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...     

VAc/BA核壳乳液聚合乳胶粒形态演化

由两种单体分阶段种子乳液聚合制得的核壳型乳胶粒 ,可能存在着多种多样的形态 .由于不同的形态在使用中具有不同的性能 ,因此 ,核壳型乳胶粒的结构形态的研究一直受到人们的十分重视 .近年来 ,Ｓｕｎｄｂｅｒｇ[1] 等指出 ,正向、反向、两半球、两种孤立粒子等四种形态是热力学平衡形态 ,其他形态则是未达平衡的过渡形态 .并且提出用界面自由能最小的方法判别其中哪一种是最终平衡形态 .显然 ,自不平衡形态到平衡形态需要链迁移 ,Ｃｈｅｎ[2 ] 、Ｊｏｎｓｓｅｎ[3 ] 、Ｇｏｎｚａｌｅｚ[4] 等指出 ,链迁移的阻力是粘性力 .对于聚醋酸乙烯酯…     

Preparation and properties of a thermo-sensitive latex film

Polymer particles with hydrophobic core and hydrophilic shell were prepared via a three-step method. First, poly(butyl methacrylate-co-methyl methacrylate) (p-(BMA-MMA)) latex was prepared through emulsion polymerization. Then, a shell of poly(glycidyl methacrylate) (p-GMA) was introduced around the p-(BMA-MMA) particles by using a redox initiation system under kinetically controlled conditions. Finally, part of the epoxy groups existing in the shell were converted into quaternary ammonium salts, resulting in an ionic hydrophilic shell. The core-shell particles could be redispersed in water to form a stable emulsion. The contact angle of the core-shell latex film with water was around 16° at 25 °C, which became larger than 90° after the film was heated at 150 °C for a short period of time. This showed that the latex film was completely switched from hydrophilicity to hydrophobicity by the action of heat. Additionally, the latex film before heat treatment could be easily washed away from the substrate with neutral water, but it could no longer be removed after the heat treatment. When an IR dye with the maximum absorption at 830 nm was incorporated into the film, it became sensitive to LD laser emitting at 830 nm and gave negative image after exposed by LD laser and developed with neutral water. This showed that the latex film might find uses in chemical-free thermal laser imaging applications.     

Synthesis and Characterization of Large Dimension PBA-P(MMA-ITA) Latex Particles with Core-Shell Morphology

In this paper, a novel large dimension poly(n-butyl acrylate)-poly(methyl methacrylate-itaconic acid) (PBA-P(MMA-ITA)) core-shell latex particles (CSR) with diameter of 200 nm～300 nm were successfully synthesized via pre-emulsion and semi-continuous seeded emulsion polymerization process. The analysis on the surface tension and coagulation rate of polymeric system, size and distribution of latex particles indicated that the composite emulsifier of sodium dodecyl sulfonate/polyoxyethylene nonyl phenyl ether (SDS/OP-10) had the best emulsified effect. The optimal ratio of SDS/OP-10 was 1:1 and its optimum dosage was 1.0% of monomer amount. FTIR analysis results confirmed that ITA participated in the copolymerization reaction and the chemical bond between P(MMA-ITA) copolymer and PBA core existed in the interfacial of core and shell. DSC analysis results showed that the glass transition temperature (T _g) of P(MMA-ITA) copolymer increased with the increase of the ITA dosage and decreased with the increase of the core shell mass ratio. TEM images revealed that CSR particles had core-shell morphology indeed, but the particles’ core-shell morphology would be changed at higher ITA dosage and core shell mass ratio. The size of CSR particles was 330 nm, and the diameter of PBA core was 290 nm. ITA content in the shell of CSR particles was analyzed by non-aqueous acid-base titration. ITA content was the highest at 6% of ITA dosage, ITA amount which chemically bonded with PBA core was the highest at 8% of ITA dosage. When the core shell mass ratio was 60/40, ITA content and ITA amount which grafted onto PBA core were both the highest. ITA content of CSR particles achieved above 1.11% in this work, and it is completely possible for using CSR particles toughening and compatibilizing polyamide 6 (PA 6).     

Synthesis and characterization of poly (n-butyl acrylate)-poly (methyl methacrylate) latex interpenetrating polymer networks by radiation-induced seeded emulsion polymerization

A series of latex interpenetrating polymer networks (LIPNs) were prepared via a two-stage emulsion polymerization of methyl methacrylate (MMA) or mixture of MMA and n-butyl acrylate (n-BA) on crosslinked poly(n-butyl acrylate)(PBA) seed latex using ⁶⁰Co γ-ray radiation. The particles of resultant latex were produced with diameters between 150 and 250 nm. FTIR spectra identified the formation of crosslinked copolymers of PMMA or P(MMA-co-BA). Dynamic light scattering (DLS) showed that with increasing n-BA concentration in second-stage monomers, the particle size of LIPN increased. Transmission electron microscope(TEM) photographs showed that the morphology of resultant acrylate interpenetrating polymer network (IPN) latex varied from the distinct core-shell structure to homogenous particle structure with the increase of n-BA concentration, and the morphology was mainly controlled by the miscibility between crosslinked PBA seed and second-stage copolymers and polarity of P(MMA-co-BA)copolymers. In addition, differential scanning calorimeter (DSC) measurements indicated the existence of reinforced miscibility between PBA seed and P(MMA-co-BA)copolymer in prepared LIPNs.     

