Study on ultrasonic induced encapsulating emulsion polymerization in the presence of nanoparticles

In this paper, the ultrasonic induced encapsulating emulsion polymerization technique was used to prepare polymer/inorganic nanoparticle composites. The main affecting factors in ultrasonic induced encapsulating emulsion polymerization were studied systematically. The experimental results suggested that the pH value, the type of monomers, the type, content, and surface properties of nanoparticles, the type and concentration of surfactant have great influence on the ultrasonic induced encapsulating emulsion polymerization and the obtained latex stability. If selecting cationic emulsifier (such as cetyl trimethylammonium bromide), low water soluble monomer (such as n‐butyl acrylate and styrene), and hydrophobic nano silica, the inorganic nanoparticles could be encapsulated by polymers through ultrasonic irradiation successfully under alkalescent condition, forming a novel polymer/inorganic nanoparticles composite. The mechanism of ultrasonic induced encapsulating emulsion polymerization and the composite latex stabilization are proposed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1130–1139, 2001     

The Preparation of Core–Shell P(St-MMA)–SiO2 Hybrid Nanoparticles and Filling in the Styrene/n-butyl Acrylate Adhesive

In this study, core–shell poly(styrene-methyl methacrylate) (P(St-MMA))–SiO₂ hybrid nanoparticles were prepared successfully by emulsion polymerization. Firstly, nanosilica particles were modified by oleic acid (OA) in order to introduce the polymerization active vinyl groups and hydrophobic groups onto the nanosilica. This was followed by graft copolymerization onto the modified nanosilica particles to obtain P(St-MMA)–SiO₂ hybrid nanoparticles. The hybrid nanoparticles were characterized by: transmission electron microscope (TEM); Fourier transform infrared spectroscopy (FT-IR); dynamic light scattering (DLS); and thermal gravimetric analysis (TGA). The results indicate that the hybrid particles had a regular spherical morphology with a diameter ranging from 50 to 80 nm. A reasonable mechanism for the preparation of the core–shell hybrid nanocomposites was presented. The obtained hybrid nanoparticles were subsequently (incorporated into) filled in the poly(styrene-n-butyl acrylate) (PSBA) latex. The effect of (hybrid nanoparticle concentration) filling content on the physicochemical properties of PSBA latex and the resulting node strength per monofilanment of the fibre glass gridding cloth was investigated. The results indicated that the node strength/monofilanment of the fibre glass gridding cloth coated with the PBSA latex filled with 1.0 wt% hybrid nanoparticles demonstrated greatest improvement among all the investigated PSBA latex. This result is related to the rheological properties of the latex. Moreover, the water-resistance property of PSBA composite film was found to be enhanced when compared with that of unfilled PSBA film.     

纳米SiO2/聚氨酯-含氟丙烯酸酯杂化乳液的合成与表征

采用种子乳液聚合法,以聚氨酯（PU）乳液为种子（在聚合过程中为壳相）,甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）、甲基丙烯酸十二氟庚酯（DFMA）和γ-甲基丙烯酰氧丙基三甲氧基硅烷（KH-570）改性的纳米SiO₂组成的混合物为核相,合成了具有核壳结构的纳米SiO₂/聚氨酯-含氟丙烯酸酯（SiO₂/FPUA）复合乳液。考察了纳米SiO₂和DFMA用量对乳液聚合过程及乳胶膜性能的影响。通过傅里叶红外光谱（FT-IR）、接触角（CA）、透射电子显微镜（TEM）、热重（TG）、差示扫描量热仪（DSC）和力学性能测试（MPT）等表征乳液的结构形态、乳胶膜的表面性能和综合性能。结果表明：乳胶粒子呈现“反相核壳”结构,以聚丙烯酸酯（PA）相为核,PU相为壳;由于纳米SiO₂和DFMA的协同作用,涂膜的疏水性和综合性能得到了较大的提高。     

Fabrication and properties of polysilsesquioxane-based trilayer core–shell structure latex coatings with fluorinated polyacrylate and silica nanocomposite as the shell layer

Polysilsesquioxanes (PSQ)-based core–shell fluorinated polyacrylate/silica hybrid latex coatings were synthesized with PSQ latex particles as the seeds, and methyl methacrylate, butyl acrylate, 3-(trimethoxysilyl) propyl methacrylate (MPS)-modified SiO₂ nanoparticles (NPs), 1H,1H,2H,2H-perfluorooctyl methacrylate (PFOMA) as the shell monomers by emulsifier-free miniemulsion polymerization. The results of Fourier transform IR spectroscopy, transmission electron microscopy, and dynamic light scattering suggested the obtained hybrid particles emerged with trilayer core–shell pattern. Contact angle analysis, x-ray photoelectron spectroscopy, and atom force microscopy results indicated that the hybrid film containing SiO₂ NPs showed higher hydrophobicity, lower surface free energy and water absorption, in comparison with the control system (without SiO₂ NPs). Compared with the control system, the hybrid latex film containing SiO₂ NPs in the fluorinated polyacrylate shell layer showed the higher content of fluorine atoms and a rougher morphology on the film surface. Additionally, thermogravimetric analysis demonstrated the enhanced thermostability of PSQ-based nanosilica composite fluorinated polyacrylate latex film.     

