PMMA/PAN核壳复合粒子的制备与表征

用无皂乳液聚合法制备粒径分布较窄的单分散聚甲基丙烯酸甲酯(PMMA)乳液粒子后,以此乳液粒子为种子,以丙烯腈为壳层单体,用种子乳液聚合法制备了粒径分布更窄、具有核壳结构形态的PMMA／聚丙烯腈(PAN)复合粒子,测定了核及核壳粒子粒径及其分布,并用透射电镜表征了其核壳形态特征。结果表明,PMMA／PAN核壳粒子的壳层厚度约为20nm,粒径分布要比PMMA粒子的窄。     

粒径可控的聚丙烯酸丁酯/聚甲基丙烯酸甲酯核壳乳液的制备及表征

采用种子乳液聚合法制备了聚丙烯酸丁酯(PBA)乳液,然后通过第二单体甲基丙烯酸甲酯的预溶胀法聚合制备了PBA/聚甲基丙烯酸甲酯(PMMA)乳液,用激光散射粒度仪和透射电子显微镜对乳液粒径和结构进行了表征.结果表明,当乳化剂十二烷基硫酸钠质量分数为丙烯酸丁酯的1.5%时,可制备粒径为53.6 nm且分布窄的PBA种子乳液;通过调整补加乳化剂、单体与种子乳液的用量,可制得粒径为53.6～443.8 nm的一系列单分散PBA乳液;PBA/PMMA乳液具有完善的核壳结构,且在核壳两相间存在着一个过渡层.     

悬浮-乳液耦合聚合制备大粒径核-壳结构PS/PMMA复合粒子

采用在苯乙烯(St)悬浮聚合不同时期滴加甲基丙烯酸甲酯(MMA)乳液聚合组分的悬浮-乳液耦合聚合方法,制备大粒径核-壳结构复合粒子。研究发现：在St悬浮聚合初期和宏观成粒基本完成的聚合后期滴加MMA乳液聚合组分,分别得到由初级粒子凝并的非核-壳结构粒子和核-壳结构不完整的复合粒子,粒径分布较宽;在St悬浮聚合中期滴加MMA乳液聚合组分,MMA和PMMA乳胶粒子易于向PS粒子扩散或粘并,制备得到平均粒径大于100gm、粒径分布窄和核-壳结构良好的PS／PMMA复合粒子。     

苯乙烯-甲基丙烯酸甲酯无皂核壳乳液合成及表征

采用溶液聚合法制得苯乙烯(St)与苯乙烯磺酸钠(NaSS)共聚物的种子乳液,将其用于甲基丙烯酸甲酯(MMA)的无皂种子乳液聚合,制得了一系列不同核壳单体配比的核壳乳液.通过对溶液聚合动力学、产物的结构与相对分子质量、种子粒径以及将其用于乳液聚合时所得产物的结构与粒子形态分析,结果表明:以溶液聚合法制得的苯乙烯型种子乳液能成功制备无皂核壳乳液,从而为制备无皂核壳乳液提供了新的途径.     

n-BMA/MMA共聚核壳乳液的合成研究

通过半连续种子乳液聚合的方法,制备了具有核壳结构的丙烯酸酯聚合物乳胶粒子。采用甲基丙烯酸甲酯(MMA)、甲基丙烯酸酯正丁酯(n-BMA)等单体进行共聚。研究了共聚合过程中,乳化剂浓度、引发剂等对聚合物乳液粒径大小、凝胶量等的影响,并利用动态光散射(DLS)、透射电镜(TEM)和差示扫描量热仪(DSC)对乳胶粒子进行表征。结果表明:核乳液聚合阶段乳化剂浓度增大,乳液粒子的粒径变小,引发剂用量对粒径及分布影响不大;TEM观察到核乳胶粒径大小及变化趋势与DLS测得的结果相一致,并且核乳胶粒子和核壳乳液粒子都呈规则的圆球状,分布均一;DLS测试核壳丙烯酸酯乳胶粒子粒径的变化呈逐渐增长的趋势;DSC测试发现制备的核壳粒子有2个玻璃化转变温度(Tg),验证了胶乳粒子核壳结构的存在。     