单分散聚丙烯酸丁酯-二氧化硅核壳粒子的制备

近年来,有机-无机核壳材料因其具有可调的光、电、磁等特性而备受关注．无机物外壳可以增强粒子的热力学稳定性、机械强度和抗拉性能．高分子乳胶粒内核具有弹性,且易成膜,外部包覆无机物的乳胶粒可结合两者特性并产生协同效应．     

Ceramic encapsulated latex composites

This work reports the encapsulation of latex particles in Al2O3-polystyrene (PS) composite films. These films were prepared from PS particles in Al2O3 dispersion at room temperature in various latex contents. Composite films were annealed at elevated temperatures in 10 min time interval above the glass transition temperature (Tg) of polystyrene. Transmitted photon intensities, I(tr) were monitored after each annealing step. AFM micrographs were also used to observe the physical changes of the composite films during annealing. It was observed that latex particles are encapsulated above a critical Al2O3 content of 33 wt% which corresponds to the critical occupation probability of p(c) = 0.33 at which the film obey the site-percolation model with a critical exponent of 0.45. Below p(c), it was seen that complete latex film formation process took place, where transparency of the film was increased by annealing.     

交联核壳结构PBA/PS和PBA/PMMA纳米微球的制备与应用

考察了聚丙烯酸丁酯/聚苯乙烯(PBA/PS)以及聚丙烯酸丁酯/聚甲基丙烯酸甲酯(PBA/PMMA)交联核壳结构纳米高分子微球的制备方法,并对其在尼龙复合材料中的应用进行了初步研究.结果表明,通过交联剂的引入使粒子核层和壳层内部均形成了高度交联的结构,可以限制亲水性较小的聚苯乙烯(PS)壳层向粒子内部迁移的趋势;制备出的微球平均粒径为40~50 nm,粒径分布很窄.采用饥饿态加料方式加入第二单体不仅可以使微球具有较高的产率和凝胶率,而且可以使其具有更理想的核壳结构和更窄的粒径分布.此外,将合成出的PBA/PMMA核壳粒子对尼龙6基体进行复合的结果表明,由于该微球表面与尼龙6基体之间具有较强的界面相互作用且微球具有较大的形变能力,可以在基体中形成良好的分散,在保持材料强度的同时有效地提高了其刚性和韧性.     

氯丁胶乳-聚甲基丙烯酸甲酯复合乳胶粒结构形态

以氯丁胶乳（Pa）为种子乳液,甲基丙烯酸甲酯（Pb）为第二单体,采用种子乳液聚合法,制备了氯丁胶乳-聚甲基丙烯酸甲酯复合乳胶粒。 热力学分析表明,当Pb的体积分数Φb＜0.69时,可同时形成Pa-Pb型正核-壳和（Pa＋Pb）分离型乳胶粒,当Φb＞0.69时,形成Pb-Pa型翻转型核壳结构乳胶粒,并伴有Pa-Pb型正核-壳结构乳胶粒的形成。 动力学分析表明,引发剂类型、第二单体的加入方式、种子乳胶粒的交联、单体/聚合物质量比是影响乳胶粒形态的主要因素。 采用水溶性引发剂过二硫酸钾（KPS）,以饥饿态方式加入单体,氯丁胶乳 聚甲基丙烯酸甲酯(PCR-PMMA)复合乳胶粒呈现正核-壳结构,以充溢态方式加入单体则不能形成明显的核-壳结构;而以油溶性偶氮二异丁腈（AIBN）为引发剂时,单体无论以充溢态方式加入还是饥饿态加入均倾向于形成翻转核-壳型粒子。 在种子乳胶粒中加入一定量交联剂二缩三乙二醇二甲基丙烯酸酯,有利于形成明显的正核壳结构。 以饥饿态进料,KPS为引发剂时,随着单体用量增加,壳层变厚,仍呈正核-壳结构,与热力学分析结果相吻合;以AIBN为引发剂时,随着单体用量增加,PCR-PMMA复合乳胶粒逐渐由翻转核壳型结构变为互穿结构。     

