Preparation of styrene‐acrylic emulsion by using nano‐SiO2 as seeds

A styrene‐acrylic/SiO₂ nanoparticle composite emulsion was prepared by using SiO₂ nanoparticles as seeds. The effect of factors such as the level of nano‐SiO₂, reaction temperature and ultrasound treatment of nano‐SiO₂ on the stability of the polymerization reaction was investigated. Water‐resistance of the emulsion was measured. The level of nano‐SiO₂ in the emulsion was determined by inductively coupled plasma (ICP) spectrometry. The particle morphology of the emulsion with nano‐SiO₂ was observed with transmission electron microscopy (TEM). The kinetics of the polymerization was also studied at various temperatures and various levels of nano‐SiO₂. They showed that the level of nano‐SiO₂ and reaction temperature had a great influence on the monomer conversion, particle size, coagulum content and viscosity of the emulsion. Nano‐SiO₂ treated by ultrasonics can increase the coagulum content greatly, but it does not improve the water resistance of the emulsion. The level of nano‐SiO₂ in the emulsion was lower than the theoretical value. The reaction kinetics indicated that the level of nano‐SiO₂ had less influence on the reaction rate than the reaction temperature. Even a small amount of nano‐SiO₂ can decrease the reaction rate. Copyright © 2004 Society of Chemical Industry     

Polypropylene/polypropylene‐grafted acrylic acid blends for multilayer films: Preparation and characterization

Polypropylene (PP) was functionalized with acrylic acid (AA) and styrene (st) as a comonomer by means of a radical‐initiated melt‐grafting reaction. FTIR, ESCA, and ¹H‐NMR spectroscopies were used to characterize the formation of polypropylene grafted with acrylic acid (PP‐g‐AA) and polypropylene grafted with acrylic acid and styrene (PP‐g‐AAst). The content of AA grafted onto PP was determined by using volumetric titration. Blends of PP with 0–100 wt % of PP‐g‐AA were prepared by melt mixing. The effect of the modified polymer content on the surfaces of cast films was characterized through FTIR–ATR and ESCA analysis as well as contact‐angle, wetting‐tension, and ink‐adhesion measurements. The influence of the content of AA on the melting and crystallization temperature of PP was investigated by DSC. The contact angles of water on cast‐film surfaces of PP/PP‐g‐AA blends decreases with increasing modified polymer content and decreasing PP‐g‐AA molecular weight. A notorious improvement on wetting tension was observed with increasing modified polymer content and decreasing PP‐g‐AA molecular weight. From FTIR–ATR and ESCA spectra of the blends, a calculation was made of the carbonyl index on the films' surfaces. It was found that the higher the carbonyl index, the lower the contact‐angle value for the polypropylene blends. An increase in crystallization temperature of PP was observed when AA monomers were grafted into PP and with increasing PP‐g‐AA content in the blend, probably caused by a nucleation effect of AA monomers that would improve the crystallization capability of PP. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1497–1505, 2001     

Preparation and characterization of acrylic latex/nano‐SiO2 composites

Acrylic/nano‐silica composite latexes were prepared by blending via high shear stirring (SS) or ball milling (BM) and in situ polymerization (IS). For comparison, composites filled with micro‐silica were also prepared. The mechanical and optical properties of the polymers formed by the composite latex filled with nano‐ or micro‐silica were investigated using an Instron testing machine, by dynamic mechanical analysis, ultraviolet–visible spectrophotometry and transmission electron micrography. The results showed that SS and BM methods could obtain better nanocomposite latex and polymers than the IS method, characterized by better dispersion of nanoparticles, higher tensile strength and T_g for SS and BM than for IS. The increase in absorbance and reduction in transmittance of UV (290–400 nm wavelength) were observed as nano‐silica content increased, whereas the UV absorbance or transmittance basically were kept unchanged for the composites filled with micro‐silica. © 2002 Society of Chemical Industry     

Mechanical and surface properties of membranes prepared from waterborne cationic hydroxyl‐terminated polydimethylsiloxane/polyurethane surfactant‐free micro‐emulsion

