聚硅氧烷/丙烯酸酯核/壳复合胶乳的粒径分布与成核机理

通过种子乳液法合成出具有高有机硅含量核 壳结构的聚硅氧烷 丙烯酸酯复合粒子 .研究了聚合方法、乳化剂浓度、引发剂浓度、单体滴加速度等工艺条件对复合乳液粒径尺寸、分布与形态的影响 ,并对复合乳液的成核机理进行了探讨 .研究表明 ,乳化剂浓度对乳液粒子的粒径分布和形态、结构有显著影响 ,引发剂浓度增加将使粒子粒径减小 ;相对一次投料法 ,种子乳液法生成的粒子分布窄 ,具有明显核壳结构 ,通过壳层单体滴加速度可以控制粒子的粒径尺寸和分布 ;而壳层丙烯酸酯聚合物主要是在聚硅氧烷种子表面的“过渡层”聚合、富集而成 .     

Polar Gradient Latex Particles with Hydrophilic Core and Hydrophobic Shell Prepared via Multistep Emulsion Polymerization

Monodisperse polar gradient particles were synthesized via a three‐step emulsion polymerization using poly(butyl acrylate‐methyl methacrylate‐methacrylic acid‐ethylene glycol dimethacrylate) (P(BA‐MMA‐MAA‐EGDMA)) as core, poly(methyl methacrylate‐methacrylic acid‐styrene) (P(St‐MMA‐MAA)) as interlayer and polystyrene (PSt) as shell. The particle growth and encapsulation in each emulsion polymerization step were followed by transmission electron microscopy (TEM), dynamic light scattering (DLS) and conductometric titration. Results indicated that the feeding mode and the interlayer were essential to prepare the polar gradient latex particles with hydrophilic core and hydrophobic shell. The morphologies of the two‐layer core/interlayer and three‐layer core/interlayer/shell particles were observed in TEM micrographs, and the sequential encapsulations of the carboxyl‐containing core and the core/interlayer particles were confirmed by an increase in the particle size as well as an increase in the buried carboxyl percentage.     

Preparation and Characterization of Polymer Core Shell Latex Particles

Stable core‐shell latex was synthesized by semicontinuous seeded emulsion polymerization with core monomers consisting of styrene (St), butyl acrylate (BA), and shell monomers consisting of methyl methacrylate (MMA), eutyl acrylate (EA), and methacrylic acid (MAA). The effects of compound emulsifier amount, mass ratio of anionic/nonionic emulsifier, and initiator amount on latex performance were investigated. By particle size analysis and transmission electron microscopy (TEM) observation, results suggest that final latex particles have clearly core shell structures.     

钛酸四丁酯水解制备聚苯乙烯/二氧化钛核壳粒子及空心二氧化钛微球

通过无皂乳液聚合方法制备了阳离子型及阴离子型聚苯乙烯(PSt)乳胶粒,并对后者用γ-氨丙基三乙氧基硅烷(KH550)进行了表面改性制得了乳胶粒表面载正电荷的乳液.在乙醇与水的混合溶剂中,分别使用以上3种PSt乳胶粒为核加入钛酸四丁酯制备了核壳型PSt/TiO2复合粒子.结果显示,仅在使用经KH550改性的阴离子PSt乳...     

Preparation and properties of novel plastisols based on acrylic core-shell lattices

A series of core-shell lattices comprising a core portion of rubbery acrylic homo- or copolymers and a surrounding shell portion of glassy methyl methacrylate (MMA) homo- or copolymers were designed as plastisols for automotive underbody coatings. The lattices were synthesized by a semi-continuous seeded emulsion polymerization and characterized by using differential scanning calorimetry (DSC) and scanning electronic microscopy (SEM). DSC investigations demonstrated that the incorporation of a hard segment of MMA into the core portion and strongly polar monomer methyl acrylic acid (MAA) or cross-linker allyl methacrylate (ALMA) into the shell portion resulted in an improvement of the glass transition temperatures. SEM micrographs verified that the latex particles were always spherical with regular structure throughout the polymerization stage. Novel plastisols were developed based on the abovementioned core-shell polymers with dioctyl phthalate (DOP) or tricresyl phosphate (TCP) plasticizers, whose core portions were compatible with the employed plasticizer and whose shell portions were incompatible with the plasticizer. Evaluation of the viscosity as a function of the storage time revealed that the storage stability of the plastisols could be obtained through incorporation of the strongly polar monomer MAA or the cross-linker ALMA into the shell portions. The mechanical properties of the plastigels were improved by incorporating MMA into the core portion or by incorporating MAA or ALMA into the shell portion of the lattices. A balance between the mechanical properties of plastigels and the storage stability of plastisols should be considered during selection of the monomers both for the core and shell.     

