紫外光引发乳液聚合的研究进展

紫外光引发乳液聚合可在室温下进行,克服了热引发的缺点,应用潜力巨大。本文介绍了其发展历程和国内外的研究进展,以及特点、应用等。     

光引发RAFT分散聚合制备单分散聚合物微球

使用聚乙二醇基的大分子可逆加成断裂链转移(RAFT)试剂,在乙醇/水介质中通过光引发RAFT分散聚合制备聚甲基丙烯酸甲酯(PMMA)微球。通过扫描电子显微镜(SEM)对聚合物微球的形成进行探究,并研究了实验中各反应条件对聚合物微球粒径以及粒径分布的影响。结果表明：光引发剂的浓度对聚合物微球的粒径和粒径分布影响都不大;大分子RAFT试剂的添加量在6wt%～14wt%范围内都能形成单分散的聚合物微球;随着单体浓度的增加聚合物微球的粒径相应增大。     

细乳液聚合制备二氧化钛/聚苯乙烯复合微球及其形貌分析

采用细乳液聚合法,以γ-甲基丙烯酰氧基丙基三甲基硅烷改性的TiO2粒子为核,制备了核壳结构的TiO2/聚苯乙烯(PS)复合微球。研究了超声细乳化时间、乳化剂十二烷基硫酸钠(SDS)的浓度、TiO2用量对细乳液粒径及其分布的影响。通过纳米粒度与Zeta电位分析仪、红外光谱、透射电镜等分析手段对产物进行了表征。结果表明,随着超声细乳化时间的增加,初始液滴的粒径变小。聚合后的乳胶粒粒径随着SDS浓度的增大而减小;TiO2用量不足导致乳胶粒粒径分布变宽,且出现双峰;制备所得的TiO2/PS复合微球粒度分布较为均匀,平均直径为176.5 nm,球形规整度较好。     

氧化还原体系引发苯乙烯乳液聚合

以不同的过氧化物引发剂分别与硫酸亚铁组成氧化还原引发体系,引发苯乙烯的乳液聚合,研究反应温度和还原剂用量等对聚合的影响.采用气相色谱、三检测体积排除色谱、动态光散射对单体转化率、聚苯乙烯的相对分子质量及其分布和乳胶粒径进行了分析.结果表明:升高温度或增加还原剂用量均会使聚合物的相对分子质量增大,聚合反应速率加快,与常规...     

等离子体引发丙烯酸(2-乙基)已酯乳液聚合

采用等离子体引发聚合的方法 ,进行了丙烯酸 ( 2 -乙基 )已酯 (简称 EHA)的乳液聚合。考察了后聚合时间、放电功率、乳化剂浓度对聚合转化率及特性粘数的影响。并对丙烯酸酯等离子体引发本体、乳液聚合进行了比较     

细乳液聚合制备磁性复合微球研究进展

介绍了细乳液聚合的特点、细乳液聚合制备磁性复合微球的一般步骤;从制备影响因素角度,对近年来国内外细乳液聚合制备磁性复合微球的研究进行了综述。磁性复合微球主要采用正相细乳液聚合,影响微球制备的主要因素有乳化剂类型和用量、磁性纳米粒子表面修饰、超声分散、助稳定剂类型、交联剂引发剂和磁流体用量等。今后,细乳液聚合制备磁性复合微球的研究仍将关注提高复合微球性能(高磁响应性能、粒子大小可控且均匀、具有表面功能基团)及产率(磁性粒子包覆率)等方面。     

无皂乳液聚合制备SiO_2/PMMA纳米复合胶体微球

采用半连续无皂乳液聚合方法在未经硅烷偶联剂改性的230 nm亲水性SiO2微球表面聚合甲基丙烯酸甲酯(PMMA)壳层,制备以SiO2粒子为核、PMMA为壳层的复合胶体微球。研究微球表面形貌、组成、粒径变化规律,探索聚合反应的成核过程和PMMA进料流量对复合微球粒径的影响。结果表明,在未经硅烷偶联剂改性的纳米SiO2表面可形成稳定规整的PMMA壳层,SiO2/PMMA复合胶体微球球型度接近1.0,单分散性较好,多分散度指数(PDI)小于0.04。聚合反应受甲基丙烯酸甲酯(PMMA)单体含量控制,随着PMMA进料流量增加,乳胶粒子成核过程由均相成核过渡为胶束成核,复合微球粒径加速增大,多分散性增强,其粒径可通过调节PMMA进料流量控制。     

