有机硅改性丙烯酸酯共聚乳液合成方法及胶膜性能的研究

用一次投料法、单体乳液滴加法和引发剂滴加法有机硅改性丙烯酸酯共聚乳液，聚合过程、胶粒形态及乳液稳定性的观测结果表明：单体乳液滴加法是合成该类乳液的最佳方法，研究了单体乳液滴加法中有机硅含量与聚合反及胶膜性能的关系，结果表明：有机硅含量在１５％以下时，聚合反应可以顺利进行，胶膜性能不仅依赖于聚合时有机硅单体的总量，而且还依赖于有机硅单体中活性硅氧烷所占的比例。     

Synthesis of silicone–acrylate copolymer latexes and their film properties

Emulsion copolymerization of silicones (octomethyl tetracyclosiloxane, D₄ and methacryloxypropyl trimethoxy silane, MATS) and acrylics was carried out using three different polymerization processes: semicontinuous monomer emulsion addition, batch and initiator solution addition. Results showed that only the semicontinuous process led to a stable latex with monodisperse particles. Various polymerizations were carried out through this process with varying silicone/acrylic ratios and MATS content. Films were obtained from different latexes: their properties are significantly influenced by silicone and MATS contents in copolymers.     

Reactive surfactants in heterophase polymerization: Colloidal properties,film‐water absorption,and surfactant exudation

In this article the results obtained with latexes prepared by emulsion polymerization with a conventional surfactant and a polymerizable surfactant (surfmer) are presented. For this study, well‐defined styrene‐butylacrylate latexes with a conventional nonreactive surfactant (sodium dodecyl sulfate) and a maleate diester surfmer, of which films can be easily cast, were used. The latex with the surfmer was prepared following a surfmer addition strategy to maximize the amount of surfmer bound to the particle surface, and not buried in the particle interior. The latex properties in terms of mechanical stability, film‐water absorption, and film‐surfactant exudation were assessed and compared. The mechanical stability and water‐absorption properties of the latex prepared with surfmer were better than those of the latex with sodium dodecyl sulfate. Additionally, by using a surfmer the surfactant migration to the film‐substrate and film‐air interfaces can be inhibited. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2994–3000, 2002     

Structure and properties of novel fluorinated polyacrylate latex prepared with reactive surfactant

The novel fluorinated polyacrylate latex was successfully prepared by emulsion polymerization of perfluorononylene allyl ether, butyl acrylate and methyl methacrylate initiated by potassium persulfate in water and emulsified with the reactive surfactant. Films of the novel fluorinated polyacrylate latex were prepared by coating the latex directly on the clean glass sheet and allowed to dry at 80°C in the bake oven. The characteristics of the film such as hydrophobicity and glass transition temperature were studied; its structure was investigated by FTIR spectrometry and NMR. The influence of the fluorinated monomer content on the emulsion polymerization and performance of the latex were also studied. It was shown that the hydrophobicity and glass transition temperature of the latex are improved when the fluorinated monomer is introduced to copolymerize with other monomers, however, the stability of emulsion polymer and the conversion rate is decreased with the increase of its content.     

Synthesis and characterization of core–shell polyacrylate latex containing fluorine/silicone in the shell and the self-stratification film

A series of core–shell polyacrylate latexes with different fluorine/silicone monomer concentrations were prepared successfully by seeded emulsion polymerization. Dodecafluoroheptyl methacrylate and perfluorooctyl methacrylate with different fluorinated side chains were employed as fluorinated monomers, and γ-methacryloxypropyl triisopropoxidesilane (MAPTIPS) was used as a silicone-containing monomer as well as a self-cross-linking agent. The morphology and chemical structure of the latexes were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, and differential scanning calorimetry, and the self-stratification properties of the latex film were verified by X-ray photoelectron spectroscopy and static contact angle measurement. The results showed that the fluorine/silicone-containing polyacrylate latexes presented a uniformly spherical core–shell structure, and the latex films displayed a preferential distribution of fluorinated composition near the surface, which was more remarkable with the synergism effect between the fluorine monomer and MAPTIPS. Additionally, the hydrophobicity and oleophobicity of the latex films exhibited high relevance with the fluorine/silicone monomer concentrations as well as the fluorinated side-chain structure.     

