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.     

核壳结构三元含氟丙烯酸酯乳液的制备及表征

以甲基丙烯酸三氟乙酯(Actyflon-G03)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)为原料,采用质量比为 1/1 的 OP-10/SDS 复合乳化荆,利用种子乳液聚合法,合成了核壳结构共聚物乳液.研究了温度对聚合反应、氟单体含量对聚合物膜吸水性及硬度的影响,采用 DSC、SEM-EDX、TEM 表征了共聚物膜的性能及乳胶粒子特征.结果表明:当 Actyflon-G03 含量为 23.28%时,核壳型结构粒子呈球形分布,粒径约为 80～110 nm,膜吸水率最低,硬度最高,并有 75.85%的最大转化率和 0.58%的最低凝胶率.SEM-EDX 分析显示,氟原子在成膜过程中向膜表面迁移,降低了膜的表面能.     

含氟共聚乳液改善浸渍滤纸抗水抗油性的研究

用核/壳乳液聚合工艺,通过改变单体组成、设计乳胶粒子的形态结构和在乳胶粒子的壳层中引入含氟丙烯酸酯单体,制备具有核/壳结构的含氟丙烯酸酯的共聚乳液。并通过FTIR1、3C-NMR、TEM等手段对共聚乳液的化学结构以及乳胶粒子形态结构进行了表征。同时研究了含氟单体种类和用量、乳化剂种类以及单体加料方式对其聚乳液性能以及浸渍滤纸抗水/油性的影响。     

反应性复合乳液的合成、表征及其交联反应

利用种子半连续乳液聚合方法合成了核层或壳层带有环氧基以及壳层带有羧基的3种不同核/壳结构的乳胶粒子,通过物理共混带环氧基和羧基的乳胶粒子,得到了两种反应性复合乳液.利用透射电镜和激光动态光散射对乳胶粒子进行了表征,其粒径分布较窄,粒径分布的多分散系数为0.062,平均粒径约76 nm,乳胶粒子具有明显的核/壳结构.通过胶膜的凝胶率和膨胀率的测定和红外光谱分析对反应性复合乳液中乳胶粒子的扩散及交联反应进行了研究,并探讨了不同核壳结构复合乳液对涂膜机械性能的影响.研究表明,当反应性复合乳液中的环氧基和羧基分别分布在乳胶粒子的核层和壳层时,有利于聚合物分子链的充分扩散和化学交联反应的进行,从而提高涂膜的物理化学性能,当甲基丙烯酸缩水甘油酯(GMA)含量为10 wt%时,涂膜的拉伸强度达20.3 MPa.     

硅烷改性含氟丙烯酸酯共聚物乳液

利用正硅酸乙酯(TEOS)水解和长链烷基三甲氧基硅烷(WD-10)的硅烷偶联剂作用,以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和甲基丙烯酸十二氟庚酯(DFMA)为原料的核壳型含氟丙烯酸酯聚合物乳液进行原位复合改性。通过XRD、FTIR、SEM-EDX、TEM、RGD、DSC、NMR等测试技术分析和讨论了合成的聚合物乳液的乳胶粒子结构和形态,以及TEOS和WD-10含量对改性的聚合物乳液稳定性和对聚合物成膜性的影响。结果表明,TEOS水解产生了S iO2,核壳型结构粒子基本呈现圆形分布,粒径为40~50 nm。TEOS的最佳质量分数为3.1%~3.8%,WD-10含量宜控制在TEOS质量分数为0.9%~0.95%之间。     