交联剂对无皂P(MMA-EA-MAA)种子聚合乳胶粒成孔的影响

采用完全无皂种子乳液聚合技术合成了粒径窄分布的P(MMA-EA-MAA)乳胶粒,通过对上述胶乳进行碱处理,制备出了具有空腔结构和多孔结构的聚合物乳胶粒,研究了交联剂的种类和用量对聚合过程、胶粒特性及胶粒结构形态的影响.结果表明,体系中加入交联剂后,单体转化率都有不同程度的提高;随交联剂用量的增加,乳胶粒粒径略有减小,交联剂用量较高时,乳胶粒粒径分布加宽;二乙烯基苯(DVB)的交联效率稍高于双甲基丙烯酸乙二醇酯(EGDMA);不加入交联剂及EGDMA用量低于0.5%时,处理后乳胶粒呈空腔结构,加入DVB及EGDMA用量高于1.0%时,处理后乳胶粒呈多孔结构,并且乳胶粒体积增量随交联剂用量的增加而减小.     

Preparation of sulphonate-containing core/shell latex particles via seeded emulsion copolymerization

<正>In this study,P(St-MAA) seed latex particles were first prepared via soap-free emulsion polymerization of styrene(St) and methacrylic acid(MAA),then the seed particles were allowed to swell with St at room temperature,and the P(St-MAA)/P(StNaSS) core/shell latex particles were then synthesized via seeded emulsion copolymerization of St and sodium styrene sulphonate (NaSS) using AIBN as initiator in the presence of N,N'-methylenebisacrylamide(BAA,water-soluble crosslinker).Results showed that the polymerization could be carried out smoothly when the ratio of BAA to total monomers was less than 3 mol%,the narrow dispersed P(St-MAA) seed particles with the diameter of 150 nm and the P(St-MAA)/P(St-NaSS) core/shell latexes with the particle size of about 200 nm were synthesized.When the 25/75 mole ratio of NaSS/(St + MAA) and 2 mol%of BAA were used in the seeded emulsion polymerization,the resulted P(St-MAA)/P(St-NaSS) latex product showed a low weight loss after water extraction,and the NaSS unit content in the whole particle and in the shell reached 11.7 mol%and 34.6 mol%,respectively.     

PU/PSt型复合乳液粒子热力学平衡形态预测

以水性聚氨酯分散液为种子采用无皂乳液聚合新技术合成出了具有核壳结构的聚氨酯 聚苯乙烯(PU PSt)型复合聚合物乳液 .采用界面张力简化计算方法 ,通过界面自由能变化最小的热力学判据对合成的复合乳液粒子的热力学平衡形态进行了预测 .并利用透射电子显微镜和接触角法测定的膜的表面极性对其进行了证实 .结果表明 ,界面自由能变化的最小判据可以推广到PU PSt体系 ,文中给出的界面张力的简化计算方法是可行的 .     

种子乳液聚合法制备多孔乳胶粒

用批量乳液聚合法制备了苯乙烯（Ｓｔ）———甲基丙烯酸甲酯（ＭＭＡ）二元共聚种子乳液Ｓ１以及Ｓｔ ＭＭＡ 丙烯酸（ＡＡ）三元共聚种子乳液Ｓ２,通过连续法无皂种子乳液聚合合成了一系列不同ＡＡ或ＭＡＡ（甲基丙烯酸）含量的Ｓｔ、ＭＭＡ三元共聚乳液．将所得复合胶乳进行碱／酸分步处理,得到具有多孔结构的乳胶粒．用透射电镜对胶粒形态进行了表征,考察了不饱和酸种类和用量、碱处理初始ｐＨ值及溶胀剂对胶粒成孔的影响．     

