Growth control and long‐range self‐assembly of poly(methyl methacrylate) nanospheres

A systematic investigation of the reaction time and role of a cosolvent (toluene) in inducing several beneficial effects on nanobead properties was performed to achieve the synthesis of poly(methyl methacrylate) nanospheres. In particular, good dimensional control in the range of 100–400 nm, very low polydispersity, and a spherical shape were consistently obtained. Different parameters affecting the self‐assembly mechanism leading to the deposition of hard‐sphere photonic crystals were studied, and the features underlying their role were examined. Photonic crystals were produced by the evaporation of nanosphere suspensions at different temperatures, relative humidities, and suspension ionic strengths and with different substrate materials. The proper conditions for obtaining large crystal domains were determined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4493–4499, 2006     

Self‐assembly of pH‐responsive acrylate latex particles at emulsion droplets interface

The self‐assembly of pH‐responsive poly (methyl methacrylate‐co‐acrylic acid) latex particles at emulsion droplet interfaces was achieved. Raising pH increases the hydrophilicity of the latex particles in situ and the latex particle acts as an efficient particulate emulsifier self‐assembling at emulsion droplet interface at around pH 10–11 but exhibits no emulsifier activity at higher pH. This effect can be reversibly induced simply by varying the aqueous phase pH and thus the latex emulsifier can be reassembled. The effect factors, including the aqueous phase pH, the surface carboxyl content, ζ‐Potential of the latex particles and oil phase solvent have been investigated. Using monomer as oil phase, the latex particles could stabilize emulsion droplets during polymerization and cage‐like polymer microspheres with hollow core/porous shell structure were obtained after polymerization. The mechanism of the latex particles self‐assembly was discussed. The morphologies of emulsion and microspheres were characterized by optical microscopy, scanning electron microscopy, and transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of polystyrene/titanium dioxide composite particles containing organic ultraviolet‐stabilizer groups

Polystyrene/titanium dioxide (TiO₂) composite particles containing organic ultraviolet (UV)‐stabilizer groups were prepared by the emulsion copolymerization of styrene and 2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxylpropoxy)benzophenone with sodium sulfopropyl lauryl maleate as a surfactant in the presence of rutile TiO₂ modified with 3‐(trimethoxysilyl) propyl methacrylate, and the product was poly[styrene‐co‐sodium sulfopropyl lauryl maleate‐co‐2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxylpropoxy) benzophenone] [poly(St‐co‐M12‐co‐BPMA)]/TiO₂ composite particles. The structures of the composite particles were characterized with Fourier transform infrared spectroscopy, ultraviolet–visible (UV–vis) absorption spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The Fourier transform infrared and UV–vis measurements showed that poly(St‐co‐M12‐co‐BPMA) was grafted from the surface of TiO₂, and this copolymer possessed a high absorbance capacity for UV light, which is very important for improving the UV resistance of polystyrene. The thermogravimetric analysis measurements indicated that the percentage of grafting and the grafting efficiency could reach 513.9 and 59.9%, respectively. The differential scanning calorimetry measurement indicated that the glass‐transition temperature of the poly(St‐co‐M12‐co‐BPMA)/TiO₂ composite particles was higher than that of poly (St‐co‐M12‐co‐BPMA).These research results are very important for preparing polystyrene with high UV resistance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation of emulsifier‐free polystyrene by conventional emulsion polymerization with a hydrolysable emulsifier

An alkali‐hydrolyzable surfactant, (1‐tetradecyloxycarbonyl)trimethylammonium chloride, was used as an emulsifier for emulsion polymerization of styrene inwater. The polymerization yielded a high molecular‐weight polymer almost quantitatively. Addition of a small amount of NaOH to the resulting latex solution precipitated the polymer immediately. Analysis of the centrifuged solid indicated almost perfection of both recovery of the polymer and removal of surface‐active species from it. Minimization of ionic species in the polymer solid was confirmed by a high contact angle of the polymer film with water. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

简述胶晶模板法制备三维有序大孔炭材料

三维有序大孔炭(3DOM)材料是近年来刚刚兴起的多孔材料领域一项重要研究课题。3DOM大孔炭材料不仅具有多孔材料的一般特点,还具有孔结构排列周期性强、孔径分布窄、大孔尺寸均匀可调,且具有较大的孔径、较高的表面积等一系列特点,在新型催化、吸附分离、电极材料等方面都具有潜在的应用价值。本文总结了近年来胶晶模板法制备三维有序大孔炭材料,分别从模板的制备、碳源的选择以及到最终大孔炭的制备三个方面加以总结概述。     

