formed, the weight-average molecular weight increases just linearly with conversion due to a very small locus of polymerization. The present investigation reveals important characteristics of gelation phenomena in a limited space. © 1996 John Wiley & Sons, Inc.     

Preparation of MMA－BA－DMAEMA Nanosized Latex

The terpolymer latex of methyl methacrylate (MMA)/butyl acrylate (BA)/ dimethyl aminoethyl methacrylate (DMAEMA) with diameter of less than 100 nm was prepared by seeding semi-continuous emulsion copolymerization using APS (ammonium pcrsulfate) / TMEDA (N,N,N,N-tetramethylethylenediamine) as the redox initiators and SDS (sodium dodecylsulfate) and OP (P-octylpolyethylene glycol phenylether) as co-emulsifiers. The factors that influenced the process stability of the copolymerization and the particle size of the latex were investigated. The addition of aqueous ammonia as coagulation inhibitor provided better process stability of the copoly- merization. The addition of acetic acid as the acidification agent caused a remarkable reduction of the latex particle size.     

接枝微球PMAA-HEMA/NVP对溶菌酶的吸附行为与吸附机理

采用反相悬浮聚合法制备了甲基丙烯酸羟乙酯(HEMA)与N-乙烯基吡咯烷酮(NVP)的交联共聚微球HEMA/NVP,然后采用"接出"法,实施了甲基丙烯酸(MAA)在交联微球表面的接枝聚合,制得了接枝微球PMAA-HEMA/NVP.以溶菌酶(LYZ)为模型碱性蛋白,深入研究了接枝微球PMAA-HEMA/NVP对碱性蛋白的吸附性能与吸附机理.测定了微球PMAA-HEMA/NVP的zeta电位,考察了PMAA接枝度、介质pH值及离子强度等因素对体系吸附性能的影响.结果表明,在较大的pH范围内,接枝微球PMAA-HEMA/NVP的zeta电位为绝对值较大的负值,即其表面携带有高密度的负电荷.在强静电相互作用的驱动下,接枝微球PMAA-HEMA/NVP对溶菌酶表现出很强的吸附能力.随介质pH值的增高,接枝微球对溶菌酶的吸附容量呈现先增大后减小的变化趋势,在与溶菌酶等电点接近的pH值处(pH=9),具有最大的吸附容量(90mg.g-1);离子强度对接枝微球的吸附能力也有较大的影响,当pH9时,溶菌酶吸附容量随NaCl浓度的增高而减小;当pH9时,吸附容量随NaCl浓度的增高而增大.     

Preparation of polyacrylate–polysiloxane core–shell latex particles

Crosslinked polymer seed latexes of butyl acrylate, methyl methacrylate and methacrylic acid were synthesized with ethylene glycol dimethacrylate as a crosslinking agent in a first step. Three different processes of seeded emulsion polymerization were used to prepare an outlayer of polysiloxane on the above seed latex particles: (A) direct anionic polymerization of D₄ (octamethyl tetracyclosiloxane) catalyzed by potassium hydroxide; (B) direct cationic polymerization of D₄ onto the seed catalyzed by dodecylbenzene sulfonic acid; (C) a vinyl-containing polysiloxane prepared by copolymerization of D₄ and vinyl septamethyl tetracyclosiloxane was added before the D₄ cationic polymerization. Characterization by transmission electron microscopy showed that only process C provided satisfactory results. Film hardness was measured, and the latex film from process C demonstrated the lowest hardness of all the films. The mechanism of polymerization is discussed.     

Double-responsive polymer brushes on the surface of colloid particles

Well-defined poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes were synthesized on the surface of polystyrene latex particles by atom transfer radical polymerization (ATRP). It was found that the surface-initiated polymerization of DMAEMA catalyzed by CuCl/CuCl(2)/bpy was under good control in the solvent of acetone/water at ambient temperature (35 degrees C). High-density PDMAEMA brushes with low polydispersity (PDI 1.21) were obtained. TEM results demonstrate that the PDMAEMA-grafted particles have core-shell structure. Dynamic light scattering studies indicate that the particles with PDMAEMA brushes are both pH and temperature responsive.     

EFFECT OF 2-HYDROXYETHYL METHACRYLATE ON SEMIBATCH EMULSIFIER-FREE EMULSION COPOLYMERIZATION OF METHYLMETHACRYLATE AND BUTYL ACRYLATE

IINTRODUCTIONSemibatchemulsionpolymerizationisanimportalmethodfortheproductionofpolymersforthecoatingsandadhesivesindustries.Thetraditionallatexproductsaregenerallystabilizedbyemulsifiers.However,theemulsifiersremaininginthelatexproductcanhaveanegativeeffectontheapplicationpropertiessuchasadhesiontosubstratesandfilmformationandwaterresistanceofthecoatingmaterials,becausethesmallandmobileemulsifiermoleculestendtomigratetothesurfacelayerofthepolymericfilm.Withtheemulsifier-freeemulsionpolym…     

EFFECT OF 2—HYDROXYETHYL METHACRYLATE ON SEMIBATCH EMULSIFIER—FREE EMULSION COPOLYMERIZATION OF METHYL METHACRYLATE AND BUTYL ACRYLATE

The semibatch emulsifier-free emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate(BA) in the presence of 2-hydroxyethyl methacrylate(HEMA) initiated by K2S2O8(PSP) was studied.The latex particles can maintain an appreciable stability during the emulsifier-free emulsion copolymerization of MMA and BA in the presence of HEMA.The average particle diameter increase with an increase of total solids content,HEMA content,PSP content,ionic strength of the system and monomer feed rate,and decrease with the monomer feed ration from 3/1 (MMA/BA:molar ration).to 1/3.The stability of this reaction system is improved by adding HEMA as nonionic comonomer,High solids content (50%) latex with monodisperse particle can be obtained using this process.     

Preparation and characterization of poly (N-isopropylacrylamide-co-dimethylaminoethyl methacrylate) microgel latexes

Monodisperse cationic thermosensitive latex microgels have been prepared by radical-initiated precipitation polymerization of N-isopropylacrylamide, methylene bisacrylamide using 2,2′-azobis(2-amidinopropane hydrochloride) as an initiator and dimethylaminoethyl methacrylate (DMAEMA) as a cationic monomer. The final microgel latexes were characterized with respect to water-soluble polymer formation, particle size and size distribution. Adding cationic monomer (DMAEMA) was found to drastically affect the particle size, but not the size distribution as observed both by transmission electron microscopy and quasielastic light scattering (QELS). However, too high a DMAEMA concentration in the feed composition led to enhanced formation of water-soluble polymer. The volume phase-transition temperature of cleaned microgels examined by QELS (particle size versus temperature) was found to be around 32 °C and was slightly dependent on the concentration of the cationic monomer. The volume phase-transition temperature range becomes broader with increasing cationic monomer concentration. In addition, the pH of the polymerization medium was found to affect the final particle size and amount of water-soluble polymer formed. Received: 29 March 2001 Accepted: 2 July 2001