乳液聚合法制备单分散性PS磁性微球的研究

用改进的乳液聚合法,以乙醇／水为反应介质,十二烷基苯磺酸钠为乳化剂,过硫酸钾为引发剂,制备出单分散性聚苯乙烯磁性微球。通过SEM观察其表面形貌、粒径大小及分布,表明具有良好的球形度和一定均匀性。为了制备出粒径小、粒径分布均匀的聚苯乙烯磁性微球,设计了正交实验来优化实验条件;探讨了反应聚合温度、引发剂用量、乳化剂用量及醇水比对微球粒径及粒径分布的影响。实验表明在实验范围内,较低的反应温度、较低的引发剂用量、较高的乳化剂用量、较低的醇水比有利于得到小粒径、高均匀性的PS磁性微球。     

微波辐射无皂乳液聚合法制备PS微球

采用无皂乳液聚合法制备聚苯乙烯（PS）微球,以微波辐射加热方式代替传统油浴或水浴加热方式,研究了聚合体系中引发剂过硫酸钾的浓度、交联剂二乙烯苯与稳定剂α-甲基丙烯酸的体积比、微波功率大小对PS微球形貌、粒径及其分布的影响。结果表明,较传统加热方式,微波辐射加热方式极大地改善了PS微球的球形度和表面形貌。PS微球粒径随着引发剂浓度的增加呈现减小的趋势,随着交联剂与稳定剂体积比及微波功率的增加均呈现先减小后增大的趋势。当引发剂浓度为6.06×10^–3 mol/L、交联剂与稳定剂体积比为2∶1、微波辐射功率为300 W时所制备的PS微球表面光滑、球形度高、粒径分布均匀,平均粒径约为240 nm。PS微球表面带负电荷且分散性良好,并通过Hertz接触理论计算得到PS微球的压缩弹性模量约为2.75 GPa。     

以芬顿( Fenton)试剂为引发剂分散聚合制备PMMA微球

采用分散聚合法以甲基丙烯酸甲酯(MMA)为单体,水/乙醇(H2O/EtOH)作为分散介质,聚乙烯吡咯烷酮(PVP)为分散稳定剂,芬顿试剂硫酸亚铁(FeSO4)和双氧水(H2O2,30％)在pH =3 ～4的弱酸性条件下作为引发剂,制备了粒径约为408 nm的单分散聚甲基丙烯酸甲酯(PMMA)微球.探讨反应机理及分散介质的配比、单体浓度、分散稳定剂用量、聚合反应时间等对PMMA微球粒径和分散性的影响.该工艺选用新型引发剂,无需除氧,聚合时间短,操作简单,和传统工艺相比具有明显的优势.     

Kinetic study of photoinitiated frontal polymerization

The frontal polymerization of a monomer exposed continuously to UV radiation in the presence of a photobleachable initiator has been studied on the basis of the rate equations. The time dependence of photoinitiator concentration profile and that of monomer conversion within the irradiated sample have been calculated, assuming steady‐state conditions. It is thus possible to visualize how fast the polymerization profile is moving within the sample and how effectively the polymerization of a monomer layer located at a given distance from the surface proceeds upon exposure to UV radiation. © 2001 Society of Chemical Industry     

无皂乳液聚合制备AANa-VAc-TFEMA纳米含氟乳液

以丙烯酸钠(AANa)、乙酸乙烯酯(VAc)和甲基丙烯酸三氟乙酯(TFEMA)为单体进行无皂乳液聚合,合成了P(AANa-VAc-TFEMA)纳米含氟乳液,考察了反应温度、引发剂用量、单体配比对聚合的影响,并着重对聚合物乳液的粒径进行了研究。结果表明:该聚合单体的转化率可达到97.00%以上,聚合得到的无皂乳液稳定性好、粒径分布均匀。通过控制单体配比中AANa的含量及VAc与TFEMA的比例,可以得到纳米含氟乳液。     