Preparation and characterization of pore wall‐functionalized three‐dimensionally ordered macroporous syndiotactic polystyrene

A versatile method for the modification of three‐dimensionally ordered macroporous (3DOM) highly syndiotactic polystyrene via chloromethylation at the pore walls has been demonstrated. This was followed by reaction with dimethylamine to establish a versatile approach to functionalization of such macroporous polymers. High syndiotacticity of 3DOM sPS is necessary for maintenance of the morphology of the original ordered pore structure after chloromethylation. The relative content of chloromethyl groups was shown to be 1.89 mmol/g3DOM sPS by TG‐titration. The functionalized 3DOM sPS was characterized by SEM, FT‐IR, and DSC to demonstrate that chloromethylation had occurred at the pore walls and that the dimethylamino moiety had replaced the chlorine atom of the chloromethyl group. DSC examination of the modified polymer indicated that the crystallinity of 3DOM sPS is little affected by functionalization. Thus the excellent properties of sPS are retained by the functionalized material. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

The microencapsulation of calcium chloride hexahydrate as a phase‐change material by using the hybrid coupler of organoalkoxysilanes

A novel method of microencapsulation for inorganic salt hydrates as phase‐change material (PCM), which is essential for their broad application, was pursued by combining sol–gel process with interfacial polymerization. Calcium chloride hexahydrate (CCH), chosen as a representative PCM of salt hydrates, was used as a core material, and organoalkoxysilane was applied to provide hybrid properties of mediating the hydrophilic core and hydrophobic shell material. The Fourier transform infrared spectra and SEM images confirmed that the siloxane and polyurea shell material successfully capsulated the CCH core. Fine morphology of microcapsules was further investigated with SEM, and it presented almost‐spherical shape and a well‐defined core–shell structure. Thermogravimetric analysis indicated that microcapsules containing CCH have sufficient thermal stability, which usually degraded in four steps. Differential scanning calorimeter investigation confirmed additionally that the microencapsulated CCH absorbs thermal energy with phase change during the melt process but undergo a severe super cooling phenomenon in the crystallizing process. In addition, the durability test was conducted to evaluate the siloxane polymer and polyurea as a shell material, protecting CCH from leaking. The effect of pH and the ratio of ingredients were studied in terms of encapsulation possibility and performance of core PCM, which include morphology of core–shell particles and essential thermal properties as a PCM. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45821.     

Preparation of silane‐terminated polystyrene and polymethylmethacrylate self‐assembled films on silicon wafer

End silane functionalized polystyrene and polymethylmethacrylate were prepared through radical chain‐transfer reaction and characterized with gel‐permeation chromatography. The chain‐transfer constants of mercaptopropyltrimethoxysilane for the polymerization of styrene and methylmethacrylate were determined to be 8.48 and 0.67, respectively, from the slopes of 1/DP_n versus [S]/[M] lines. The ultrathin films of the end silane–terminated polymers were prepared by self‐assembly onto hydroxylated silicon wafers. The water contact angle on the resulting ultrathin films and the film thickness were measured. The morphology and chemical features of the films were observed and investigated by means of atomic force microscopy and X‐ray photoelectron spectroscopy. Results indicated that the chain‐transfer agent played a key role in making it possible for the silane‐terminated polystyrene and polymethylmethacrylate to be self‐assembled on Si(111), whereas the thickness and surface quality of the ultrathin films were dependent on the molecular weights of the polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1695–1701, 2004     

Long‐range‐ordered,hexagonally packed nanoporous membranes from degradable‐block‐containing diblock copolymer film templates

Polystyrene (PS)‐b‐polylactide (PLA) diblock copolymers with different molecular weights and fractions were synthesized through a combination of living anionic polymerization and controlled ring‐opening polymerization. Then, the PS–PLA films were guided to phase‐separate by self‐assembly into different morphologies through casting solvent selection, solvent evaporation, and thermal and solvent‐field regulation. Finally, perpendicularly oriented PS–PLA films were used as precursors for PS membranes with an ordered periodic nanoporous structure; this was achieved by the selective etching of the segregated PLA domains dispersed in a continuous matrix of PS. Testing techniques, including IR, ¹H‐NMR, gel permeation chromatography, scanning electron microscopy (SEM), and atomic force microscopy (AFM), were used to determine the chemical structure of the PS–PLA copolymer and its film morphology. AFM images of the self‐assembled PS‐PLA films indicate that vertical tapers of the PLA domains were generated among PS continuum when either toluene or tetrahydrofuran was used as the annealing solvent. The SEM images certified that the chemical etching of the PLA component from the self‐assembled PS–PLA films led to a long‐range‐ordered array of hexagonally packed nanoporous membranes with a diameter about 500 nm and a center‐to‐center distance of 1700 nm. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39638.     