核壳型聚丙烯酸丁酯/聚(苯乙烯-甲丙烯酸甲酯)乳胶粒子形态设计及模拟

在简化及限制的实验条件下，提出了一套界面张力的简化推算方法，通过计算证实了采用该简化算法所得界面张力可较为准确地预测丙苯体系复合乳胶粒子的热力学平衡形态．并且根据性能要求，通过界面自由能变化最小的热力学判据对核壳型聚丙烯酸丁酯／ 聚（ 苯乙烯 甲基丙烯酸甲酯） 复合乳胶粒子进行形态设计，采用种子半连续乳液聚合法制备复合乳胶，利用电镜对设计粒子的最终核壳形态进行了证实．     

SBA/PVC复合树脂的制备与表征

采用聚丙烯酸正丁酯(PBA)改性的丁苯(SBR)胶乳为种子乳液(SBA),通过乳液接枝共聚氯乙烯制备了SBA/PVC复合树脂.通过粒径分析仪、动态力学分析仪(DMA)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)等测试手段,表征了复合胶乳粒的粒径与形态,以及材料的形态结构.粒径分析表明PVC确实包覆在SBA上;TEM研究结果显示SBA/PVC胶乳粒子呈现明显的核壳结构,PBA加入可提高SBR在复合材料中的分散性;DMA分析表明SBA/PVC复合树脂在低温区呈现了一个宽而弱的转变峰,揭示了接枝过渡层的微观结构特征;研究了交联剂和PBA用量对材料性能的影响,结果表明在PBA含量较低时,SBA/PVC复合树脂就显示了优良的冲击性能,且SEM照片显示材料断面形貌为特征性韧性断裂.     

The formation mechanism of poly(vinyl acetate)/poly(butyl acrylate) core/shell latex in two-stage seeded semi-continuous starved emulsion polymerization process

In this paper, the morphological evolution of latex particles on poly(vinyl acetate) (PVAc)/poly(butyl acrylate) (PBA) in two-stage seeded semi-continuous starved emulsion polymerization is studied, and the thermodynamic analysis and a mathematic model are derived to describe the interfacial free energy changes corresponding to various possible thermodynamically unstable morphologies during the polymerization process. The comparisons between the morphological evolution and the related thermodynamic analysis show that the morphological evolution of latex particles is oriented to the thermodynamic preferred morphology which is an inverted core/shell structure with PBA as core and PVAc as shell. Based on the comparisons, the possible morphological developmental pathway of PVAc/PBA core/shell latex is described. The possible morphological developmental pathway suggests that the observed multi-particle morphology in the polymerization process is due to restricted chain mobility related to high internal viscosity. The formation mechanism of PVAc/PBA core/shell latex, based on the experiments as well as the thermodynamic and dynamic analyses, is proposed, which signifies that PBA is first formed outside the PVAc seed and then migrate to the inside of the PVAc seed.     

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 application of cross-linked core-shell PBA/PS and PBA/PMMA nanoparticles

This paper reports the preparation of cross-linked core-shell poly(butyl acrylate)/polystyrene (PBA/PS) and poly(butyl acrylate)/poly(methyl methacrylate) (PBA/PMMA) nanoparticles via seeded emulsion polymerization and their application in nylon-based composites. A highly cross-linked structure was formed in both the cores and the shells by using a cross-linking agent, which could prevent the migration of hydrophobic PS shells to the inside of particles. There were covalent bonds on the interfaces between the cores and the shells of both particles. The average particle sizes were 40–50 nm, and the size distributions were narrow. The kinetics of polymerization was investigated. Well-defined core-shell structure and narrow particle size distribution could be achieved under starved conditions of monomer feeding. Furthermore, PBA/PMMA particles were used to fill nylon 6, good dispersion was obtained because of the strong interfacial interaction between the nanoparticles and the nylon 6 matrix and the good deformation ability of nanoparticles, and the toughness and rigidity of the composites were improved evidently. __________ Translated from Acta Polymerica Sinica, 2005, (6) (in Chinese)     

Preparation of epoxy-acrylic latex based on bisphenol F epoxy resin

Bisphenol F based epoxy-acrylic latex with different amount of epoxy resin was successfully prepared by semi-continuous seeded emulsion polymerization. The resulting composite latexes had a narrow size distribution of about 105 nm in diameter. The DSC result showed that the epoxy resin and polyacrylate were grafting copolymerization. The FTIR spectra showed that the epoxy group had been introduced into the epoxy acrylic latex system, and the composite latex could be crosslinked with epoxy hardener at room temperature. The crosslinked composite latex film exhibited a high Tg compared to epoxy-acrylic latexes. The surface of the films with the epoxy resin was regular, and diffused into the polyacrylate phase in the epoxy-acrylic latexes films. Since the curing reactions occurred before latex particle coalescence stage, the surfaces of the cured epoxy-acrylate latex films had a number of interface particle. Compared with the acrylic latex, the thermal stability of the epoxy-acrylate latex was increased, and the stability of the cured film increased with increasing epoxy content.     