Properties of organic–inorganic composite materials prepared from acrylic resin emulsions and colloidal silicas

To design an organic–inorganic composite material with colloidal silica as the inorganic component, an acrylic resin emulsion and an organic silane hybridized acrylic resin emulsion were prepared by emulsion polymerization. The organic–inorganic composite films were prepared by blending the emulsion and the colloidal silica. The contact angles for water, gloss at 60°, and the transparencies of those films were measured. The dispersion state of colloidal silica in films was observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM). From these results, the contact angle for water of the organic–inorganic composite film obtained from the silane hybridized acrylic resin emulsion was lower than that of the organic–inorganic composite film obtained from an acrylic resin emulsion. The contact angles for water in organic–inorganic composite films with colloidal silicas were lower than those of the films without the colloidal silicas. The films prepared from silane hybridized acrylic resin emulsion composites with colloidal silicas of less than 100 nm were more hydrophilic. SEM and TEM observations demonstrated that some aggregations of the small colloidal particle silica were densely dispersed on the film surface. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2051–2056, 2006     

纳米SiO_2/聚丙烯酸酯组装杂化乳液的合成及表征

通过乳液聚合法成功合成了纳米SiO2/聚丙烯酸酯杂化乳液。首先将纳米SiO2经过表面官能团化处理,使其表面含有活性官能团,然后经过乳液聚合使丙烯酸酯单体在纳米SiO2表面引发聚合,合成了具有核壳结构的纳米杂化乳液。采用透射电子显微镜(TEM)对乳液的微观结构进行了表征,并对胶膜进行了机械力学性能测试和表面润湿性能测试。结果表明纳米SiO2的表面官能团化处理改善了纳米粒子在乳液中的稳定性,当纳米SiO2质量分数为0 2%时,杂化乳液胶膜的拉伸强度和断裂伸长率同时达到最大值。其表面润湿性与SiO2质量分数有关,SiO2质量分数为0 5%时其杂化乳胶膜的接触角最大,耐水性最好。     

核壳型纳米SiO2/含氟聚丙烯酸酯复合乳液的合成与表征

采用原位乳液聚合法,在可聚合阴离子乳化剂/非离子乳化剂复配体系下,以γ-甲基丙烯酰氧丙基三甲氧基硅烷(KH-570)改性的纳米SiO2、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)等为核相组成,以MMA、BA及甲基丙烯酸十二氟庚酯(DFMA)为壳相单体,合成纳米SiO2/含氟聚丙烯酸酯复合乳液.考察了纳...     

Preparation and properties of polydimethylsiloxane/polyacrylate composite latex initiated by 60Co γ‐ray irradiation

In this study, polydimethylsiloxane (PDMS)/polyacrylate composite polymer latex was synthesized via polymerization of the acrylate monomer in the presence of vinyl‐containing PDMS seeded latex. The polymerization was initiated by ⁶⁰Co γ‐ray irradiation. The morphology of the PDMS/polyacrylate composite polymer latex was a core–shell structure with PDMS as the core and polyacrylate as the shell. There was an interpenetration layer between the PDMS core and the polyacrylate shell. The composition of the vinyl‐containing PDMS and the PDMS/polyacrylate composite latex were investigated with NMR and Fourier transform infrared spectroscopy, respectively. The effect of irradiation dose on the seeded emulsion polymerization conversion is discussed. Finally, the mechanical properties of latex film, such as water‐absorption ratio, tensile strength, pendulum hardness, and heat‐decomposed temperature, were tested. The results showed that the mechanical properties of the PDMS/polyacrylate film were remarkably improved when compared to the polyacrylate film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2732–2736, 2003     

Polymer/carbon nanotube composite emulsion prepared through ultrasonically assisted in situ emulsion polymerization

