有机硅/丙烯酸酯共聚复合乳液结构形态的研究

利用红外光谱及扫描电镜对合成的有机硅-丙烯酸酯共聚复合乳液的化学结构、粒子形态进行了研究.结果表明:所合成的有机硅一丙烯酸酯复合乳液为具有核壳形态结构的新型乳胶液,其核/壳间存在化学键合.与纯丙乳液和硅-丙共聚乳液相比,核壳型复合乳胶膜在耐水性方面有显著提高.     

醋-丙乳液型压敏胶的研发和生产

概述了将增粘树脂和纳米无机粒子引入丙烯酸酯乳液,采用特殊乳化剂和特殊单体合成丙烯酸酯乳液以及在核-壳乳液共聚等方面开展的研究,并就其研制开发成果和工业化生产作了介绍。     

核壳型短链含氟丙烯酸酯乳液的合成及表征

该文研究了核壳型短链含氟丙烯酸酯乳液的合成与表征。以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)的共聚体为核,短氟碳链2-(全氟己基)乙基甲基丙烯酸酯(FMA6)和非氟烷基丙烯酸酯的共聚体为壳,采用多步乳液聚合法,合成系列具有核壳结构的含氟丙烯酸酯乳液,研究了壳相中氟单体用量和非氟烷基丙烯酸酯的烷基链长度n(链长n=4、8、12、16、18)对产物疏水疏油性能的影响,并对产物进行表征。结果表明:当采用氟单体用量为总单体质量的8.5%,甲基丙烯酸十六酯(CMA)的共聚体为壳层时,由合成乳液制得的乳胶膜的疏水疏油性最佳,对水接触角为124.67°,对二碘甲烷接触角为112.76°。FTIR、TEM和DSC/TGA表征表明,原料单体均参加了反应;乳液颗粒具有明显的核壳结构;聚合物存在两个玻璃化温度(-18.87℃和32.08℃),热分解温度比不含氟的聚合物提高了近20℃。由此说明,用合成的核壳型短链含氟丙烯酸酯乳液制得的涂膜具有优异的疏水疏油性和耐热性能。     

高阻尼性涂层用环氧-丙烯酸酯复合乳液的合成

采用分步乳液聚合法合成了一种具有核-壳结构的环氧-丙烯酸酯复合乳液,通过核层和壳层之间的化学交联使涂膜具有较高的阻尼性能。通过透射电镜观察到乳胶粒子呈均匀的核-壳球形结构,红外光谱(FTIR)结果表明复合乳液涂膜实现了环氧与丙烯酸树脂的交联反应。动态热机械分析(DMA)显示该乳液涂膜具有较高的损耗因子和较宽的阻尼温域,加热成膜的最大损耗因子(tanδ)达到2.12,明显高于传统阻尼涂料,在tanδ0.3的阻尼温域为40℃,在金属阻尼涂层材料领域具有良好的应用潜能。     

硅溶胶/聚丙烯酸酯复合乳液的结构和性能研究

采用普通乳液聚合的方法,制备了硅溶胶/聚丙烯酸酯复合乳液.通过透射电镜(TEM)、傅里叶红外光谱仪(FT-IR)和动态激光散射仪(DLS)等对复合乳液中乳胶粒子的结构进行表征,并对复合乳液的涂膜性能进行研究.结果表明,所制备的复合乳液粒子具有核-壳结构,其中核是纳米级的SiO2粒子,壳是聚丙烯酸酯.性能测试结果表明,核-壳结构的存在使得复合乳液的涂膜在硬度、附着力和化学稳定性等方面均优于纯丙乳液及硅溶胶/聚丙烯酸酯的共混乳液.     