Synthesis and properties of soap-free poly(methyl methacrylate-ethyl acrylate-methacrylic acid) latex particles prepared by seeded emulsion polymerization

In order to obtain functional polymer latex particles with clean surface and with surface carboxyl groups, P(MMA-EA) seed particles with the diameter of 335 nm were first synthesized via soap-free batch emulsion polymerization of methyl methacrylate (MMA) and ethyl acrylate (EA), and then the seeded emulsion copolymerization of MMA, EA and MAA (methacrylic acid) onto the seed particles were performed in the absence of emulsifier. Influences of ingredients and conditions on polymerization, latex particle size (D_p) and its distribution were investigated. Results showed that most of the monomers polymerized onto the seed latex particles in the second step of polymerization by using drop-wise addition method, and D_p increased from 483 nm to 829 nm with the mass ratio of core/shell monomers [C]/[S] decreased from 1:2 to 1:15. It was found that D_p decreased with the increase of MAA and initiator amounts, and the size of the latex particles became uniform with the decrease of MAA amount and with the increase of [C]/[S] value.     

Synthesis and characteristics of poly(methacrylic acid‐co‐N‐isopropylacrylamide) thermosensitive composite hollow latex particles and their application as drug carriers

In this work, the poly(methacrylic acid‐co‐N‐isopropylacrylamide) thermosensitive composite hollow latex particles was synthesized by a three‐step reaction. The first step was to synthesize the poly(methyl methacrylate‐co‐methacrylic acid) (poly(MMA‐MAA)) copolymer latex particles by the method of soapless emulsion polymerization. The second step was to polymerize methacrylic acid (MAA), N‐isopropylacrylamide (NIPAAm), and N,N′‐methylenebisacrylamide in the presence of poly(MMA‐MAA) latex particles to form the linear poly(methyl methacrylate‐co‐methacrylic acid)/crosslinking poly(methacrylic acid‐co‐N‐isopropylacrylamide) (poly(MMA‐MAA)/poly(MAA‐NIPAAm)) core–shell latex particles. In the third step, the core–shell latex particles were heated in the presence of ammonia solution to form the crosslinking poly(MAA‐NIPAAm) thermosensitive hollow latex particles. The morphologies of poly(MMA‐MAA)/poly(MAA‐NIPAAm) core–shell latex particles and poly(MAA‐NIPAAm) hollow latex particles were observed. The influences of crosslinking agent and shell composition on the lower critical solution temperature of poly(MMA‐MAA)/poly(MAA‐NIPAAm) core–shell latex particles and poly(MAA‐NIPAAm) hollow latex particles were, respectively, studied. Besides, the poly(MAA‐NIPAAm) thermosensitive hollow latex particles were used as carriers to load with the model drug, caffeine. The effect of various variables on the amount of caffeine loading and the efficiency of caffeine release was investigated. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5203–5214     

Synthesis and characteristics of poly(methyl methacrylate‐co‐methacrylic acid)/poly(methacrylic acid‐co‐N‐isopropylacrylamide) thermosensitive semi‐hollow latex particles and their application to drug carriers

In this work, the poly(methyl methacrylate‐co‐methacrylic acid)/poly(methacrylic acid‐co‐N‐isopropylacrylamide) thermosensitive composite semi‐hollow latex particles was synthesized by three processes. The first process was to synthesize the poly(methyl methacrylate‐co‐methacrylic acid) (poly (MMA‐MAA)) copolymer latex particles by the method of soapless emulsion polymerization. The second process was to polymerize methacrylic acid (MAA), N‐isopropylacrylamide (NIPAAm), and crosslinking agent, N,N′‐methylenebisacrylamide, in the presence of poly(MMA‐MAA) latex particles to form the linear poly(methyl methacrylate‐co‐methacrylic acid)/crosslinking poly(methacrylic acid‐co‐N‐isopropylacrylamide) (poly(MMA‐MAA)/poly(MAA‐NIPAAm)) core–shell latex particles with solid structure. In the third process, part of the linear poly(MMA‐MAA) core of core–shell latex particles was dissolved by ammonia to form the poly(MMA‐MAA)/poly(MAA‐NIPAAm) thermosensitive semi‐hollow latex particles. The morphologies of the semi‐hollow latex particles show that there is a hollow zone between the linear poly(MMA‐MAA) core and the crosslinked poly(MAA‐NIPAAm) shell. The crosslinking agent and shell composition significantly influenced the lower critical solution temperature of poly(MMA‐MAA)/poly(MAA‐NIPAAm) semi‐hollow latex particles. Besides, the poly(MMA‐MAA)/poly(MAA‐NIPAAm) thermosensitive semi‐hollow latex particles were used as carriers to load with the model drug, caffeine. The processes of caffeine loaded into the semi‐hollow latex particles appeared four situations, which was different from that of solid latex particles. In addition, the phenomenon of caffeine released from the semi‐hollow latex particles was obviously different from that of solid latex particles. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3441–3451     