含氟丙烯酸酯共聚乳液的制备及表征

采用十二烷基硫酸钠和壬基酚聚氧乙烯醚(OP-10)混合乳化剂，制备了粒径为40-50nm的甲基丙烯酸全氟辛基乙酯(FMA8)-甲基丙烯酸丁酯(BMA)-甲基丙烯酸(MA)共聚物乳液。通过DSC、、FTIR、^1H-NMR等手段对共聚物进行了表征。考察了乳液的稳定性、乳胶膜的吸水性和耐溶剂性以及全氟单体的含量对聚合反应的影响。     

聚苯胺膜电极在苯胺单体聚合反应中的电催化性能

自从第一个导电高聚物掺碘的聚乙炔问世以来［1］,人们又陆续开发研制了聚 苯胺(PAn)、聚吡咯和聚噻吩等导电高分子材料. 在众多的导电高分子材料中,聚苯胺以其原 料廉价易得,制备方法简便,导电性能优良,耐高温及抗氧化性能良好等优点而成为最具应用 前景的品种之一. 迄今为止,有关聚苯胺的链结构,掺杂反应,以及导电机理等基础理论方面 的研究已有大量的文献和综述报道［2～6］. 这些基础理论的研究为其应用研究奠定 了坚实的基础. 早在60年代,人们就发现,聚苯胺对氧化亚氮分解及丁二烯异构化反应具有独 特的催化作用;同时,聚苯胺具有超出几何表面的活性表面,故可对某些反应具有选择性的催 化作用. 因此,人们开始研究聚苯胺膜电极对某些电极反应的电催化性能［7～12］. 我国科学工作者在这一领域也做了许多有益的工作,如董绍俊等［13］研究了聚苯胺 膜修饰电极对抗坏血酸的电催化氧化,罗维忠等［14］研究了聚苯胺膜电极对Fe(Ⅱ) 和Sb(Ⅲ)的电催化作用. 本文主要讨论了扫描速度、苯胺单体浓度及温度对聚苯胺膜电极在 苯胺单体聚合过程中电催化性能的影响,为利用聚苯胺处理含苯胺废水提供了一定的理论依 据.     

硅丙型核壳结构乳胶粒子的制备及成膜过程

采用分步乳液聚合方法, 分别在不同步骤中将乙烯基硅氧烷单体作为共聚单体引入聚丙烯酸酯类乳液共聚合体系中, 制备出具有窄分布多层核壳结构形态的硅丙型乳胶粒子. 利用透射电子显微镜(TEM)表征, 乳胶粒子具有硅丙型核壳结构; 动态激光散射(DLS)分析得到的乳胶粒子的直径与TEM数据相符; 同时由多频调制差示扫描量热(TOPEM-DSC)技术分析得到的乳胶粒子的3个玻璃化转变温度与实验设计相符, 证实乳液粒子的核壳结构; 利用Horus成膜仪对乳胶粒子成膜过程进行全程监控. 利用多种助剂制得水性木器涂料, 其漆膜的硬度、耐丙酮性、耐水性、耐醇性及耐压痕等性能优异.     

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.     

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/...     

含氟侧链在自交联含氟乳胶膜上的排列

借助JC2000A静态接触角测量仪和XPS对所制备的自交联含氟乳液涂膜进行表征及分析, 分别利用实验法和基团贡献法计算涂膜的表面自由能, 探讨含氟侧链在自交联含氟乳胶膜的排列. 结果表明, 增加含氟单体的用量, 可以降低含氟聚合物涂膜的表面自由能, 但当含氟单体用量超过20.3％时, 涂膜的表面自由能的变化不大, 含氟乳胶膜具有良好的自我恢复性能. 进一步的研究结果表明, 含氟聚合物乳液成膜后含氟侧链在涂膜表面的排列是一种无规则排列.     