高阻尼性涂层用环氧-丙烯酸酯复合乳液的合成

采用分步乳液聚合法合成了一种具有核-壳结构的环氧-丙烯酸酯复合乳液,通过核层和壳层之间的化学交联使涂膜具有较高的阻尼性能。通过透射电镜观察到乳胶粒子呈均匀的核-壳球形结构,红外光谱（FTIR）结果表明复合乳液涂膜实现了环氧与丙烯酸树脂的交联反应。动态热机械分析（DMA）显示该乳液涂膜具有较高的损耗因子和较宽的阻尼温域,加热成膜的最大损耗因子（tan δ）达到2.12,明显高于传统阻尼涂料,在tan δ >0.3的阻尼温域为40℃,在金属阻尼涂层材料领域具有良好的应用潜能。     

含氟核壳纳米粒子的制备及其表征

通过半连续的加料工艺制备了聚甲基丙烯酸三氟乙酯（PTFEMA）为壳,以聚丙烯酸甲酯（PMA）为核的纳米核壳乳液。并通过SEM、TEM、DSC、DLS等对合成的乳液进行表征,结果表明：所合成的粒子具有核壳结构,粒子形貌较为规整,且成球效果很好。     

具有核壳结构的有机硅改性丙烯酸酯乳液的结构及性能

采用甲基三甲氧基硅烷在丙烯酸酯单体中水解的原位乳液聚合法,制备了具有核壳结构的有机硅改性丙烯酸酯乳液(硅丙乳液),并用傅里叶变换红外光谱、透射电子显微镜和x射线光电子能谱对其结构进行了表征,考察了硅丙乳液的疏水性.结果表明,所合成的硅丙乳液具有稳定的核壳结构,核为甲基三甲氧基硅烷树脂,壳为丙烯酸酯聚合物;硅丙乳液的疏水性较纯丙乳液强.     

以核壳结构聚合物模板合成P(St-co-DEA)/SiO_2杂化粒子

本文采用聚(苯乙烯-co-甲基丙烯酸-N,N-二甲氨基乙酯)[P(St-co-DEA)]核壳纳米粒子为模板,在环境条件下以四甲基硅氧烷(TMOS)为前体,原位可控沉积纳米结构SiO2,合成了具有PSt核和PDEA-SiO2杂化的壳层纳米粒子,将杂化粒子进一步煅烧可得到空心的SiO2纳米微球。采用FT IR、TEM以及DLS对所合成的杂化纳米粒子进行了详细的表征。TEM观察证实了纳米结构SiO2在粒子壳层中的沉积,随着矿化反应的进行,体系形成了具有核壳结构的树莓状纳米粒子。研究表明:杂化粒子的表面粗糙程度及大小可以通过简单改变体系试验参数(如TMOS的用量和矿化时间等)而控制。     

核壳型常温自交联丙烯酸酯乳液的合成

根据"粒子设计"原理,采用种子预乳化半连续核壳乳液聚合工艺,引入常温自交联单体,合成了具有硬核软壳结构、常温自交联的可用于木器涂料的丙烯酸酯乳液。通过试验表明,核组分玻璃化温度为80~85℃、壳组分玻璃化温度为-5～0℃,并且核壳质量比为6∶4;自交联单体DAAM添加量为4%,且在壳组分含量为3%;MAA添加量为1.5%,核/壳中添加的羧基质量比为1∶3时,聚合物乳液抗粘连性、耐醇性、成膜性等综合性能好。     

聚合工艺对纳米SiO_2在原位乳液聚合中分散性的影响

采用原位乳液聚合法将未经表面处理的纳米SiO2引入到聚丙烯酸酯乳液,考察了纳米SiO2的引入方式、乳化剂在预乳液与釜底的分配、种子乳液的来源等对其分散性的影响。TEM及粒径分析表明,纳米SiO2能有效地被分散成为初次粒子并以纳米量级与原位生成的聚丙烯酸酯复合,纳米SiO2因界面作用被吸附嵌入到乳胶粒子的表面,使粒子具有“草莓”般的形貌。     

聚合物-纳米无机粒子复合微球研究新进展

近年来,聚合物-纳米无机粒子复合微球相关的设计、制备、以及应用研究得到了科学界众多学者的广泛关注与探索。本文论述了单体聚合法制备聚合物-纳米无机粒子复合微球的研究近况,主要介绍了悬浮聚合、乳液聚合(微乳液聚合、Pickering乳液聚合、细乳液聚合、反相乳液聚合、无皂乳液聚合)、分散聚合及溶液聚合的制备方法。概述了聚合物-纳米无机粒子复合微球在生物医药、光电材料、保护涂层、催化等方面的应用,展望了聚合物-纳米无机粒子复合微球的发展趋势。     

