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...     

不同粒径含氟丙烯酸酯共聚乳液的合成及膜表面疏水性能研究

采用半连续种子乳液聚合的方式,以丙烯酸丁酯、甲基丙烯酸甲酯和甲基丙烯酸六氟丁酯为原料制备了粒径分别为30nm、75nm、210nm左右的含氟丙烯酸酯共聚物乳液。通过乳胶粒核壳结构设计与大小粒径乳液机械共混改性2种方法研究了如何在较少含氟单体用量的情况下达到较好的表面疏水性能。利用X射线光电子能谱、动态光散射仪、接触角测定仪等分析手段,研究了共聚物膜的表面性能和共聚物乳液粒径的大小及分布,测试结果表明,核壳结构乳液成膜后壳层含氟量较高,膜表面接触角大于90,°疏水性能强;而大小粒径乳液共混物成膜后表面含氟量较低,却仍能得到90°以上的接触角,表明乳胶膜表面具有粗糙结构,具有一定的仿荷叶效应。     

Synthesis and characterization of fluorinated polyacrylate latex emulsified with novel surfactants

The fluorinated polyacrylate latex were successfully prepared with semi- continuous seeded emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA) and hexafluorobutyl methacrylate (HFMA) which was initiated with potassium persulfate (KPS) initiator and emulsified with the novel mixed surfactants of sodium lauryl glutamate (SLG) and alkylphenol ethoxylates (OP-10). The structure of the resultant latex was confirmed by Fourier transform infrared spectroscopy (FTIR). The particle size of the latex was measured by Zetatrac dynamic light scattering detector. The film of latex was tested by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and contact angle (CA). The optimum conditions of preparing the novel fluorinated polyacrylate latex are optimized and the results are as follows: the amount of emulsifiers is 4.0%; mass ratio of SLG to OP-10 is 1:1, the amount of the initiator is 0.6%. The mass ratio of MMA to BA is 1:1 and the amount of HFMA is 7.0%. In this case, the conversion is high and the polymerization stability is good. In addition, the water resistance and thermal properties of the latex films were improved significantly in comparison with the film of the latex prepared without the fluorinated monomer.     

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.     

有机无机杂化物作乳化剂的苯丙乳液制备及其性能表征

A poly (St-co-BA) latex was successfully synthesized by using an organic-inorganic hybrid compound (OIHC), an aliphatic carboxylate sodium/nano-silica composite, as the emulsifier, and investigated by particle size analyzer, transmission electron microscope (TEM), optical contact angle measurement (OCA) and dynamic mechanical analyzer (DMA). It was found that the protective agent, sodium polyacrylate (PA),could obviously improve the polymerization stability and the functional monomer, glycidyl methacrylate (GMA), could enhance the store stability of the latex. The particle size of poly(St-co-BA) latex decreased and then leveled off as OIHC content increased. TEM shows that the prepared polymers were a~:tually organic-inorganic nanocomposites, and these films have better waterproof property than those prepared by traditional poly(St-co-BA) latex or organic silicone modified poly(St-co-BA) latex. The nanocomposite polymer has much higher glass transition temperature than organic silicone modified poly(St-co-BA) polymer containing the same organic silicone content.     

细乳液聚合制备纳米SiO2／含氟丙烯酸酯复合乳液及其性能研究

采用溶胶-凝胶法,以正硅酸乙酯为前驱物,在丙烯酸酯单体为油相介质中原位生成纳米SiO2粒子,并通过细乳液聚合,制备出纳米Si02／含氟丙烯酸酯复合乳液。研究了含氟单体和SiO2的用量对复合乳胶膜性能的影响,并采用FT-IR,DSL等分析手段对产物进行了表征。结果表明：该乳液具有良好的稳定性,粒径分布较窄。当（甲基丙烯酸十二氟庚酯）FA与SiO2的用量分别为6％和5．5％时,乳胶膜表现出良好的疏水性能,对水的接触角达到了102．7°,吸水性降低到6．9％。     

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。     

Colloidal and polymer properties difference of fluorinated acrylate latex prepared with different fluorinated monomers

Fluorinated acrylate latex was prepared by copolymerizing fluorinated monomer, butyl acrylate, and methyl methacrylate, which was initiated by potassium persulfate in the water. The resultant fluorinated latex and its film were characterized with contact angle determinator, dynamic light scattering detector, and differential scanning calorimetry, respectively. Influence of type of fluorinated monomers on colloidal and polymer properties of fluorinated acrylate latex was studied. Results show that the coagulation rate, particle size, contact angle, glass transition temperature, and chemical resistance are increased with the increase of the number of fluorine atom in the fluorinated monomer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

纳米SiO2／氟改性聚丙烯酸酯复合乳液的制备

以正硅酸乙酯为前驱物,采用溶胶一凝胶法原位制备纳米Si02粒子,然后通过细乳液聚合制得纳米Si02／氟改性聚丙烯酸酯复合乳液。采用傅里叶变换红外光谱（FTIR）和动态光散射（DLS）对产物进行了表征。研究了含氟单体和纳米Si02用量对复合乳胶膜性能的影响。结果表明：随着氟含量的增加,乳胶膜的水接触角增加,吸水性降低;体系中加入纳米Si029可以降低聚合物乳胶膜的吸水率。     