In this study, ultrasonic irradiation and in situ emulsion polymerization were combined to prepare stable poly(methyl methacrylate‐co‐n‐butyl acrylate) (P(MMA‐BA))/carbon nanotubes (CNTs) composite emulsion, which solves the dispersion problem of CNTs in the latex. Two stages were adopted. In Stage I, ultrasonically initiated in situ emulsion polymerization was conducted to disperse CNTs and prepare the seed emulsion containing polymer coated CNTs. In Stage II, conventional in situ emulsion polymerization was conducted to further enhance the monomer conversion and solid content. The dispersion behavior of MWCNTs in aqueous solution under ultrasonic irradiation was investigated by spectrophotometry. The effects of CNTs content on the emulsion stability and mechanical properties of composite film were studied. The results suggest that in the composite emulsion the long CNTs with a diameter of 20–40 nm are separated and dispersed by the formed polymer latex nanoparticles with a size of 20–40 nm. The spherical polymer latex nanoparticles adhere to the wall of CNTs to form a structure like “grapes on the twig.” The smooth, uniform, and flexible polymer/CNTs composite films were prepared from the composite emulsion. The CNTs can be individually dispersed in P(MMA‐BA)/CNTs composite film. Tensile tests suggest that with the increase in the CNTs content, the Young's modulus and the yield strength of the film increase. Only at 1 wt % CNTs, the Young's modulus increases from 124 to 289 MPa, and the yield strength is improved about ～14%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3123–3130, 2006     

Preparation of fluorinated polyacrylate composite latex with in situ generated nano-silica dispersion and film durability

Nano-silica dispersion was generated in situ through the hydrolysis and condensation of tetraethyl orthosilicate with methyl methacrylate and butyl acrylate in micelles as dispersing media, hydrochloric acid as catalyst and methacryloxypropyl trimethoxysilane as modifier. Then, the nano-silica/fluorinated polyacrylate composite latexes were prepared via emulsion polymerization directly using the in situ generated nano-silica dispersion as seeds. Dodecafluoroheptyl methacrylate (DFHMA) as functional monomer was incorporated into shell layer of the composite particles by semi-continuous starved condition at the second stage. Fourier transform infrared spectroscopy indicated that silica was generated in situ and DFHMA took part in the copolymerization. Transmission electron microscopy showed uniform composite latex particle morphology and obvious core–shell structure. Dynamic light scattering demonstrated that DNS-86 could control the composite latex particle size ranging from 90 to 180 nm. DFHMA had an important effect on the particle size. Zeta potential (ζ) revealed that the composite latex had good stability. The resulted composite films were characterized by angle-resolved X-ray photoelectron spectroscopy, contact angle measurements and thermo-gravimetric analysis. The well-tailored composite latex particle structure of nano-silica core and fluorinated polyacrylate can effectively improve the hydrophobicity of the resultant films. Water contact angle could reach 123.5° when 6 wt% DFHMA was incorporated in the film. Moreover, water contact angles remained 106° after water immersion in the range of the experimental sample films. In addition, the incorporation of fluorinated monomer and nano-silica contributed to the improvement of thermal stability of the composite film.     

聚醋酸乙烯酯/纳米SiO_2复合乳液的制备与性能

采用原位乳液聚合法制备了聚醋酸乙烯酯／纳米二氧化硅复合乳液。考察了纳米二氧化硅在聚醋 酸乙烯酯乳液内及乳胶膜中的分散性:纳米二氧化硅用量对复合乳液性能的影响。结果表明:与普通乳液相 比,复合乳液的干态粘接强度和耐水性明显提高。     

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     

反应型乳化剂在核壳丙烯酸酯乳液合成中的应用

本研究采用种子乳液聚合法,将反应型乳化剂、非离子型乳化剂和阴离子型乳化剂进行复配,以BA、St、MMA、AA为单体合成了具有核壳结构的聚丙烯酸酯类乳液。试验表明：乳化剂用量为2.5%,G-30∶NP40∶HAPS比例为1∶2∶1,乳化剂在核壳中的比例为2∶1,得到的乳液具有核壳结构,胶膜综合性能良好。     

阳离子型含氟丙烯酸酯共聚乳液的微波辐射制备

在微波辐射下,以十八烷基三甲基氯化铵为乳化剂,2,2-偶氮2甲基丙基脒-二盐酸盐（AIBA）为引发剂,将丙烯酸丁酯（BA）、甲基丙烯酸甲酯（MMA）、甲基丙烯酸十二氟庚酯（GO-4）以及甲基丙烯酰氧乙基三甲基氯化铵（DMC）进行乳液聚合,成功制备了Zeta电位在315mV左右、粒径为55~75nm的阳离子型含氟丙烯酸酯乳液。通过测定乳胶膜中氟元素含量,发现微波辐射能提高含氟单体共聚效率,使乳胶膜中氟元素含量增加。用固含量1％的阳离子型含氟丙烯酸酯共聚物乳液处理棉布织物,结果发现,棉布对水和正十六烷的接触角可分别达到111．3°、60．6°,表面自由能降至1581mJ／m2,棉布的静态吸水时间可以超过4h。     