A convenient approach to synthesize stable silver nanoparticles and silver/polystyrene nanocomposite particles

In this study, silver nanoparticles were prepared by the reduction of silver nitrate in SDS+ isopentanol/styrene/H₂O reverse microemulsion system using sodium citrate as reducing agent. The Ag/PS nanocomposite particles were prepared by in situ emulsion polymerization of the styrene system containing silver nanoparticles that did not separate from the reaction solution. The polymerization dynamic characteristic was studied, at the same time, silver nanparticles and the encapsulation of composite particles were characterized by Fourier‐transform‐infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X‐ray diffraction (XRD) measurement, UV–vis diffuse reflectance spectroscopy, and X‐ray photoelectron spectroscopy (XPS). The results of TEM and UV–vis absorption spectra showed that well‐dispersed silver nanoparticles have a narrow size distribution. XRD showed that Ag and Ag/PS nanocomposite particles were less than 10 and 20 nm in size, which is similar to those observed by TEM. The results of XPS spectra revealed that the microemulsion system can stabilize the silver nanoparticles from aggregation and provided supporting evidence for the polystyrene encapsulated silver nanoparticle structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

Synthesis and friction properties of copper/PMMA composites by soapless emulsion polymerization

Copper (Cu)‐doped polymethylmethacrylate (PMMA) composites were prepared by soapless emulsion polymerization. In this process, copper nanoparticles were modified by sodium oleate (SOA) and the surface property of Cu nanoparticles changed from hydrophilic to hydrophobic. The hydrophobic Cu nanoparticles could not only avoid the oxidation of Cu in air but also improve the compatibility between Cu nanoparticles and PMMA. The TEM micrographs revealed that Cu nanoparticles were encapsulated in PMMA polymer microspheres. In addition, the uniform Cu/PMMA composite microspheres could be synthesized in such a soapless emulsion polymerization process. It was worth mentioning that the friction property in oil was well improved when little nanocomposites were added into the base oil, which indicated that the composites can be widely used in lubricating oil. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

PSt乳胶纳米粒子的制备

采用乳液原子转移自由基聚合法,成功制备出了聚合物乳胶纳米粒子。用光子相关光谱(PCS)和透射电子显微镜(TEM)对聚合物乳胶粒子的形貌、粒径和粒径分布进行了表征,结果表明:聚合物乳胶粒子的粒径小于100nm。研究了乳化剂的用量对乳胶粒子粒径大小的影响,研究发现:聚合物乳胶粒子的粒径随乳化剂用量的增大而减小。     

SiO2/PBA/PMMA和CaCO3/PBA/PMMA核壳结构纳米材料的制备与表征

利用γ 甲基丙烯酰氧丙基三甲氧基硅烷(KH-570)对纳米二氧化硅和纳米碳酸钙有机化处理,红外光谱(FTIR)测试表明,纳米二氧化硅通过有机化处理可以在表面接枝上有机基团,表现在表面处理后波数在2955,2860和1460cm-1有甲基的吸收峰,而纳米碳酸钙由于表面上已有有机基团,表面上没有接枝上新的有机基团。然后利用乳液聚合的方法制备了以表面处理过的纳米二氧化硅或纳米碳酸钙为核,丙烯酸丁酯和甲基丙烯酸甲酯为壳的有机-无机杂化材料。用凝胶渗透色谱(GPC)测定了其各种相对分子质量及其相对分子质量分布后发现,加入纳米碳酸钙后其相对分子质量有所降低,相对分子质量分布变宽;加入纳米二氧化硅后其相对分子质量有所增大,相对分子质量分布变窄。透射电镜(TEM)和粒度分布仪测试表明,乳液聚合前粒子大部分以团聚体的形式存在,粒径在1～2μm左右;乳液聚合后粒子大部分以纳米尺寸存在,粒径10～200nm。实验证明,乳液聚合是制备有机-无机纳米杂化材料非常有效的方法。     