With the action of catalyst and cosolvent, a series of hydroxyl‐terminated polydimethylsiloxane (HPMS) based polyurethane (PU) micro‐emulsion were gotten by surfactant‐free copolymerization. They were successfully prepared by reacting isophorone isocyanate, poly(tetramethylene glycol), and HPMS with N‐methyldiethanolamine (MDEA) as chain extender and trimethylolpropane (TMP) as crosslinker. After neutralizing with dimethyl sulfate and inversing the emulsion polymerization with deionized water, a series of microemulsions were obtained. The emulsions were then cast into membranes named as PU–HPMS. The mechanical properties and water absorption of the PU–HPMS were determined and simultaneously the effects of the content of hard segment, solvent, TMP, MDEA, HPMS, and the molecular weight of soft segment were studied. It is noticed that the tensile strength decreased and elongation at break increased in the HPMS/PU when compared with pure PU, which confirm that PU was end‐capped with PDMS. It is also noticed that water absorption increased in the HPMS/PU when compared with pure PU. As HPMS content increased from 0.0 to 25.0 wt %, the surface free energies decreased from 0.3446 to 0.2317 mN/cm and water absorption decreased from 11.2% to 0.14%. The surface free energies of the membranes were decreased by more than 32.76%, which demonstrate that the membrane surfaces have excellent water and oil repellency. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 40–46, 2006     

Preparation of core–shell poly(acrylic acid)/polystyrene/SiO2 hybrid microspheres

Core–shell poly(acrylic acid)/polystyrene/SiO₂ (PAA/PS/SiO₂) hybrid microspheres were prepared by dispersion polymerization with three stages in ethanol and ethyl acetate mixture medium. Using vinyltriethoxysilane (VTEOS) as silane agent, functional silica particles structured vinyl groups on surfaces were prepared by hydrolysis and polycondensation of tetraethoxysilane and VTEOS in core stage. Then, the silica particles were used as seeds to copolymerize with styrene and acrylic acid sequentially in shell stage I and stage II to form PAA/PS/SiO₂ hybrid microspheres. Transmission electron microscope results show that most PAA/PS/SiO₂ hybrid microspheres are about 40 nm in diameter, and the silica cores are about 15 nm in diameter, which covered with a layer of PS about 7.5‐nm thick and a layer of PAA about 5‐nm thick. This core–shell structure is also conformed by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and differential scanning calorimetry. FTIR results show that silica core, PS shell, and PAA outermost shell are bonded by covalents. In the core–shell PAA/PS/SiO₂ hybrid microsphere, the silica core is rigidity, and the PAA outermost shell is polarity, while the PS layer may work as lubricant owning to its superior processing rheological property in polymer blending. These core–shell PAA/PS/SiO₂ hybrid microspheres have potential as new materials for polar polymer modification. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1729–1733, 2006     

SEM studies of surfactant‐assisted micro‐mixing of melamine and wax particles

The validity of the micro‐mixing phenomenon was investigated by mixing a melamine dispersion, stabilized by low molecular mass poly(acrylic acid) (～5000 Daltons) and a wax emulsion, stabilized by an ethoxylated alkyl phenol surfactant. The wax particles were observed to be attached to the melamine surface because of the interaction between the poly(acrylic acid) dispersant and the ethoxylate group of the wax surfactant, resulting in the sedimentation of mixed particles. This phenomenon has potential application in the mixing of solid particles that require intimate contact and homogeneous mixing. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2554–2557, 2006     

SiO2／聚丙烯酸酯复合乳液的制备和表征

通过半连续种子乳液聚合法．在Si02溶胶存在情况下,利用有机硅单体乙烯基三乙氧基硅烷（A-151）的桥接作用,制备得到Si02／丙烯酸酯共聚物杂化乳液。对有机硅单体和二氧化硅用景对复合乳液稳定性能的影响进行了研究,采用投射电镜（TEM）和热重分析（TGA）对制备得到的复合乳液的形貌和耐热性进行测试表征。结果表明：在有机硅单体乙烯基三乙氧基硅烷用量为总单体4．0wt％,SiO2溶胶用鲢为单体15wt％以内,可制备出稳定的SiO2／丙烯酸酯共聚物杂化乳液。由于有机硅单体的桥接作用,部分SiO2粒子形成与乳胶粒上,形成草莓状的复合结构,且复合乳液其有较高的耐热性。     

水性聚氨酯-SiO_2纳米复合材料研究进展

介绍了水性聚氨酯纳米氧化硅复合材料的优异性能、纳米氧化硅的制备及分散方法、纳米氧化硅水性聚氨酯复合材料的制备方法及测试手段。     

Preparation and properties of poly(siloxane‐ether‐urethane)‐acrylic hybrid emulsions