Site percolation model for latex film formation in soft polymer matrix

The UV-visible (UVV) technique was used to monitor latex film formation in a soft polymer matrix. Various film samples were prepared by increasing the amount of poly(methyl methacrylate) (PMMA) particles in a poly(isobutylene) (PIB) matrix. These samples were then annealed above the glass transition temperature to promote latex film formation. Transmitted photon intensities, Itr, were measured for each film. It is observed that Itr decrease as the latex content is increased, which was explained by the increase in scattered light intensity, Isc. The drastic increase in Isc above a certain latex content is attributed to the site percolation of latex particles in the PIB matrix. The percolation threshold and the critical exponent were measured and found to be 0.3 and 0.4, respectively. The increase in Itr by annealing of film samples above Tg was explained with the void closure process below 0.8 occupation probability. When the film is occupied completely with the latex particles, interdiffusion of polymer chains was observed. Viscous flow and chain diffusion activation energies were determined and found to be 8 and 51 kcal/mol, respectively.     

纳米SiO_2/聚丙烯酸酯复合乳液的制备与表征

根据核壳乳液聚合理论,以经过硅烷偶联剂表面改性的纳米SiO2为种子,采用适当的乳液聚合工艺,制备了纳米SiO2/聚丙烯酸酯复合乳液,并表征了其性能.结果表明,纳米SiO2经过改性后,硅烷偶联剂接枝在其表面;以其为种子制备的复合乳液具有核壳结构,其热稳定性有所提高.     

Morphology and grafting in polybutylacrylate-polystyrene core-shell emulsion polymerization

The morphology of polybutylacrylate–polystyrene (PBA–PS) core-shell latex particles prepared by seeded emulsion polymerization was investigated as a function of the addition method of styrene (St). The thin layer chromatography/flame ionization detector (TLC–FID) technique was used to characterize the morphology of the core-shell latexes. It was found that grafting PS to the PBA core occurs during seeded emulsion polymerization. The percentage of grafting depended on the method of addition of St, being greatest for the batch reaction, less for the preswollen batch reaction, and least for the semibatch reaction. Upon aging the PBA core-polymer migrated out of the latex particles with a low degree of grafting to form dumbellshaped particles, whereas the PBA–PS core-shell particles with a high degree of grafting remained spherical because of the emulsifying ability of graft copolymer.     

纳米TiO_2粒子静电吸附引发剂及其原位锚固丙烯酸丁酯聚合

调节体系酸碱度使分散于水分散液中的纳米TiO2粒子表面带负电,进而通过静电作用高效稳定吸附上偶氮盐类引发剂2,2′-偶氮二异丁脒二氯化氢(AIBA).实验发现引发剂在TiO2粒子表面的静电吸附存在一个稳定吸附上限,其值在pH=10的体系中为0.084mmol/g(相对于TiO2的量).进一步通过原位乳液聚合在TiO2粒子表面就地引发丙烯酸丁酯(BA)的锚固聚合,制备得到了PBA/TiO2复合乳胶.对聚合动力学和聚合产物的观察发现,吸附引发剂在其中起到重大作用,只有当引发剂用量略低于稳定吸附上限时,反应过程稳定性和聚合产物分散性才较好.此时聚合反应阻聚期短、反应速率快、单体转化率高、实验重现性好.热重分析(TGA)和红外光谱分析(FTIR)结合抽提实验证实,通过原位乳液聚合可在TiO2粒子表面锚固上13.5%的不可抽提PBA聚合物.动态激光粒度分析(DLS)发现,原位锚固改性对TiO2粒子软团聚体具有稳定的解团聚作用,可有效提高纳米TiO2粒子在体系中的分散性和分散稳定性.这一化学改性作用与超声分散所带来的物理性的可逆解软团聚作用有着本质区别.     

DMS AND ~(13)C NMR STUDIES ON THE COMPATIBILITY AND DYNAMICS OF LATEX BIDIRECTIONAL IPNS AND LATEX IPN OF PVAc/PBA

The compatibility and dynamics of latex bidirectional/nterpenetrating polymer networks (LBIPNs) and latex IPN(LIPN) of poly(vinyl acetate)(PVAc) and poly (butyl acrylate )(PBA) are investigated by means of dynamic mechanical spectroscopy (DMS) and nuclear magnetic resonance (NMR) techniques. The results of DMS show that the compatibility of the LBIPNs is much better than that of the corresponding LIPN and depends to, a large extent on the distribution of PVAc both in the core and in the shell. The results of NMR measurements indicate that the rotational correlation times of the side- groups of PBA in the LBIPN are longer than those in the LIPN. The relation between the ~(13)C linewidths of PBA and temperature is also discussed.