Aqueous core polystyrene microspheres fabricated via suspension polymerization basing on a multiple pickering emulsion

Multi‐hollow or hollow polymer particles are of great interest in many fields. Here we successfully fabricate polystyrene microspheres with aqueous cores through w/o/w Pickering emulsion stabilized by modified SiO₂ nanoparticles. The final structure and constituents of the microspheres is investigated via SEM, X‐ray photoelectron spectra, and thermo‐gravimetric analysis. The results demonstrate that the size and amount of aqueous cores in the microspheres can be tuned by the original structure of the multiple emulsions: when the volume fraction of inner water is 0.2, the inner structure of the microspheres obtained is porous and each pore is not interconnected; when the volume fraction of inner water is increased to 0.7, the resulting products are hollow microspheres and when 0.3% wt/vol of salt is added to the inner aqueous phase, the inner pores of the resulting microspheres enlarge or even coalesce. The multi‐hollow or hollow polystyrene microspheres with aqueous cores are expected to be candidates for encapsulation in biotechnology. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39761.     

Surfactant‐directed morphology of cross‐linked styrene‐ or vinylbenzyl chloride‐based materials

Polystyrene (PSt) or poly(vinylbenzyl chloride) (PVBC) crosslinked with divinylbenzyl (DVB) materials were synthesized through free radical polymerization into templates formed by the surfactant polyoxyethylene (4) lauryl ether (Brij‐30). The chemical composition of the final products was verified through attenuated total reflectance infrared spectroscopy (ATR‐IR) and the thermal behavior was investigated through thermogravimetric analysis (TGA). Depending on the organization of Brij‐30 in aqueous solution, three characteristic structures, namely spherical nanoparticles, platelet‐like objects and three‐dimensional networks, were identified through scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The spherical nanoparticles and the platelet‐like objects form rather stable dispersions, especially in aqueous surfactant solutions, as exemplified by the evolution of the turbidity of the PSt‐based materials, using sodium dodecyl sulfate as surfactant. All materials retain their integrity even after thermal treatment at high temperature (～200–250°C). The benzyl chloride group of the PVBC‐based materials offers a significant potential for further elaboration and practical applications, since they can be further functionalized while retaining their integrity. This potential is demonstrated here through hydrolysis to obtain hydroxyl‐functionalized three‐dimensional networks. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43297.     

Water‐dispersible porous polyisoprene‐block‐poly(acrylic acid) microspheres

Two polyisoprene‐block‐poly(tert‐butyl acrylate) (PI‐b‐PtBA) samples and a poly(tert‐butyl acrylate) (PtBA) homopolymer (hPtBA) were prepared by anionic polymerization and characterized by light scattering, size exclusion chromatography, and NMR. The tert‐butyl groups were removed from one of the diblocks to yield amphiphilic polyisoprene‐block‐poly(acrylic acid) (PI‐b‐PAA). PI‐b‐PAA was then used as the surfactant to disperse dichloromethane containing PI‐b‐PtBA and hPtBA at different weight ratios as oil droplets in water. Solid microspheres containing segregated polyisoprene (PI) and PtBA/hPtBA domains were obtained after dichloromethane evaporation. Permanent microspheres were obtained after PI domain crosslinking with sulfur monochloride. Porous microspheres were produced after the hydrolysis of PtBA and the extraction of the homopoly(acrylic acid) chains. The shape and connectivity of the poly(acrylic acid)‐lined pores were tuned by changes in the PtBA/hPtBA content in the precursor microspheres. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2785–2793, 2003     

Preparation of polystyrene/poly(vinyl acetate) nanocomposites with a core–shell structure via emulsifier‐free emulsion polymerization