Poly(siloxane‐ether‐urethane)‐acrylic (PU‐AC) hybrid emulsions were prepared by introducing different hydroxyethoxypropyl‐terminated polydimethylsiloxane (PDMS) content into the acrylic‐terminated poly(ether‐urethane) backbone and then in situ copolymerizing with methyl methacrylate and butyl acrylate via emulsion process. The effects of PDMS on the particle size and viscoelastic behavior of the hybrid emulsions were investigated. Meanwhile, the hydrogen bonding, mechanical and thermal mechanical properties, water resistance, the surface gloss, and wettability of the resultant hybrid films were also studied. The results showed that all the hybrid emulsions showed shear‐thinning behaviors, and the introduction of PDMS resulted in the formation of the hybrid emulsions with increased average particle size and decreased viscosity. The chemical bonds built between PU and AC yielded higher than 73% crosslinking fraction in all the hybrid materials, but this value decreased with increasing PDMS content because PDMS reduced the hydrogen bonding interactions and enhanced the phase separation. As a result, an increase in the PDMS content led to an increase in the elongation, water resistance, surface roughness, and water hydrophobic of the films, but the tensile strength, hardness, storage modulus, and glass transitions temperature decreased. It is suggested that introduction of PDMS can provide the hybrid materials with the improved flexibility, water resistance, and surface hydrophobicity, which has potential application value in the fouling‐release coatings, biomaterials, and surface fishing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44927.     

Kinetics and mechanism of styrene‐acrylonitrile copolymerization in micro‐emulsion

Stable and transparent poly(styrene‐acrylonitrile) latexes were produced by the polymerization of styrene‐acrylonitrile in ternary o/w micro‐emulsions containing sodium dodecyl sulfate as an anionic surfactant. Kinetics of copolymerization was studied at different temperatures using different concentrations of potassium persulfate and hydrogen peroxide/ascorbic acid. The suitability of existing model for homopolymerization was examined for styrene‐acrylonitrile copolymerization after appropriate modification. The latexes were characterized for particle size and number of particles by dynamic light scattering and TEM. The isolated products were characterized by ¹H and ¹³C NMR as well as by thermal analysis. The overall size of particles was found to be between 15 and 20 nm. © 2000 Society of Chemical Industry     

硅烷偶联剂改性空心SiO2纳米球对纯丙乳液性能的影响

采用硅烷偶联剂A-172改性空心SiO2纳米球,使其表面带有富含碳碳双键的活性基团,有效地增强了空心SiO2纳米球的疏水性,明显减少了团聚现象.进一步将其引入到纯丙乳液中,研究了其对纯丙乳液性能的影响.使用扫描电镜(SEM)、高倍透射电镜(HRTEM)观察了改性前后空心SiO2纳米球的形貌;使用傅里叶红外(FT-IR)、热重分析(TG)、附着力测试等对改性纯丙乳液的结构及性能进行了表征.结果表明:硅烷偶联剂改性后的空心SiO2纳米球在有机溶剂中的分散性明显增强,且并未破坏其形貌结构;空心SiO2纳米球改性后的纯丙乳液热稳定性及附着力明显提高.     

Preparation and characterization of nano‐SiO2 reinforced alginate‐based nanocomposite films (II)

Crosslinked alginate‐based nanocomposites at different SiO₂ contents were prepared successfully by blending the nano‐SiO₂ solution into low concentration alginate solution (0.5 wt %), with the alginate concentration increased step by step to the resulted concentration, in this course glycerol was used as plasticizer and 5 wt % CaCl₂ as crosslinker. The combined effect of SiO₂ content (1.5–8 wt %) on the microstructural, physical, mechanical, and optical properties of the nanocomposite films were investigated. The results showed that tensile strength and elongation was improved by about 40.33% and 89%, respectively, upon increasing the SiO₂ content to 4.5 wt %. In addition, water vapor permeability and swelling degree decreased by 19% and 16% with increasing SiO₂ content up to 8 and 4.5 wt %, respectively with respect to pure crosslinked alginate film. Thermogravimetric analysis also revealed that nano‐SiO₂ can improve the thermal stability of sodium alginate films produced by this method. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45286.     