含氨基、羟基丙烯酸乳液聚合的稳定性

采用间歇及半连续乳液聚合方式,以过硫酸铵/亚硫酸钠为引发体系,合成了甲基丙烯酸甲酯/丙烯酸丁酯/甲基丙烯酸羟乙酯/甲基丙烯酸二氨基乙酯四元共聚物胶乳.系统研究了乳化剂种类和浓度、聚合温度、乳化单体进料方式及进料速率对聚合过程稳定性的影响.聚合温度降低,乳化单体进料速度减慢有利于聚合过程的稳定,采用种子半连续聚合方式比间歇聚合过程更稳定,乳化剂浓度的增加有利于聚合稳定性的提高和乳胶粒子的均匀化.     

室温交联型硅丙微胶乳的合成研究Ⅲ.聚合工艺对聚合稳定性及胶膜性能的影响

采用两种聚合工艺(种子微乳液聚合法和单体预乳化法)分别合成了室温交联型有机硅改性丙烯酸酯聚合物微胶乳，研完了不同工艺条件对聚合稳定性、乳胶粒径和胶膜的结构性能的影响．     

Synthesis of Sub-100 nm and Narrow Particle Size Distribution Cationic Latex by One-Step Emulsion Polymerization

A novel approach to synthesize narrow particle size distribution cationic latex particles based on styrene and butyl acrylate was proposed. The effect of monomer/water ratios, surfactant (cetyltrimethylammonium chloride) concentrations, and monomer compositions on the evolution of particle size, distribution, number, and morphology as a function of monomer conversion was concerned in order to confirm the optimum polymerization condition. As expected, the particle size of the ultima latex increased with monomer/water ratios and styrene contents decreased with increasing surfactant concentrations. Continuous nucleation phenomena occurred when monomer/water ratio was lesser than 30/70, resulting in a gradual increase in the number of particles in the whole polymerization process. Combined with the previous work (Colloid and Polymer Science, 2014, 292: 519–525), it was concluded that particle coagulation easily took place in cationic emulsion polymerization of styrene. Thus, the narrow particle size distribution cationic latexes with particle scale between 50 nm and 80 nm, 30 wt% solid content could be prepared in a short reaction time.     

Effect of the acrylic acid content on the permeability and water uptake of poly(styrene-co-butyl acrylate) latex films

In this contribution, a theoretical modeling of the latex film formation is presented and compared to experimental results: water vapor permeability and latex film capacitance are studied as a function of acrylic acid content in poly(styrene-co-butyl acrylate) latex films. It has been shown that both water uptake and water vapor permeability are mainly affected by film morphology which in turn is defined by intercolloidal interaction and drying rate.     

氟代丙烯酸酯三元共聚物细乳液的合成与表征

在低乳化剂用量和不加助乳化剂的条件下,采用细乳液聚合方法,合成了平均粒径在110～150nm的氟代丙烯酸酯(FA)、甲基丙烯酸甲酯(MMA)及甲基丙烯酸丁酯(BMA)三元共聚物乳液.利用GPC,FTIR及¹HNMR谱表征了共聚物分子量和结构组成,采用激光光散射法研究了聚合过程中粒径变化规律,通过接触角方法对共聚物表面性能进行了表征.结果表明,油溶性引发剂AIBN引发FA-MMA-BMA三元细乳液共聚合的主要成核场所为单体液滴.即每个单体液滴都是一个独立的微型反应器,可避免因为单体水溶性的差异而使共聚组成产生漂移.细乳液聚合合成含氟共聚物乳液的分子量分布窄(1.3～1.5),乳液稳定性能好,共聚物在低含氟量下即表现出优异的疏水疏油性能.     

Synthesis and surface properties of self-crosslinking core–shell acrylic copolymer emulsions containing fluorine/silicone in the shell