Polystyrene/poly(vinyl acetate) latex nanoparticles with a core–shell morphology in an emulsifier‐free emulsion polymerization system were prepared with purified styrene and vinyl acetate (VAc) as monomers and 2,2′‐azo bis(2‐amino propane) dihydrochloride (ABA,2HCl) as the initiator and emulsifier. The optimized conditions of polymerization of VAc, on top of the already‐formed polystyrene as a core polymer, with a core–shell morphology were obtained using various parameters such as volume ratio of the first and second stages, type of process, and reaction time. The morphologic structure of the nanoparticles was studied by scanning electron microscopy and transmission electron microscopy. The latex nanoparticles and polymers were characterized by differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2409–2414, 2006     

Preparation of nano‐ and microparticles through self‐assembly of azobenzene‐pendent ionomers

The particle formation of azobenzene‐containing ionomers, through self‐assembly, in aqueous media (THF/H₂O solvent) was studied. The ionomers were synthesized by copolymerization between azobenzene‐pendent methacrylate and methacrylic acid. It was revealed by UV–vis spectra and light scattering measurements that the extent of H‐aggregation of the azobenzene units first decreased, and then increased with increasing volume fraction of H₂O of the solvent. The H₂O fraction at which the extent of H‐aggregation began to increase became lower, when the copolymers contained more azobenzene units. Colloidal particles were prepared by slow addition of various concentrations of aqueous NaOH to the copolymer THF solutions. The hydrodynamic diameters of the particles obtained by the procedures were several hundreds of nanometer. When the azobenzene unit content in the copolymer was smaller, the diameters of the particles became smaller. When the colloidal particles dispersions were cast on a carbon sheet and dried, the particles aggregated and formed larger spherical particles, with diameters of several micrometers. The size of the particles obtained by the drying process became smaller, when higher concentrations of aqueous NaOH solutions were used. Therefore, the particle sizes were controlled by the azobenzene units content in the copolymers and the concentration of aqueous NaOH solutions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3913–3918, 2006     

Synthesis of sub‐micrometer core–shell rubber particles with 1,2‐azobisisobutyronitrile as initiator and deformation mechanisms of modified polystyrene under various conditions

BACKGROUND: Sub‐micrometer core‐shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) copolymers with various ratios of polybutadiene (PB) core to polystyrene (PS) shell were synthesized by emulsion grafting polymerization with 1,2‐azobisisobutyronitrile (AIBN) as initiator. These graft copolymers were blended with PS to prepare PS/PB‐g‐PS with a rubber content of 20 wt%. The mechanical properties, morphologies of the core‐shell rubber particles and deformation mechanisms under various conditions were investigated. RESULTS: Infrared spectroscopic analysis confirmed that PS could be grafted onto the PB rubber particles. The experimental results showed that a specimen with a ‘cluster’ dispersion state of rubber particles in the PS matrix displayed better mechanical properties. Transmission electron micrographs suggested that crazing only occurred from rubber particles and extended in a bridge‐like manner to neighboring rubber particles parallel to the equatorial plane at a high speed for failure specimens, while the interaction between crazing and shear yielding stabilized the growing crazes at a low speed in tensile tests. CONCLUSION: AIBN can be used as an initiator in the graft polymerization of styrene onto PB. The dispersion of rubber particles in a ‘cluster’ state leads to better impact resistance. The deformation mechanism in impact tests was multi‐crazing, and crazing and shear yielding absorbed the energy in tensile experiments. Copyright © 2009 Society of Chemical Industry     

胶体晶体模板法制备三维有序排列的大孔SiO2材料

将粒径为480 nm的聚苯乙烯微球离心组装为胶体晶体模板,以正硅酸乙酯为硅源配制SiO₂溶胶并填充到模板间隙,原位形成凝胶,最后通过焙烧去除模板,得到三维有序大孔（3DOM）SiO₂。通过SEM检测,大孔以六方有序的方式排列,其孔径及孔径收缩率分别为360 nm和25％。大孔之间由小窗口连通,构成内部三维交联的大孔网络。低温N₂吸附测试表明,大孔孔壁上存在中孔孔隙,其中在3～4 nm有一集中的孔分布。XRD显示,制备的3DOM材料由无定形SiO₂组成。     

Dispersion polymerization of uniform cross‐linked polystyrene microspheres in butan‐1‐ol

Butan‐1‐ol can be used as the solvent in the synthesis of poly(styrene‐co‐divinylbenzene‐co‐acrylic acid) microspheres by dispersion polymerization of a mixture of styrene, divinylbenzene (DVB), and acrylic acid (AA). Varying the proportion of the crosslinker DVB affects the size distribution and particle morphology profoundly, with 0.5–1.0% w/w producing spherical particles, whereas 2.0% w/w DVB produces irregular, concave morphologies. Varying the amount of AA from 5–7% w/w increases the average diameter of the spherical particles, whereas 9% w/w AA results in ovoid particles with dimpled surface morphology. In an optimized synthesis using 1.0% w/w DVB and 5% AA, uniform polymer microspheres with an average diameter of 0.8 µm and a coefficient of variation (CV) of diameter of 8.2% are produced. The use of a medium‐polarity solvent, such as butan‐1‐ol, as the solvent for dispersion polymerization will facilitate the incorporation of non‐polar moieties, such as organically‐passivated quantum dots, into the polymer during synthesis. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43103.     