阳离子聚丙烯酰胺微球浓乳液制备及粒径演化

浓乳液聚合产品稳定性好,颗粒尺寸更接近地层孔隙尺寸,在油田开发中具有较大的应用价值。基于微乳液制备了一系列甲基丙烯酰氧乙基三甲基氯化铵和丙烯酰胺的浓乳液,通过电导率测试、流变性分析、显微镜观察,研究了聚合前后浓乳液结构、粒径分布及稳定性。结果表明浓乳液的黏度及屈服应力,随着水相单体浓度（C_M）增加而降低,随着油相中表面活性剂含量（m_S）增加先升高后降低,乳液稳定性有相同趋势;浓乳液在C_M>40%及m_S=2.5 g时的失稳,原因分别是渗滤作用和高黏度下乳化不充分;聚合前液滴粒径分布在1～30 mm,聚合后微球粒径在0.4～5 mm,且粒径分布由聚合前双峰变为聚合后单峰,这一现象可以由Kolmogoro-Hinze的乳化理论解释,并由微球乳液的黏度增加至原始浓乳液的10倍证实。     

乳液聚合法聚丙烯酸树脂的制备研究

介绍了以丙烯酸、苯乙烯、丙烯酸丁酯、丙烯酸羟丙酯为单体,采用过硫酸铵作为引发剂,以非离子乳化剂聚氧乙烯醚(OP-10)和阴离子乳化剂十二烷基硫酸钠(SDS)作为复合乳化剂,经过乳液聚合,制得了一种水性涂料用缔合型增稠剂.考察了丙烯酸单体含量、乳化剂用量对乳液性能和增稠剂黏度的影响.优化了反应条件,反应过程和最终乳液都很...     

Preparation of magnetic poly(glycidyl methacrylate) microspheres by emulsion polymerization in the presence of sterically stabilized iron oxide nanoparticles

With the aim to synthesize water‐dispersible superparamagnetic nanoparticles, iron oxide was precipitated in aqueous solution of dextran, (carboxymethyl) dextran (CM‐dextran), (DEAE‐dextran), or D ‐mannose. Glycidyl methacrylate (GMA) was emulsion‐polymerized in the presence of the nanoparticles and the effect of iron oxide modification on the product properties was investigated. The main factors affecting the morphology, size, and size distribution of the latex particles are the type and concentration of emulsifier (Disponil AES 60, Tween 20, Triton X‐100) and initiator [ammonium persulfate (APS) and 4,4′‐azobis(4‐cyanovaleric acid) (ACVA)]. Disponil AES 60 and ACVA are the preferred emulsifier and initiator, respectively, because oxirane groups hydrolyzed during the APS‐initiated polymerization. Up to some 5 wt % of iron was found in poly(glycidyl methacrylate) (PGMA) microspheres obtained by emulsion polymerization in the presence of dextran‐coated iron oxide and emulsified with Disponil AES 60. The size of magnetic PGMA microspheres could be controlled in the range ? 70–400 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4348–4357, 2006     

Preparation and properties of urethane/acrylate composite by emulsion polymerization technique

Aqueous polyurethane–acrylic hybrid emulsions were prepared by semibatch emulsion polymerization of a mixture of acrylic monomers (styrene, butyl acrylate and acrylic acid) in the presence of polyurethane dispersion. Equivalent physical blends were prepared by mixing acrylic emulsion and polyurethane dispersion. The weight ratio between acrylic and polyurethane components was varied to obtain enhanced performance properties and microphase structure of hybrid latexes. The synthesized emulsion hybrids and physical blends were characterized by fourier transform infrared spectroscopy, thermogravimetric analysis. The experimental results indicate better acrylic–polyurethane compatibility in hybrid emulsions than in physical blends, resulting in improved chemical and mechanical properties. The blend ratio 50:50% (w/w) exhibited synergistic effects between the two polymers and revealed remarkable improvement in various coating properties over other blend ratios and the individual resin components.     