SiO2/聚甲基丙烯酸叔丁酯核壳复合微粒的制备与表征

以甲基丙烯酸-3-(三甲氧基硅基)丙酯(MPS)修饰的SiO2胶体粒子为种子,甲基丙烯酸叔丁酯(tBMA)为单体、十二烷基硫酸钠(SDS)为乳化剂,采用种子乳液聚合法制备了SiO2/聚甲基丙烯酸叔丁酯的核壳复合微粒。微粒经水解后形成具有pH敏感性的无机/有机复合微粒。研究了影响核壳复合微粒形态结构的因素,结果发现,控制SiO2种子乳液的质量分数在1.5%～2%,可避免聚合过程中生成纯聚甲基丙烯酸叔丁酯乳胶粒子;反应体系中乳化剂SDS的用量超过质量分数0.3%时,易形成纯聚合物乳胶粒子;SDS用量低于质量分数0.15%时,生成的核壳复合微粒易产生团聚;单体和交联剂用量升高,核壳复合微粒的壳层厚度增加,用量过高会导致核壳复合微粒出现团聚现象,并且有纯聚合物乳胶粒子生成。采用TEM、NMR和FTIR及接触角测试技术分析结果表明,复合微粒是由SiO和聚甲基丙烯酸叔丁酯组成的核壳结构微粒。     

核壳型含氟丙烯酸酯共聚物的合成及性能

采用饥饿态半连续种子乳液聚合方法, 在十二烷基硫酸钠(SDS)/辛基苯基聚氧乙烯醚(TX-10)复合乳化剂的作用下, 分别选用甲基丙烯酸三氟乙酯(TFEM)、甲基丙烯酸六氟正丁酯(HFBM)和甲基丙烯酸十二氟庚酯(DFHM)为含氟单体, 合成以丙烯酸正丁酯(BA)、甲基丙烯酸甲酯(MMA)和含氟单体为原料的核壳型结构含氟丙烯酸酯共聚物乳液. FTIR, 1H NMR, TEM和DSC分析结果显示, 获得了BA/MMA/含氟单体的共聚物乳液, 且乳液具有明显的核壳结构. DSC, TGA和SEM-EDX的分析显示, 核壳型结构的共聚物具有优异的热力学稳定性能和成膜性能; 长侧链或短侧链含氟单体对共聚物的热稳定性影响不明显, 但侧链较长的含氟单体所获得的聚合物在成膜过程中更易向表面迁移, 更能体现含氟聚合物的优点.     

含氟/硅丙烯酸酯核壳型乳液的合成及性能

采用半连续种子乳液聚合法, 在十二烷基硫酸钠(SDS)/辛基苯基聚氧乙烯醚(TX-10)复合乳化剂的作用下, 合成了以丙烯酸丁酯(BA)为核, 以甲基丙烯酸甲酯(MMA)、甲基丙烯酸十二氟庚酯(DFHMA)、3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPTMS)和甲基三甲氧基硅烷(MTMS)为壳的核壳型含氟/硅丙烯酸酯聚合物乳液. 利用FTIR, TEM, SEM-EDX和DSC等手段对乳液组成、乳胶粒子结构、膜表面及断面形态等进行了表征, 讨论了氟/硅含量对聚合物膜性能的影响. 结果表明, 核-壳粒子尺寸为20~30 nm, 乳液膜的性能与膜表面氟和硅的含量及相容性有较大的相关性, 当m(氟)∶m(硅单体)=3∶1时, 形成的膜均匀透明, 吸水率较低, 尺寸稳定性较好.     

核壳型聚丙烯酸酯乳胶粒子及其乳液的研究进展

综述了目前制备核壳型聚丙烯酸酯乳胶粒子的常用方法,如种子乳液聚合法、无皂乳液聚合法、反相乳液聚合法、细乳液聚合法以及种子分散聚合法;分析了聚合工艺、单体种类、温度、乳化剂和引发剂种类及用量等因素对聚丙烯酸酯核壳乳液合成及性能的影响;并对聚丙烯酸酯核壳乳液的研究现状进行了归纳;最后,展望了聚丙烯酸酯核壳乳液的发展方向。     

核壳乳液聚合法制备含氟硅丙烯酸酯乳液

以氟醇RfCH2CH2OH和乙烯基硅氧烷VTES为原料合成的氟硅单体,与甲基丙烯酸甲酯、丙烯酸丁酯在复合乳化体系中通过核壳乳液聚合制备了稳定的氟硅共聚乳液。对氟硅单体和氟硅丙烯酸酯共聚物的结构用红外光谱进行了表征,结果表明,得到了目标单体和共聚物。共聚物的TEM形态观察发现,乳胶粒子具有明显的核壳结构,平均粒径在125 nm左右。与丙烯酸酯共聚物相比,氟硅丙烯酸酯共聚物乳胶膜的吸水率降低至8.32%,热分解温度提高了23℃,耐溶剂性与氟硅单体的含量关系不大。     