Emulsion polymerization of styrene using mixtures of hydrophobically modified inulin (polyfructose) polymeric surfactant and nonionic surfactants

Polystyrene latex dispersions were prepared by emulsion polymerization, using a mixture of hydrophobically modified Inulin (INUTEC® SP1) and various nonionic surfactants (cosurfactants). Two series of nonionic surfactants were used, namely Synperonic A (C_13–15 alkyl chain with 7, 11, and 20 moles of ethylene oxide, EO) and Synperonic NP (nonylphenol with 10 and 15 moles of EO). For 5 wt % latex, the INUTEC SP1 concentration was kept constant at 0.0165 wt % and the initiator concentration was also kept constant at 0.0125 wt %, whereas the cosurfactant concentration was varied between 0.1 and 0.5 wt %. With the exception of Synperonic A20, all other cosurfactants showed an initial increase in particle diameter followed by a decreased reaching a value comparable with that obtained using INUTEC SP1 alone. However, A20 produced a continuous reduction in particle diameter with increase of surfactant concentration, reaching a value of 100 nm at 0.5 wt % which is lower than the value obtained using INUTEC SP1 alone (188 nm). In all cases, addition of a cosurfactant enhanced the stability of latexes by co‐adsorption at the solid–liquid interface. The enhanced stability produced by the addition of cosurfactants to INUTEC SP1 could be illustrated by using the mixture of INUTEC SP1 and Synperonic A7 at 40 wt % of styrene latex concentration. In this case, the mixture produced lower particle size, much lower polydispersity index and much higher stability. These results are of significant value for industrial applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of a self‐compatibility alloy via a seed‐graft concentrated‐emulsion pathway

A novel polymerization procedure, the concentrated‐emulsion graft polymerization of styrene monomer with poly(butyl acrylate) seed, was proposed for the production of a self‐compatibility macromolecule alloy. The effects of the butyl acrylate content, sodium dodecyl sulfate concentration, and polymerization temperature on the graft ratio were investigated. Scanning electron microscopy, transmission electron microscopy, and impact strength were used to characterize the microstructure and mechanical performance of the self‐compatibility macromolecule alloy. The results showed that increasing the butyl acrylate content, reducing the sodium dodecyl sulfate concentration, and improving the polymerization temperature all favored an increased graft ratio, which resulted in increased impact strength of the self‐compatibility macromolecule alloy. Therefore, the concentrated‐emulsion polymerization method is particularly suitable for seed‐graft polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2915–2920, 2002; DOI 10.1002/app.10288     

Preparation of raspberry‐shaped styrene‐butadiene‐methyl acrylate‐acrylic acid latex particles by emulsion polymerization followed by alkali/heating method

Monodispersed raspberry‐shaped polystyrene‐butadiene‐methyl acrylate‐acrylic acid particles were made by semi‐batch emulsion polymerization followed by alkali and heat treatment. The particle sizes and size distributions were studied by hydrodynamic chromatography and transmission electronic microscopy. The morphology of the particles was observed by SEM, cryo‐SEM, and TEM. Treatment temperature was found to have a significant impact on the particle size and morphology of the treated latexes. Higher temperatures lead to larger particle sizes and more discernible raspberry domains with sizes around 50 nm on the particle surfaces. Higher levels of alkali did not significantly change the particle size but did increase the total titratable acid amount, presumably due to the hydrolysis of methyl acrylate during the treatment. GPC results showed that higher amount of oligomers or polymers are produced in the serum for the heat‐treated latexes. Divinylbenzene crosslinking agent at the levels of 0.05–3% limited the particle expansion and decreased the serum acid. A possible mechanism of raspberry particle formations was proposed, which involves migration of hydrophilic and hydrophobic species during the heat treatment. Lastly, potential applications for raspberry particles in paper coating were explored. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011