Stable emulsions of a core–shell acrylic copolymer (non-crosslinkable V0, and crosslinkable V2, V4, V6, and V8, where the numbers indicate the wt% of crosslinking agent based on the total acrylate monomer content) containing butyl acrylate (BA, 45 wt%), glycidyl methacrylate (GMA, 45 wt%), heptadecafluorodecyl methacrylate (PFA, 10 wt%), and various contents of crosslinking agent (vinyltriethoxysilane, VTES) were synthesized using a three-stage seeded emulsion polymerization process with a small amount of surfactant. The average particle size and viscosity of emulsions increased significantly with increasing VTES content. This study examined the effects of the VTES content on the surface/mechanical properties of self-crosslinked copolymer film samples containing a fixed acrylate monomer content to find the optimum VTES content. XPS showed that the film–air surface of the copolymer samples had a higher fluorine/silicone content than the film–dish interface. The tensile strength/modulus, thermal stability, and two Tgs (α and β Tgs) of the film samples increased significantly with increasing VTES content. The contact angle of the film samples increased with increasing VTES content up to approximately 6 wt%, and then decreased slightly. The optimum VTES content was approximately 6 wt% based on the total acrylate monomer content to obtain a high water/oil repellent coating material (V6) with the highest water/methylene iodide-contact angles (118.2°/81.8°) and lowest surface energy (18.4 mN/m).     

Controllable preparation of high-yield magnetic polymer latex

In order to overcome the low conversion and complex post-treatment, four different polymerization procedures were adopted to prepare the magnetic polymer latexes. The results clearly show that the strategy using magnetic emulsion template-dosage is the most effective and feasible. Based on the optimized procedure, various factors including the type of initiators such as oil soluble initiator, water soluble initiator, redox initiator system, crosslinking agent, functional monomers etc. were systematically studied. Magnetic polymer latex with high monomer conversion of 83% and high magnet content of 31.8% was successfully obtained. Besides, core-shell structured magnetic polymer latex with good film forming property was also prepared, which is promising for potential applications such as magnetic coatings and modification of cementitious materials with controlled polymer location.     

Film‐formation property of vinylidene chloride‐methyl methacrylate copolymer latex. I. Effect of emulsion‐polymerization process

Changes in minimum film‐formation temperature (MFFT) during storage of latexes prepared from 91:9 wt % vinylidene chloride (VDC)‐methyl methacrylate (MMA) monomer mixture by seeded batch and seeded semicontinuous emulsion polymerization were investigated, with attention centered on polymer‐crystallization behavior during storage in the dispersed state. MFFT of latex prepared by the seeded batch process rose to 47 °C, whereas that of latex prepared by seeded semicontinuous process remained below 14 °C with storage at 20 °C for 12 weeks. Infrared absorption of latexes in the dispersed state and wide‐angle X‐ray diffraction of powder polymers obtained by lyophilization of fresh and stored latexes both indicated a much greater increase in polymer crystallinity during storage with latex prepared by the seeded batch process than with that prepared by the seeded semicontinuous process. Analysis of the copolymer composition drift calculated from reactivity ratios and ¹H NMR analysis indicated a wider sequence distribution and longer VDC sequences in polymer prepared by the seeded batch process than in polymer prepared by the seeded semicontinuous process. This explained the higher rate of crystallization during storage with latex prepared by the seeded batch process than with that prepared by the seeded semicontinuous process. Rising crystallinity during storage in the dispersed state is believed to have caused the MFFT rise. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 939–947, 2002     

有机硅改性磺酸型聚氨酯/丙烯酸酯复合乳液的制备

将磺酸型聚酯多元醇、异佛尔酮二异氰酸酯（IPDI)和三羟甲基丙烷(TMP)在无有机溶剂参与的情况下进行预缩聚,以硅烷偶联剂γ-氨丙基三乙氧基硅烷（KH550）作为改性剂,加入双官能团单体甲基丙烯酸-β-羟乙酯(HEMA),得到含乙烯基和有机硅封端的聚氨酯作为种子乳液,然后与甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)混合单体共聚,合成了有机硅改性磺酸型聚氨酯/丙烯酸酯复合乳液。 红外光谱的表征确定了有机硅改性磺酸型聚氨酯/丙烯酸酯复合乳液的化学结构;透射电子显微镜观察证实了此复合乳液具有明显的核壳结构;热重分析表明,经有机硅和丙烯酸酯改性后,胶膜的最大热失重温度提高了20 ℃,X射线衍射分析表明胶膜的结晶度降低,有利于提高膜的韧性。 力学性能测试及吸水率测试结果表明,当有机硅含量为1.9%时,胶膜的拉伸强度最高达到25.03 MPa,断裂伸长率为328%,此时膜的吸水率最低。