PAN基碳纳米微球的制备及表征

通过种子乳液聚合得到聚丙烯腈/聚甲基丙烯酸甲酯(PAN/PMMA)核壳结构的纳米微球。将经冷冻干燥后得到的PAN/PMMA纳米微球进行预氧化和炭化处理,成功制备出粒径为50 nm的碳纳米微球(Carbon Nanospheres,CNSs)。并利用光散射、傅立叶红外线光谱(FTIR)、透射电镜(TEM)等技术对所合成的PAN/PMMA纳米微球和CNSs进行分析。实验结果表明,PMMA的加入有利于降低PAN基CNSs的粒径,且炭化温度在500～600℃之间得到的CNSs的分散性最好。     

核壳型聚苯乙烯/聚甲基丙烯酸甲酯复合乳液的制备

以过硫酸铵(APS)为引发剂,用种子乳液聚合方法,合成出以聚苯乙烯(PSt)为核, 聚甲基丙烯酸甲酯(PMMA)为壳的复合乳液。透射电子显微镜观察了核壳复合乳胶粒的形态,光散射粒径分布仪(PCS)测量胶乳粒径大小及其分布。最终成功地制得了核壳型PS/PMMA复合乳液,所得复合乳胶粒粒径大小在60～90nm左右,且单分散性较好。     

PBA/PMMA核壳结构乳胶粒子粒径分析

采用种子乳液聚合制备出了PBA/PMMA核壳结构乳胶粒子，研究并分析了MMA在3种不同投料方式（间歇法、半间歇法和平衡溶胀法）下粒子粒径变化情况。实验发现第二单体采用间歇法投料可获得较理想的核壳结构乳胶粒。     

引发体系对细乳液聚合制备PAN纳米粒子的影响

为制备出规则球形的聚丙烯腈(PAN)纳米粒子,探究水溶性较大的单体的细乳液聚合机理,分别采用过硫酸钾(KPS)、偶氮二异丁腈(AIBN)和双氧水/L-抗坏血酸(H2O2/LAA)氧化还原引发剂进行丙烯腈(AN)的细乳液聚合。通过乳液外观的变化比较了三种引发剂对聚合过程的影响,对比了三种PAN纳米粒子的形态、粒径和结晶情况。结果发现;采用热引发剂时,由于AN的水溶性增大,单体扩散明显,所制备出的PAN纳米粒子为不规则颗粒;而采用氧化还原引发剂能够获得规则球形的PAN纳米粒子。说明了水溶性较大的单体进行细乳液聚合时,温度是影响液滴成核主导地位的关键因素;均相成核是造成PAN颗粒表面结晶进而导致PAN粒子形状不规则的主要原因。     

以PVC为外壳层的ACR抗冲改性剂的合成及其对PVC的增韧作用

以聚丙烯酸丁酯(PBA)为内核,通过种子乳液聚合制备了分别以聚甲基丙烯酸甲酯(PMMA)、聚氯乙烯(PVC)、PMMA/PVC为壳层的纯丙烯酸酯(ACR)和PVC改性ACR乳液.扫描电镜观察发现,纯ACR乳胶粒子具有明显的核-壳结构,进一步包覆PVC后形成疏松外层.考察了不同结构ACR与PVC共混物的相态结构、抗冲性能和断面形貌,发现用PVC部分或完全替代PMMA壳层的改性ACR在PVC基体分散良好,具有与纯ACR相当的增韧PVC作用,冲击断面呈现典型的韧性断裂特征.     

原位聚合法制备高透光率韧性PMMA复合树脂的研究

采用原位聚合法制备PMMA/P(BA-St)/PMMA三层韧性有机玻璃复合树脂,分子设计方法的使用,保持了材料的透明性。考察了韧性粒子粒径、橡胶相组成以及橡胶含量对材料力学和光学性能的影响。借助透射电镜、扫描电镜和动态光散射方法对复合胶乳粒子以及所制材料的形态结构进行了表征。结果表明:橡胶相的折光指数对材料的透光率有明显影响,橡胶相玻璃化温度越低,越有利于增韧。     

聚苯乙烯-聚甲基丙烯酸甲酯核-壳粒子的制备

由种子乳液聚合法制备了聚苯乙烯-聚甲基丙烯酸甲酯核-壳粒子。以过硫酸钾(KPS)为引发剂,辛基酚聚氧乙烯醚(OP-10)为乳化剂,合成了聚苯乙烯(PS)种子核;连续滴加甲基丙烯酸甲酯(MMA),在核表面富集MMA,制备了粒径范围在0.16~0.67μm的核-壳粒子;当单体苯乙烯与甲基丙烯酸甲酯(St/MMA)的比为30∶70(质量比)时,所得粒径在0.18μm,粒径分布为0.012。差示扫描量热(DSC)研究显示,复合粒子的玻璃化转变温度(Tg)为97.2℃,峰形单一,表现出良好的热性能。     