Effect of acrylic monomer content on the properties of waterborne poly(urethane‐urea)/acrylic hybrid materials

Stable waterborne poly(urethane‐urea) (WBPU; soft segment content: 57%; dimethylol propionic acid: 19 mol %/5.8 wt %)–polyacrylate(methyl methacrylate/n‐butyl acrylate) (weight ratio: 4/1) hybrid latex (emulsions) with different acrylic contents [0, 10, 20, 30, and 40 wt % based on poly(urethane‐urea)] and without external surfactant were successfully prepared by in situ polymerization during a prepolymer mixing process. However, the as‐polymerized hybrid latex containing 50 wt % of acrylic monomer content was found to be unstable, indicating that about 50 wt % of acrylic monomer content was beyond the limit value of self‐emulsifying ability of WBPU anionomer prepared in this study. The breadth of particle size distribution of hybrid latex increased markedly from 20–75 to 55–275 nm with increasing acrylic monomer content from 0 to 40 wt %. The pristine WBPU and hybrid latex samples containing 10, 20, and 30 wt % of acrylic monomer showed unimodal distributions, whereas the hybrid sample having 40 wt % acrylic monomer content displayed a bimodal distribution with the broadest breadth. As acrylic monomer content increased, the yield point of stress–strain curve, hardness, glass transition, and water resistance of hybrid film samples increased, whereas their abrasion resistance, elongation at break, and elasticity decreased. The tensile strength of hybrid film samples (10–30 wt % of acrylic monomer content) was almost the same as that of pristine WBPU film sample, indicating the intimate molecular mixing between poly(urethane‐urea) and polyacrylate molecules in hybrids. However, the hybrid sample having 40 wt % acrylic monomer showed significantly diminished performance, which might be due to the deviation from intimate molecular mixing. From these results, the optimum acrylic monomer content was found to be about 30 wt %, which realized reasonably advantages of both poly(urethane‐urea) and acrylic polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization behavior of PA66/SiO2 organic‐inorganic hybrid material

The poly 2‐hydroxy propylmethacrylate‐methyl methacrylate (PHPMA‐MMA)/SiO₂ composite, derived from 2‐hydroxy propylmethacrylate (HPMA), methyl methacrylate (MMA), and tetraethoxysilane (TEOS), was used to synthesize polyamide 66(PA66)/SiO₂ organic‐inorganic hybrid material. X‐ray diffraction (XRD) was used to investigate the lattice spacing change of the PA66/SiO₂ hybrid material. It was found that the addition of PHPMA‐MMA/SiO₂ composite nearly did not change the crystal form of PA66. The nonisothermal crystallization kinetics of PA66 and PA66/SiO₂ hybrid material was investigated by differential scanning calorimetry (DSC) with various cooling rates. At every given cooling rate, the start crystallization temperature of the PA66/SiO₂ hybrid material was higher than that of PA66, while the crystallization temperature range was narrower than that of PA66. Avrami analysis modified by the Jeziorny method, the Ozawa method, and a method developed by Liu were employed to describe the nonisothermal crystallization process of the samples. The results showed that the Jeziorny method and the Ozawa method were not suitable to describe the nonisothermal crystallization process of PA66/SiO₂ hybrid material; however, when the relative degree of crystallinity X (t) was less than 1 ? 1/e, ln [? ln (1 ? X (t))] was still linear to lnt. The Liu method was successful to describe the nonisothermal crystallization processes for both PA66 and the PA66/SiO₂ hybrid material. It was confirmed that the presence of PHPMA‐MMA/SiO₂ composite could increase the crystallization rate and had a hetero phase nucleation effect on the PA66 matrix. Moreover, the introduction of PHPMA‐MMA/SiO₂ could improve the crystallization active energy ?E calculated by the Kissinger equation, attributing to the strong interaction between the polyamide chains and the PHPMA‐MMA/SiO₂ composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 810–817, 2006     

The structure and properties of acrylic‐polyurethane hybrid emulsions and comparison with physical blends

Aqueous acrylic‐polyurethane hybrid emulsions were prepared by semibatch emulsion polymerization of a mixture of acrylic monomers (butyl acrylate, methyl methacrylate, 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 varied to obtain different emulsion properties, microphase structure, and mechanical film properties of hybrid emulsions and physical blends. Particle size and molecular mass measurements, scanning electron microscopy, glass transition temperature, and rheological measurements performed characterization of the latex system. The mechanical properties were investigated by measuring tensile strength and Koenig hardness of dried films. The experimental results indicate better acrylic‐polyurethane compatibility in hybrid emulsions than in physical blends, resulting in improved chemical and mechanical properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 67–80, 2000     

Water‐dispersible conducting polyaniline/nano‐SiO2 composites without any stabilizer