Preparation of micron‐size monodispersed PS/P(St/MAA) microspheres by seeded dispersion polymerization

Uniform polystyrene (PSt) particles with the size of 1.9 μm were first prepared via dispersion polymerization, and then used as the seeds in a second‐stage dispersion copolymerization of styrene (St) and methacrylic acid (MAA) to produce carboxyl‐carrying microspheres. The PSt seed particles were swollen by monomer mixture of St and MAA, including an oil‐soluble initiator 2,2′‐azobisiso‐butyronitrile (AIBN), before polymerization. Finally, uniform PS/P(St/MAA) (polydispersity index, PDI = 1.02) microspheres with the size of 2.2 μm were obtained. The average particle size and size distribution of the final microspheres were investigated. MAA contents between 54 and 97 mg/g were detected from the PS/P(St/MAA) particles produced under different conditions. Dispersion medium has great influence on the kinetics of polymerization, due to its effect on the partitioning of monomers, solvents, and initiator in the particle phase, probably as well as on the conformation of the dispersion agent on the surface of the particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3586–3591, 2006     

种子乳液聚合法制备纳米SiO_2/苯丙复合乳液

采用种子乳液聚合工艺,用经硅烷偶联剂改性后的纳米SiO2原位合成了纳米SiO2/苯丙复合乳液。通过正交实验确定了最佳原料配比和聚合工艺条件,并对复合乳液性能进行了分析与表征。结果表明,当功能单体的用量为单体总量的5%、阴离子乳化剂十二烷基硫酸钠(SDS)与非离子乳化剂辛基苯基聚氧乙烯醚(OP-10)质量比为1颐1、复合乳化剂总量3%、纳米SiO2含量为单体总量的1.5%、聚合温度为80℃时,可制备具有良好综合性能的复合乳液,其涂膜耐水性、硬度、附着力等均优于普通苯丙乳液。该复合乳液乳胶粒粒度呈单峰分布,平均粒径为101nm,具有核/壳结构。     

Poly(methyl methacrylate) nanoparticles prepared through microwave emulsion polymerization

The emulsifier‐free emulsion polymerization of methyl methacrylate (MMA) was conducted with microwave irradiation. Superfine and monodisperse poly(methyl methacrylate) (PMMA) microspheres were obtained. Microwave irradiation notably promoted the polymerization reaction. This phenomenon was ascribed to the acceleration of the initiator [potassium persulfate (KPS)] decomposition by microwave irradiation. The experimental results revealed that the apparent activation energy of KPS decomposition decreased from 128.3 to 106.0 kJ/mol with microwave irradiation. The average particle size of the prepared PMMA latex was mainly controlled with the MMA concentration; it increased linearly from 103 to 215 nm when the MMA concentration increased from 0 to 0.3 mol/L and then remained almost constant at MMA concentrations of 0.3–1.0 mol/L. The KPS concentration had no effect on the average particle size, but the particle size dispersity was significantly reduced by a high KPS concentration. With a mixed polymerization phase (water/acetone = 1:3 v/v) or a redox initiation system, PMMA nanoparticles were obtained with an average particle size of 45 or 67 nm, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2815–2820, 2004     

Synthesis of chitosan‐modified poly(methyl methacrylate) by emulsion polymerization

Emulsion polymerization of methyl methacrylate (MMA) in the presence of chitosan was studied and a reaction mechanism was proposed. It was proved in the companion article that potassium persulfate (KPS) free radicals can degrade chitosan chains into chain free radicals. Therefore, it is possible to produce a chitosan copolymer when the monomer and the KPS initiator are added into the chitosan solution. According to the proposed mechanism, concentrations of different species such as the initiator, total free radicals, and degraded chitosan chain were calculated with the reaction time. All the results agreed with the experimental observation. The results showed that the polymerization rate varied with 0.83‐ and 0.82‐order of the total free‐radical concentration and chitosan repeating unit concentration, respectively. It was also verified that chitosan played multiple roles in the reaction system. If the monomer was added into the chitosan solution before the addition of KPS, chitosan served mainly as a surfactant. Consequently, the polymer particle number was increased with the chitosan addition and so was the polymerization rate. However, if the monomer was added into the solution where the chitosan was already degraded by KPS, the polymerization rate was decreased with the predegradation time of chitosan. In both cases, the final polymer particles consisted of the poly(methyl methacrylate) (PMMA) homopolymer and the chitosan‐PMMA copolymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3047–3056, 2002