Investigation of fluorinated polyacrylate latex with core–shell structure

Fluorinated polyacrylate latices with core–shell structure were prepared by semi‐continuous emulsion polymerization, using a mixed emulsifier system composed of a reactive emulsifier and a small amount of anionic emulsifier. The conversion and chemical components of the final latices were studied by gravimetric methods and Fourier‐transform infrared (FTIR) spectrometry, respectively. The structure of the latex particles was determined by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and particle size analysis. The latex films exhibited a low surface energy and high water‐contact angles. The surface analysis from X‐ray photoelectron spectroscopy (XPS) revealed that the fluorinated components preferentially self‐organized at the film–air interface. From XPS depth profiling of the film, it was found that a gradient concentration of fluorine existed in the structure of the latex film from the film–air interface to the film–glass interface. Compared with the core–shell structure with a fluorinated core, the core–shell structure with a fluorinated shell was more effective for modifying the properties of the latex films. Copyright © 2005 Society of Chemical Industry     

Role of acrylic acid in the synthesis of core‐shell fluorine‐containing polyacrylate latex with spherical and plum blossom‐like morphology

The core‐shell fluorine‐containing polyacrylate latex was successfully synthesized by two‐stage semicontinuous emulsion copolymerization of methyl methacrylate (MMA), butylacrylate (BA), acrylic acid (AA), and dodecafluoroheptyl methacrylate (DFMA). The fluorine‐containing polyacrylate latex was characterized by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential, thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC). The effects of AA content on monomer conversion, polymerization stability, particle size, corsslinking degree, carboxyl groups distributions (latex surface, aqueous phase or buried in latex), as well as mechanical properties and water absorption rate of latex film were investigated. The obtained fluorine‐containing polyacrylate latex exhibited core‐shell structure with a particle size of 120–150 nm. The introduction of AA was beneficial for the increase of monomer conversion and the polymerization stability, and had little effects on the mechanical property of latex film. However, the hydrophilicity of AA made the water resistance of latex film get bad. With the increase of AA content, the carboxyl groups preferred to distribute on aqueous phase, and the possibility of homogeneous nucleation increased and more oligomers particles were formed. Moreover, the oligomers would distribute to the latex and continued to grow up, making the latex morphology changed from spherical to plum blossom‐like. The core‐shell latex had two T_g corresponding to the rubber polyacrylate core and hard fluorine‐containing polyacrylate shell, and the latex film possessed excellent thermal stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42527.     

Synthesis of ambient temperature self-crosslinking VTES-based core–shell polyacrylate emulsion via modified micro-emulsion polymerization process

Modified micro-emulsion polymerization was successfully used to synthesize a kind of ambient temperature self-crosslinking core–shell emulsion, consisting of polyacrylate core and vinyltriethoxysilane (VTES) modified polyacrylate shell, by varying the ratio of soft monomer (BA) and hard monomer (MMA) which is different in the core and shell. The emulsion and its film formed at ambient temperature were characterized by attenuated total reflectance-fourier transform infrared spectroscopy (ATR-FTIR), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Core–shell structure was clearly shown in TEM micrographs, and two distinct glass transition temperatures (T _g) were confirmed by DSC analysis. Lower T _g of core phase analyzed by DSC and self-crosslinking properties of VTES characterized by crosslinking degree cause latex particles form continuous film at ambient temperature. Thermal and mechanical properties and the surface properties of the latex films were also investigated. Results showed that the core–shell latex films containing 5 and 7.5 % VTES exhibited higher thermal stability, better mechanical properties, higher contact angle, and water resistance compared with pure polyacrylate film.     

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。     

Preparation and surface properties of core‐shell polyacrylate latex containing fluorine and silicon in the shell

The core‐shell polyacrylate latex particles containing fluorine and silicon in the shell were successfully synthesized by a seed emulsion polymerization, using methyl methacrylate (MMA) and butyl acrylate (BA) as main monomers, dodecafluoroheptyl methacrylate (DFMA), and γ‐(methacryloxy) propyltrimethoxy silane (KH‐570) as functional monomers. The influence of the amount of fluorine and silicon monomers on the emulsion polymerization process and the surface properties of the latex films were discussed, and the surface free energy of latex films were estimated using two different theoretical models. The emulsion and its films were characterized by particle size distribution (PSD) analysis, transmission electron microscopy (TEM), Fourier transform infrared spectrum (FTIR), nuclear magnetic resonance (¹H‐NMR and ¹⁹F‐NMR) spectrometry, contact angle (CA) and X‐ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and thermogravimetry (TG) analysis. The results indicate that the average particle size of the latex particles is about 160 nm and the PSD is narrow, the synthesized latex particles exist with core‐shell structure, and a gradient distribution of fluorine and silicon exist in the latex films. In addition, both the hydrophobicity and thermal stability of the latex films are greatly improved because of the enrichment of fluorine and silicon at the film‐air interface, and the surface free energy is as low as 15.4 mN/m, which is comparable to that of polytetrafluoroethylene (PTFE). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚合工艺条件对含氟涂膜表面性能的影响