pH值和前驱体用量对核壳结构PSt/SiO2复合微球结构形态的影响

首先通过无皂乳液聚合法制得表面含羧基、粒径为360 nm的单分散聚苯乙烯(PSt)种子乳液,并在EtOH/H2O混合介质中用γ-氨丙基三乙氧基硅烷(KH-550)对其进行改性,制得表面含有活性硅乙氧基并带有正电荷的改性PSt乳胶粒,然后再加入原硅酸乙酯(TEOS)进行共水解与共缩聚反应,制备出了核壳结构PSt/SiO2...     

碱溶性无规共聚物表面活性剂的合成及在乳液聚合中的应用研究

合成了碱溶性无规共聚物聚 (甲基丙烯酸甲酯 丙烯酸乙酯 甲基丙烯酸 ) (MMA EA MAA) ,并对其结构、表面活性进行了表征研究 .以合成的P(MMA EA MAA)作高分子表面活性剂 ,进行甲基丙烯酸丁酯的乳液聚合 .研究了反应温度 ,引发剂浓度 ,表面活性剂浓度等因素对反应速率 (Rp)的影响 .结果表明 ,聚合速率随引发剂浓度 ,表面活性剂浓度的增加而增加 ;该体系的表观活化能为 85 19kJ·mol- 1 .用透射电镜 (TEM)表征了所制备的乳胶粒子形态 ,乳胶粒子呈较明显的核 壳结构 .     

ACR-g-PVC复合粒子结构与对PVC的增韧效率

采用丙烯酸丁酯 (BA)和丙烯酸 2 乙基己酯 (EHA)交联共聚物为核 ,BA与EHA或甲基丙烯酸甲酯(MMA)与苯乙烯 (St)或MMA与丙烯酸乙酯 (EA)交联共聚物为壳 ,合成了 3种聚丙烯酸酯 (ACR) [P(BA EHA)、ACRⅠ、ACRⅡ ]胶乳 .以 3种ACR胶乳为种子 ,分别与氯乙烯 (VC)进行乳液接枝共聚 ,制备了相应 3种复合粒子 (ACR g PVC) .借助动态光散射法和透射电镜考察了ACR与复合乳胶粒的粒径与结构 ,表征了所研制材料的形态和冲击韧性 .研究结果表明 ,3种ACR g PVC材料的常温缺口冲击强度随ACR含量增加而显著提高 ,其突跃点的发生具有等橡胶量效应 ,其临界橡胶含量约为 4 % ,并采用脆 韧转变的临界粒子间距模型对其进行了解释 ;P(BA EHA)比核 壳ACRⅠ或ACRⅡ具有更高的增韧效率 ,依据复合粒子的两种理想结构模型对其增韧效率进行了分析 .     

核/壳乳液聚合工艺中乳化剂的定量研究

以十二烷基硫酸钠(SDS)为乳化剂,采用多步种子乳液聚合方法制备了核/壳结构乳液,研究了乳化剂加入量以及加料速率对核壳乳液聚合的影响,并推导了核及壳乳液聚合阶段所需乳化剂量的计算公式.研究表明,当种子、核、壳乳液聚合阶段单体量分别为12g、50g和50g,种子乳液聚合阶段加入的乳化剂量为0.44g时,控制核、壳乳液聚合阶段乳化剂的加入量分别在0.64～2.07g及0.04～2.12g之间,且预乳化单体的滴加速度低于2.3g/min时,可以防止二次成核及新乳胶粒子的形成,制得粒径分布窄、核/壳结构明显的乳胶粒子.利用透射电镜(TEM)对所制备的核壳结构乳胶粒子的结构形态进行了验证,试验结果与理论预测结果一致.     