纳米SiO2／丙烯酸酯复合乳胶粒子的调控及光吸收特性

基于纳米SiO2／丙烯酸酯单体分散液,采用半连续一饥饿态乳液聚合技术合成了纳米SiO2／丙烯酸酯复合乳液,研究了影响复合乳胶粒子大小与分布的因素及其光吸收特性。结果表明,反应温度、DNS-86用量,纳米SiO2的量均可调控粒径大小和多分散系数,SiO2用量的增加使复合粒子具有更强的紫外吸收特性。     

Mechanical and surface hardness properties of ultraviolet‐cured polyurethane acrylate anionomer/silica composite film

An organic‐inorganic composite was prepared by mixing silica emulsion with urethane acrylate anionomer (UAA) emulsion. The silica emulsion was prepared by sol‐gel process, and stabilized by a steric stabilizer, polyvinyl pyrrolidone. UAA/silica composite film was made by an ultraviolet curing method. The mechanical and rheological properties of the UAA/silica composite were greatly improved. This composite also showed thermal stability during increase of temperature. Surface hardness was improved with increasing silica content up to proper amount of silica. However, in abrasive test, because UAA/silica composite film has a more abrasive contact area than UAA film, the former was abraded much more than the latter. In comparison to UAA film, the UAA/silica composite showed much smoother abrasive surface and less roughness. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 968–975, 2000     

Preparation of spherical nanocomposites consisting of silica core and polyacrylate shell by emulsion polymerization

Nanocomposite particles consisting of silica (inorganic core) and polyacrylate (organic shell) were prepared in a form of emulsion by a new and simple method—the emulsion polymerization of acrylic monomers in the presence of silica sol. The key technique of the present emulsion polymerization, which made the formation of the nanocomposites successful, is the usage of nonionic surfactant above its cloud point. The morphology of the composite was investigated by DLS, AFM, and TEM, which clearly showed formation of the core‐shell‐type particles. A transparent film was prepared by casting the emulsion, which showed high resistibility against organic solvents. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 659–669, 2006     

原位水解法聚丙烯酸酯/纳米二氧化硅复合乳液的性能研究

将甲基丙烯酸羟乙酯(HEMA)与硅酸四乙酯经酯交换制得的二甲綦丙烯酰氧基硅酸二乙酯与丙烯酸酯进行乳液聚合,制得了不同硅酸酯用量的稳定聚丙烯酸酯/纳米二氧化硅复合乳液。利用红外光谱、透射电镜、差热扫描及热失重对乳胶膜进行了分析表征。结果表明,利用乳液聚合可以获得原位水解并稳定分散的聚丙烯酸酯/纳米二氧化硅复合乳液,二氧化硅的存在可提高材料的热性能。     

含氟硅丙烯酸酯核壳乳液及涂膜表面性能

在可聚合阴离子乳化剂体系下,以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为主要单体,甲基丙烯酸十二氟庚酯(DFMA)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)为功能单体,采用半连续种子乳液聚合法合成了含氟硅丙烯酸酯核壳乳液。考察了DFMA和KH-570用量对乳液聚合过程和乳胶膜表面疏水性能的影响,并对乳胶膜的表面自由能进行了估算。采用傅里叶红外光谱(FT-IR)、差示扫描量热仪(DSC)、热重(TG)、接触角(CA)及X射线光电子能谱(XPS)对氟硅丙乳液及乳胶膜进行了表征。研究结果表明,氟硅单体有效地参与了聚合,乳胶膜中氟硅元素呈梯度分布,当氟硅丙乳液中DFMA和KH-570用量分别为16%和5%（质量分数）时,涂膜-空气界面与去离子水的接触角为110.6°,涂膜的表面能低至15.4 mN·m^-1,其疏水性和耐热性有较大幅度提高。     

Fabrication and characterization of polysiloxane/polyacrylate composite latexes with balanced water vapor permeability and mechanical properties: effect of silane coupling agent

In order to improve the water vapor permeability and mechanical properties of latex films, polysiloxane/polyacrylate (PSi/PA) composite latexes were fabricated via seeded emulsion polymerization of methyl methacrylate and butyl acrylate onto PSi latex particles, and the effects of the silane coupling agent 3-methacryloyloxypropyl trimethoxysilane (MATS) on the morphologies of the latex particles and films, as well as the microphase separation degree, the water vapor permeability and the mechanical properties of the latex films were investigated. Results indicated that MATS was essential for obtaining the PSi/PA composite latex particles with PSi as core and PA as shell and made a great contribution to restrict the phase separation. The PSi/PA core/shell latex films showed similar tensile strength and elongation with pure PA film, while exhibiting promising water vapor permeability. It was found that the influences of MATS content on the water vapor permeability and mechanical properties were opposite, and on the premise of the requirements for mechanical properties, lower MATS content could provide the PSi/PA core/shell latex films with better water vapor permeability.