运用种子乳液聚合法制备了较高性价比的含氟乳液。FTIR光谱和DSC测试表明,含氟单体参与了聚合反应。运用KrussK12型动态表面能分析仪,测定聚合工艺中以不同用量的乳化剂、引发剂、含氟单体、N 羟甲基丙烯酰胺(N MA)在不同的单体滴加速度下合成的乳液涂膜对水和十六烷的接触角,结果表明,w(乳化剂)=3 5%、w(引发剂)=0 45%、w(N MA)=4%、聚合物中x(F)=14%时,乳液涂膜对水和十六烷的接触角较佳,对水的接触角达115°,涂膜表现出良好的表面性能。     

Preparation and properties of core–shell nanosilica/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) latex

A core–shell nanosilica (nano‐SiO₂)/fluorinated acrylic copolymer latex, where nano‐SiO₂ served as the core and a copolymer of butyl acrylate, methyl methacrylate, and 2,2,2‐trifluoroethyl methacrylate (TFEMA) served as the shell, was synthesized in this study by seed emulsion polymerization. The compatibility between the core and shell was enhanced by the introduction of vinyl trimethoxysilane on the surface of nano‐SiO₂. The morphology and particle size of the nano‐SiO₂/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) [P(MMA–BA–TFEMA)] core–shell latex were characterized by transmission electron microscopy. The properties and surface energy of films formed by the nano‐SiO₂/P(MMA–BA–TFEMA) latex were analyzed by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, and static contact angle measurement. The analyzed results indicate that the nano‐SiO₂/P(MMA–BA–TFEMA) latex presented uniform spherical core–shell particles about 45 nm in diameter. Favorable characteristics in the latex film and the lowest surface energy were obtained with 30 wt % TFEMA; this was due to the optimal migration of fluorine to the surface during film formation. The mechanical properties of the films were significantly improved by 1.0–1.5 wt % modified nano‐SiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of trilayer core–shell polysilsesquioxane–fluoroacrylate copolymer composite emulsion particles

Polysilsesquioxane–fluoroacrylate copolymer [poly(methyl methacrylate)–butyl acrylate–dodecafluoroheptyl methacrylate)] (FPSQ) composite latex particles with a trilayer core–shell morphology were manufactured by seeded emulsion polymerization, where PSQ latex particles bearing reactive methacryloxypropyl moieties were first produced by the hydrolysis‐condensation of (3‐methacryloxypropyl)trimethoxysilane, and then they were utilized as seeds, with methyl methacrylate, butyl acrylate, and dodecafluoroheptyl methacrylate as the inner and outer shell monomers. Fourier‐transform infrared spectra and ¹H‐NMR confirm the structure of the FPSQs. Transmission electron microscopy and scanning electron microscopy demonstrate that the obtained composite emulsion particles emerge with the trilayer core–shell pattern. Due to the anchoring of PSQ nanoparticles, the thermal stabilities of the FPSQ films are strengthened, and the resistance to heat is gradually improved along with the increase of the fluoroacrylate dose in the polymer matrix composite. X‐ray photoelectron spectroscopy, atomic force microscopy (AFM), and hydrophobicity investigations indicate that the fluorinated chain segments tend to concentrate at the film–air two‐phase interface. In addition, the AFM result denotes that importing more fluorine into the FPSQ hybrid material will engender greater phase separation and enrichment of the fluoroalkyl segments and a rougher morphology. Thus, the water contact angle of the FPSQ film can ultimately reach 121.4°. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44845.     

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     

水性含氟丙烯酸酯核壳乳液的制备及性能研究

采用半连续乳液聚合法合成了以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为成核单体,甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和丙烯酸六氟丁酯(HF)为成壳单体的核壳型微乳液。通过TEM、SEM、FT-IR对乳液及乳液固化膜性能进行了表征;对乳液的稳定性做了测试,用接触角法对乳液固化膜表面性能进行了研究。结果表明:当含氟单体质量分数为19.34%时,核壳型结构粒子呈球形分布,乳液稳定性良好,成膜性较好,乳液固化膜的表面能为24.26 mJ/m2,与之相对应的无氟乳液固化膜的表面能为52.73 mJ/m2。根据本研究得出的原料、配方及工艺方法制备的乳液及其膜有较优的性能。     

Polymeric particles prepared with fluorinated surfmer

Fluoro-containing particles have been obtained by miniemulsion polymerization of styrene and n-butyl methacrylate in presence of fluorinated monomer mono-fluoroalkyl maleate (MFM) which acts as a surfmer providing efficient stability to obtained dispersion and functionalization of particle surface with fluoro-groups. Increase of the MFM concentration in reaction mixture reduces the particle size and dispersions with narrower particle size distribution can be obtained. Blends of fluorinated latexes with styrene-butadiene copolymer latex were examined with regard to formation of low free energy surfaces. It has been shown that blends containing MFM-functionalized polymeric particles possess more hydrophobic surfaces then similar latex films, where particles prepared by polymerization of expensive fluorinated monomer have been applied.