Preparation of crosslinked composite nanoparticles

Crosslinked composite nanoparticles were prepared by adding a trifunctional monomer (trimethyol propane trimethacrylate) or a difunctional monomer (divinyl benzene) as a crosslinker into the emulsion polymerization system of styrene in the presence of inorganic nanosilica. A coupling agent, 3‐methacryloxypropyltrimethoxysilane (MPS), was added along with the monomer, crosslinker, and silica to improve the interfacial interaction between silica and polymer and thus to obtain high binding efficiency. The role of MPS was examined. The effects of crosslinkers on the kinetics of emulsion polymerization, monomer conversion, and yield were investigated. The morphology of the composite particles was observed by TEM. The particle size and size distribution of composite latex particles were measured by the dynamic light scattering method. The binding efficiency and swelling ratio were determined by reluxing the sample in xylene using a Soxhlet extraction apparatus. FTIR spectra and TGA verified the participation of crosslinker and silica. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1538–1544, 2005     

Growth mechanism and pH-regulation characteristics of composite latex particles prepared from Pickering emulsion polymerization of aniline/ZnO using different hydrophilicities of oil phases

A Pickering emulsion polymerization of aniline, using different hydrophilicities of oil phases, was stabilized by ZnO nanoparticles and performed to synthesize composite latex particles of polyaniline/ZnO. Ammonium peroxydisulfate (APS) was used as an oxidizing agent. The morphologies and growth mechanisms of the resulted composite latex particles were studied. The pH-regulation capacity of the composite latex particles was discussed. When toluene was used as the oil phase, the composite latex particles showed hollow structure, irregular morphology, and hundreds of nanometer in size. It was ascribed to the polymerization of aniline on the interfaces of droplets/water. ZnO nanoparticles, with 50-100 nm in size, acted as surfactants to stabilize the emulsion. When THF was used as an oil phase, the composite latex particles showed spherical morphology and enwrapping ZnO nanoparticles. It was attributed to the homogeneous nucleation of polyaniline in the aqueous phase. ZnO nanoparticles acted as templates for the polyaniline particles. The stability of the Pickering emulsion polymerization was affected by the volume ratio of the oil phase to water. The aqueous solution with pH 3-9 could simply be regulated to about pH 7 by the composite latex particles. It was contributed by the dissolution of ZnO nanoparticles and doping-dedoping of polyaniline in the acidic and alkaline aqueous solutions.     

Facile preparation of pH-responsive gelatin-based core-shell polymeric nanoparticles at high concentrations via template polymerization

Adopting gelatin as template macromolecules and acrylic acid (AA) as monomers, core-shell polymeric nanoparticles at a concentration of 30 mg/mL was successfully prepared via template polymerization, in which polymerization of the monomer and self-assembly between the polymer and the template take place simultaneously. The self-assembly was driven by specific interactions between gelatin and PAA produced in-situ, leading to nanoparticles with insoluble inter-polymer complexes of PAA and gelatin as the core and soluble gelatin as the shell. DLS and electrophoretic light scattering techniques were used to monitor the in-situ polymerization process, which indicated a size shrinkage and a surface charge decrease of the nanoparticles. The structure and morphology of the nanoparticles were characterized by FT-IR, TEM and SFM. The structure stability of the nanoparticles was improved by selectively crosslinking gelatin with glutaraldehyde. The nanoparticles also exhibit excellent pH-response: when pH changed from acid to base, the particles' volume expanded more than 80 times.     

聚苯乙烯纳米粒子模板的组装

利用微乳液法制备了平均粒径约为600nm的聚苯乙烯纳米粒子,聚苯乙烯纳米粒子在溶胶水分子缓慢自然挥发过程中,可自发地在固体基底表面形成单层或多层自组装规则结构,通常每层聚苯乙烯粒子都采用密堆积方式排列,其自组装排列为典型的立方面心密堆积结构.探讨了温度、质量分数对模板粒子排列的影响,利用SEM和TEM检测了模板的形状和粒径.