A water‐dispersible conducting polyaniline/ nano‐SiO₂ composite, with a conductivity of 0.071 S cm^?1 at 25°C, was prepared by the oxidative polymerization of aniline in the presence of amorphous nano‐SiO₂ particles. And the structure, morphology, thermal stability, conductivity, and electroactivity of this composite were also investigated. This composite has been steadily dispersed in the aqueous solution for about 10–36 h without the need for any stabilizer. It would significantly impulse the commercial applications of conducting polyaniline/nano‐SiO₂ composite as fillers for antistatic and anticorrosion coatings. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The influence of interphase on nylon‐6/nano‐SiO2 composite materials obtained from in situ polymerization

Three commercially available silane, titanate and aluminate based coupling agents were used to pretreat nano‐SiO₂ for the preparation of nylon‐6/nano–SiO₂ composites via in situ polymerization. The interphases formed in different composite systems and their influence on material properties were investigated. Results indicated that the interfacial interactions differed between composite systems, whereas rigidity and toughness of composites were all improved by addition of pretreated silicas at an optimal content of 4.3 wt%. The presence of pretreated silicas did not have a distinct influence in the non‐isothermal crystallization behaviour of the nylon matrix. The composites containing pretreated silicas had slightly higher dynamic viscosities and superior storage moduli at high frequency, compared with neat nylon‐6. Copyright © 2003 Society of Chemical Industry     

Influence of stone particles on the rheological behavior of a novel photopolymerizable siloxane‐modified acrylic resin

A study was made of the effects of calcarenitic stone particles, known as pietra gentile, inclusions on the rheological behavior of photopolymerizable siloxane‐modified acrylic formulations, intended as protective for the calcarenitic stone structures. Different amounts of stone particles (ranging from 15% wt to 35% wt) were added to the modified acrylic mixture to achieve a natural color matching for calcarenitic stone substrates. The presence of stone particles was expected to modify the rheological behavior of the protective formulation. Therefore, the viscosity of the mixtures was studied at ambient temperature as function of the shear rate and the solid volume fraction. A relationship was obtained to predict the modification of viscosity of each formulation as a consequence of inclusions of different amounts of stone. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

原位生成纳米SiO_2/丙烯酸树脂皮革涂饰剂的研究

该研究用乳液聚合法原位合成了纳米S iO2/丙烯酸树脂复合涂饰剂。考察了单体配比,体系pH,引发剂、乳化剂及正硅酸乙酯(TEOS)用量等因素对乳液性能的影响,并分析表征了纳米复合涂饰剂的宏观、微观结构,测试了聚合物膜的物理机械性能以及用于皮革涂饰后革样的各项性能。结果为:透射电镜(TEM)观察发现,粒径小于100 nm的S iO2颗粒均匀分散于纳米复合涂饰剂乳液内,且无明显团聚现象;差示扫描量热(DSC)分析得出,纳米S iO2的加入使丙烯酸树脂的玻璃化温度(Tg)提高了12.2℃;傅里叶红外光谱(FTIR)分析表明,纳米复合涂饰剂中形成了—S i—O—S i—结构。纳米S iO2/丙烯酸树脂复合涂饰剂应用于皮革涂饰后,其各项性能较丙烯酸树脂涂饰有明显提高,如透水汽性提高了7.42%,透气性提高了7.33%,耐干、湿擦性能均提高一级。     

Mechanical properties of films prepared from model high‐glass‐transition‐temperature/low‐glass‐transition‐temperature latex blends

The mechanical properties of films prepared from model high‐glass‐transition‐temperature (T_g)/low‐T_g latex blends were investigated with tensile testing and dynamic mechanical analysis. Polystyrene (PS; carboxylated and noncarboxylated) and poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) [P(BMA/BA); noncarboxylated] were used as the model high‐T_g and low‐T_g latexes, respectively. Carboxyl groups were incorporated into the PS latex particles to alter their surface properties. It was found that the presence of carboxyl groups on the high‐T_g latex particles enhanced the Young's moduli and the yield strength of the PS/P(BMA/BA) latex blend films but did not influence ultimate properties, such as the stress at break and maximum elongation. These phenomena could be explained by the maximum packing density of the PS latex particles, the particle–particle interfacial adhesion, and the formation of a “glassy” interphase. The dynamic mechanical properties of the latex blend films were also investigated in terms of the carboxyl group coverage on the PS latex particles; these results confirmed that the carboxyl groups significantly influenced the modulus through the mechanism of a glassy interphase formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2788–2801, 2002