Synthesis of polyacrylate core-shell structure latex by radiation techniques

A series of poly(butyl acrylate-co-methyl methacrylate)/poly (ethyl acrylate-co-acrylic acid) interpenetrating polymer network (IPN) was synthesized in latex form by emulsion polymerization. The multiphase morphology of the latex particles was studied after two-stage polymerization by using transimission electron microscope (TEM), the result indicated that the morphology of the particles comprises gradient shell structure, cellular structure and core-shell structure. The change of morphology might stem from emulsion polymerization by radiation initiation or chemical initiation and the weight composition of poly(EA-co-MMA) seed latex which formed the core. By radiation techniques, we successfully synthesized poly( BA-co-MMA)/poly(EA-co-AA) latex of core-shell structure having (42-8)/(46-4) weight compositions. The PA core-shell structure latex applied to textile as a water proofing coating showed higher water-pressure and easier handling than that with PA homogeneous phase structure latex.     

Synthesis, modification and characterization of core-shell fluoroacrylate copolymer latexes

Core-shell fluoroacrylate copolymer latex, typically used for the protection of ancient stone monument, was synthesized in this paper by semi-continuous seed emulsion polymerization with butyl acrylate (BA) served as the core, methyl methacrylate (MMA), BA and dodecafluoroheptyl methacrylate (DFHMA, C₁₁H₈O₂F₁₂) served as the shell. At the same time, the above core-shell fluoroacrylate latex was modified by hydrolysis of tetraethyl orthosilicate (TEOS, Si(OC₂H₅)₄) in the presence of silane coupling agent dodecyltrimethoxysilane (DTMS, C₁₂H₂₅Si(OCH₃)₃). The chemical component of the final latex was analyzed by FT-IR. Morphology structure and the particle size of core-shell latex were determined by TEM. The effect of DFHMA and TEOS content on the latex and film properties was characterized by SEM-EDX, AFM, TEM, DSC and UV-vis. The analysis results indicated that the copolymer latex particle presented uniform sphere core-shell structure with 40-50 nm in diameter. About 30 wt% DFHMA gave favorable characteristics both in latex and in film properties. Compared with core-shell fluoroacrylate latex, the modified fluoroacrylate copolymer displayed, when TEOS was controlled in 2.2-3.8 wt%, sound performances in hydrophobic, mechanics, thermodynamics and resistance to ultraviolet.     

荧光探针法研究核壳结构有机硅-丙烯酸酯乳液的聚合行为

以芘为荧光探针,探讨了有机硅-丙烯酸酯核壳乳液聚合过程中,芘的第一振动峰(373 nm处)与第三振动峰(384 nm处)荧光强度的比值I1/I3与乳化剂、有机硅单体(D4)和引发剂(KPS)用量之间的关系,并结合聚合过程中探针芘的I1/I3峰值与单体转化率及乳胶粒形态演变之间的关系,研究了核壳结构有机硅-丙烯酸酯乳液的聚合行为.研究结果表明,探针芘的I1/I3峰值随乳化剂用量,D4用量,KPS用量不同发生相应的变化,随单体转化率的增加而增大.当乳化剂用量、D4用量、KPS与总单体的质量比依次为2 g、8 g、0.7%时,得到的乳液具有优良的综合性能.聚合反应过程中,当种子乳胶粒转变为核壳乳胶粒时,芘的I1/I3峰值仍呈现出明显的转变,说明有机硅-丙烯酸酯核壳乳液具有互穿聚合物网络结构.因此,荧光探针可用于研究有机硅-丙烯酸酯核壳乳液聚合反应进程.     