有机硅/丙烯酸酯乳液的粒径与分散行为研究

采用半连续乳液聚合法合成了以丙烯酸丁酯和甲基丙烯酸甲酯为成核单体,丙烯酸丁酯(MAA)、甲基丙烯酸甲酯(BA)、丙烯酸(AA)和γ―甲基丙烯酰氧基丙基三甲氧基硅烷为成壳单体的核壳结构乳液。采用马尔文纳米粒度仪等研究了乳液的粒径及其分布与引发剂和乳化剂用量之间的关系,粒径对乳液稳定性的影响以及乳液粒径与温度的关系,通过透射电镜对乳液微粒形态进行了分析。结果表明,乳液的粒径随着引发剂和乳化剂用量的增加而减小,乳液粒径在30～60℃时较为稳定,当引发剂过硫酸铵质量分数为0.55%,乳化剂十二烷基苯磺酸钠质量分数为2%时,制得的乳液粒径在120 nm左右,具有明显的核壳结构和较好的稳定性。     

Preparation of polystyrene/poly(methyl methacrylate) core‐shell composite particles by suspension‐emulsion combined polymerization

Suspension‐emulsion combined polymerization process, in which methyl methacrylate (MMA) emulsion polymerization constituents (EPC) were drop wise added to styrene (St) suspension polymerization system, was applied to prepare polystyrene/poly(methyl methacrylate) (PS/PMMA) composite particles. The influences of the feeding condition and the composition of EPC on the particle feature of the resulting composite polymer particles were investigated. It was found that PS/PMMA core‐shell composite particles with a narrow particle size distribution and a great size would be formed when the EPC was added at the viscous energy dominated particle formation stage of St suspension polymerization with a suitable feeding rate, whereas St‐MMA copolymer particles or PS/PMMA composite particles with imperfect core‐shell structure would be formed when the EPC was added at the earlier or later stage of St suspension polymerization, respectively. It was also showed that the EPC composition affected the composite particles formation process. The individual latex particles would exist in the final product when the concentrations of MMA monomer, sodium dodecyl sulfate emulsifier, and potassium persulfate initiator were great in the EPC. Considering the feature of St suspension polymerization and the morphology of PS/PMMA composite particles, the formation mechanism of PS/PMMA particles with core‐shell structure was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and physical properties of rubber-modified epoxy resin using poly(urethane acrylate)/poly(glycidyl methacrylate-co-acrylonitrile) core-shell composite particles

Poly(urethane acrylate)/poly(glycidyl methacrylate-co-acrylonitrile) core-shell composite particles were prepared using two-stage emulsion polymerization. Composite particle sizes were varied from 48 to 200 nm by introducing polyoxyethylene groups into the urethane acrylate molecules. The morphology of the two-stage composite latex was inferred using surface energy measurements and titration of the emulsion. In the two-stage latex, which was prepared using relatively small core particles (about 40 nm), an inverted core-shell morphology was obtained. It was believed that the high polarity of the core surface and the low stage ratio of core to shell made the core-shell morphology more unstable thermodynamically. When the core of the two-stage latex was more crosslinked, the morphology was perfectly prevented from inverting because a higher kinetic barrier between the core-shell and inverted core-shell structures was achieved. The impact strength of the modified epoxy resin increased with the decrease of composite particle sizes and the increase of the shell thickness. In particular, when the average size of the composite particle was 50 nm and the stage ratio was 70/30, the impact strength of the modified epoxy resin increased more than 20 times compared to that of pure epoxy resin. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1589–1600, 1997     

Synthesis and characterization of poly(butyl acrylate)/silica and poly(butyl acrylate)/silica/poly(methyl methacrylate) composite particles