苯乙烯-甲基丙烯酸甲酯悬浮-乳液复合聚合过程中聚合物复合粒子组成的变化

采用苯乙烯(St)悬浮聚合过程中滴加甲基丙烯酸甲酯(MMA)乳液聚合组分,悬浮乳液复合聚合(SECP)方法,制备大粒径聚苯乙烯聚甲基丙烯酸甲酯(PS- PMMA)复合粒子.采用FTIR、1H- NMR、13C- NMR分析方法,研究SECP各个时期复合粒子中MMA- St链节摩尔比,发现悬浮粒子中MMA St链节摩尔比逐渐增大,而PMMA乳胶粒子中逐渐减少,表明悬浮相和乳液相间存在物质传递过程.悬浮粒子中MMA链节质量与MMA总投料质量比主要由乳胶粒子生成速率和乳胶粒子向悬浮粒子凝聚速率决定.最终得到的复合粒子除含PS和PMMA均聚物外,还含少量MMA-St共聚物.     

种子乳胶粒表面修饰法制备核壳结构PSt/TiO_2复合微球

首先采用无皂乳液聚合法合成了表面带负电荷、粒径为360 nm的单分散聚苯乙烯(PSt)乳液,并利用聚乙烯亚胺(PEI)在25℃下对PSt乳胶粒表面进行修饰,得到了表面带有正电荷的PSt种子乳液;然后以乙醇和水的混合物为反应介质,采用种子乳液加入法,使钛酸正丁酯(TBT)在修饰后的乳胶粒表面进行水解与缩合,制备出了核壳结构PSt/TiO2复合微球,利用电镜对复合微球的结构形态进行了表征.结果表明,PSt乳液改性时体系的zeta电位随着PEI用量的增加而升高,当PEI用量为PSt聚合物重量的15%时,体系的zeta电位从原来的-40.3 mV升高到了38.3 mV,达到对PSt乳胶粒表面改性的最佳值;在制备PSt/TiO2复合微球时,TiO2包覆量随着反应时间的延长而增加,反应7 h时达到90.2%的最大值;随介质中水含量的增加,吸附到复合微球表面上的TiO2纳米颗粒逐渐减少,复合微球表面逐渐变得光滑,当EtOH/H2O质量比为100/6.0时,得到结构均一、壳层厚度为29 nm的核壳结构PSt/TiO2复合微球.     

悬浮-乳液复合聚合聚苯乙烯-聚甲基丙烯酸甲酯复合粒子的颗粒特性和成粒机理

采用在苯乙烯 (St)悬浮聚合过程中滴加甲基丙烯酸甲酯 (MMA)乳液聚合组分的悬浮 乳液复合聚合方法 ,制备大粒径聚苯乙烯 聚甲基丙烯酸甲酯 (PS PMMA)复合粒子 .研究聚合物粒径分布和颗粒形态的变化发现 ,在St悬浮反应中期滴加MMA乳液聚合组分后 ,聚合体系逐渐由悬浮粒子与乳胶粒子并存向形成单峰分布复合粒子转变 ,最终形成核 壳结构完整的大粒径PS PMMA复合粒子 ;在St悬浮反应初期滴加MMA乳液聚合组分 ,St与MMA一起分散成更小液滴 ,反应后期凝并成非核 壳结构复合粒子 ;在St悬浮反应后期滴加MMA乳液聚合组分 ,PMMA乳胶粒子与PS悬浮粒子基本独立存在 .根据以上结果 ,提出了St MMA悬浮 乳液复合聚合的成粒机理 .     

PMMA/CA核壳纳米微粒的制备与表征

采用乳液聚合方法,不使用任何乳化剂,将甲基丙烯酸甲酯(MMA)在干酪素(CA)存在下使用叔丁基过氧化氢为引发剂,通过接枝聚合制备了直径在150 nm左右的具核壳结构的PMMA/CA纳米复合乳胶粒,乳胶粒的核壳结构通过透射电镜得到了证实.探讨了反应温度、引发剂用量、核壳质量比等条件对单体转化率和接枝效率的影响.阐明了制备...