Comparative study between core-shell and interpenetrating network structure polyurethane/polyacrylate composite emulsions

Anionic aqueous polyurethane dispersion was prepared by using carboxyl acid group to make the polyurethane dispersible, and then nanograde core-shell and crosslinked IPN structure polyurethane/polyacrylate composite latex (PUA) were synthesized by soap-free emulsion polymerization method with polyurethane dispersion as seed. FTIR, DSC, dynamic light scattering, TEM, ESCA, TGA, electronic tensile machine were employed to investigate the structures and properties of the composite latex and their polymers. Meanwhile the core-shell composite PUA emulsion and the crosslinked IPN composite PUA emulsion were compared. The results showed that the particle morphology of PUA composite emulsion is inverted core-shell structure with polyacrylate as the core and with polyurethane as the shell. The morphology of the crosslinked PUA emulsion was multi-core structure. The surface in core-shell PUA contains rich PU phase. The phase structure of the crosslinked PUA is more uniform. Three transition temperatures are observed for the core-shell composite PUA, two transitions are observed for the film from the crosslinked PUA. The TGA curves of core-shell PUA and crosslinked PUA exhibit two stages, the first stage corresponds to the thermal decomposition of hard segments in seed polyurethane; the second stage corresponds to the decomposition of soft segments in PUA and decomposition of polyacrylate. With the increase of glycidyl methacrylate (GMA) amounts in PUA composite emulsions, the tensile strength of the PUA films as well as the average diameter of the PUA composite emulsion particles increase, the elongation at break of the PUA films decreases.     

EFFECT OF THE PHASE STRUCTURE EVOLUTION ON THE PROPERTIES OF FILMS FORMED FROM PBA/P(St-co-MMA) COMPOSITE LATEX

A group of heterogeneous latexes poly(butyl acrylate)/poly(styrene-co-methyl methacrylate)(PBA/P(St-co-MMA)) were prepared by a semi-continuous seeded emulsion polymerization process under monomer starved conditions.The glass transition temperature(T_g)and the mechanical properties of the film formed from the composite latex changed with the evolution of the particle morphology.A photon transmission method was used to monitor the phase structure evolution of films which were prepared from core-shell PBA/...     

Synthesis of water-soluble hyperbranched polymer and its application in acrylic latex

A water-soluble hyperbranched polymer (WHBP), obtained from a second generation of hyperbranched polyester and maleic anhydride, was studied. Its effects on the properties of acrylic latexes, which were based on emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA), acrylic acid (AA) and WHBP, and latex film were discussed. The characteristics of WHBP were determined by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared (FTIR) and gel permeation chromatography (GPC). Particle size and morphology of latex particles were confirmed by dynamic light scattering (DLS) and transmission electron microscope (TEM). The investigation showed that WHBP could be used in emulsion polymerization, and that latex of poly(BA-MMA-WHBP) was more stable than that of poly(BA-MMA-AA). The hardness of latex film increased from 2B to HB when WHBP was used.     

Preparation and Characterization of Nano-TiO2/poly (methyl methacrylate) Hybrid Latex by Reverse Microemulsion Method and In-Situ Polymerization

The organic nano-TiO₂ was synthesized in reverse (W/O) microemulsion, using tetrabutyl titanate (TBOT) as precursor and γ-methacryloxypropyl trimethoxy silane (KH-570) as modifier. After phase inversion from W/O microemulsion to oil-in-water (O/W) emulsion, nano-TiO₂/poly(methyl methacrylate) hybrid latex was prepared via in-situ polymerization based on the O/W emulsion containing organic nano-TiO₂. Fourier transform infrared spectroscopy (FTIR) indicated that KH-570 was successfully grafted onto the surface of TiO₂ particles. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) demonstrated that the average diameter of nano-TiO₂ was about 10 nm and the hybrid latex had obvious core-shell structure with particle size of 155 nm. The TBOT content and the mass ratio of KH-570 to TOBT have important effect on the polymerization stability and storage stability of the hybrid latex. When the TBOT content was 5% and the mass ratio of KH-570 to TOBT was 0.6, the coagulation rate (C_r) was 3.0% and the zeta potential reached 36.1 mV. The possible formation mechanism of the hybrid latex was also proposed.