Poly(butyl acrylate)/poly(methyl methacrylate) (PBA/PMMA) core–shell particles embedded with nanometer‐sized silica particles were prepared by emulsion polymerization of butyl acrylate (BA) in the presence of silica particles preabsorbed with 2,2′‐azobis(2‐amidinopropane)dihydrochloride (AIBA) initiator and subsequent MMA emulsion polymerization in the presence of PBA/silica composite particles. The morphologies of the resulting PBA/silica and PBA/silica/PMMA composite particles were characterized, which showed that AIBA could be absorbed effectively onto silica particles when the pH of the dispersion medium was greater than the isoelectric potential point of silica. The critical amount of AIBA added to have stable dispersion of silica particles increased as the pH of the dispersion medium increased. PBA/silica composite particles prepared by in situ emulsion polymerization using silica preabsorbed with AIBA showed higher silica absorption efficiency than did the PBA/silica composite particles prepared by direct mixing of PBA latex and silica dispersion or by emulsion polymerization in which AIBA was added after the mixing of BA and silica. The PBA/silica composite particles exhibited a raspberrylike morphology, with silica particles “adhered” to the surfaces of the PBA particles, whereas the PBA/silica/PMMA composite latex particles exhibited a sandwich morphology, with silica particles mainly at the interface between the PBA core and the PMMA shell. Subsequently, the PBA/silica/PMMA composite latex obtained had a narrow particle size distribution and good dispersion stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3425–3432, 2006     

Poly(methyl methacrylate)/polyacrylonitrile composite latex particles with a novel surface morphology

Precipitation polymerization of acrylonitrile in aqueous phase was performed in the presence of submicrometer-sized poly(methyl methacrylate) (PMMA) seed particles. The resulting PMMA/polyacrylonitrile (PAN) composite latex particles showed a novel well-defined surface morphology like rambutan. The formation of such surface structure was ascribed to the facts that PAN polymer is crystalline and scarcely swollen by its monomer. The composite particles had a core/shell structure with a PAN shell surrounding a PMMA core.     

PMMA/MC复合胶粒的制备及在尼龙中的应用

采用原位乳液聚合法制备了聚甲基丙烯酸甲酯(PMMA)／三聚氰胺氰尿酸盐(MC)复合胶粒,对其进行X光电子能谱及热重分析结果显示,在MC阻燃剂颗粒表面覆盖了一层PMMA胶膜,形成了具有核-壳结构的PMMA／MC复合胶粒;MC能影响PMMA的热降解过程并促进其成炭;在尼龙6(PA6)中的应用结果表明,PMMA／MC复合胶粒能改善PA6的力学性能和阻燃性能。     

St-BA-BVP无皂共聚物阳离子乳胶粒大小及形态研究

合成阳离子共单体 1-丁基 ,4 -乙烯吡啶溴化铵 ( BVP) ,并以偶氮二异丁基咪盐酸 ( A IBA)作引发剂 ,制备苯乙烯 /丙烯酸丁酯 ( St/ BA )共聚物乳液 ,通过 TEM研究改变 BVP的浓度、St/ BA主单体的配比及单体加料方式对 P( St/ BA / BV P)乳胶粒大小形态的影响 ,结果表明批量法和单体全滴加法制备的乳胶粒形状规则、分布均匀、半连续法制备的乳胶粒子呈多分散分布 ,粒径相差很大 ,且 P( St) / P( BA)得到的乳胶粒呈明显的核壳结构。     

核壳结构聚硅氧烷/丙烯酸酯复合乳液(Ⅰ)乳化剂对乳液聚合过程及粒径分布和粒子形态的影响

采用种子乳液半连续法合成了具有高有机硅含量的聚硅氧烷/丙烯酸酯核壳结构复合乳液,研究乳化剂的种类、复配比例及质量浓度对有机硅／丙烯酸酯壳核乳液性能与乳胶粒径、分布和结构的影响.结果表明：阴离子乳化剂十二烷基硫酸钠(SDS)、十二烷基磺酸钠(SDS-2)、十二烷基苯磺酸钠(SDBS)所合成的乳胶粒子粒径依次增大,SDS与非离子型乳化剂OP-10复配使用时,随OP-10质量分数的增加,聚合速率和转化率降低,化学稳定性增加,乳胶粒子粒径增大,分布变宽,确定了复合乳化剂的最佳配比.随复合乳化剂浓度的增加,聚合速率加快、转化率增加,乳胶粒子粒径减小而分布加宽.通过改变乳化剂加入方式可减小乳胶粒子的粒径分布.为减少壳层聚合物新粒子的产生,需严格控制乳化剂的浓度,使加入的壳层单体处于“饥饿”状态,在乳胶粒子表面富集、引发聚合,形成表层“过渡层”,最终形成核壳结构复合粒子.