Synthesis of poly(styrene‐co‐4‐vinylpyridine) microspheres via dispersion polymerization: Effect of the concentration of 4‐vinylpyridine

Amphiphilic copolymer microspheres of poly(styrene‐co‐4‐vinylpyridine) were prepared by dispersion polymerization in an alcohol/water medium. The synthesis of poly(styrene‐co‐4‐vinylpyridine) microparticles was successfully carried out, and the latexes had a spherical morphology with good monodispersity. The degree of conversion in the early stage of polymerization decreased with increasing 4‐vinylpyridine (4VP) monomer content, but the final conversions were similar (>95%). The copolymerization rate decreased with increasing 4VP content, and a broad particle size distribution was observed with 20 wt % 4VP because of the prolonged nucleation time. With the 4VP concentration increasing, the molecular weight of the copolymer microspheres decreased, and the glass‐transition temperature of the copolymers increased; this indicated that all the copolymers were random and homogeneous. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Highly crosslinked poly(styrene‐co‐divinylbenzene) microspheres prepared by precipitation polymerization: Effects of the polymerization parameters on the characteristics of the particles

Highly crosslinked poly(styrene‐co‐divinylbenzene) microspheres with a 1.0–2.5‐μm diameter were prepared by precipitation polymerization in neat acetonitrile. The effects of various polymerization parameters such as the monomer and initiator concentration, comonomer composition, and cosolvents on the properties of the resulting particles were studied. The particle diameter increased with the monomer concentration, whereas the particle size distribution remained almost constant. The resulting yield of the particles reached 41.1% when 6 wt % 2,2′‐azobisisobutyronitrile (based on the total monomer) was used as the initiator. The styrene fraction in the monomer composition and toluene fraction in the solvent mixture also significantly affected the morphology and size of the resulting particles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Magnetite‐coated polystyrene hybrid microspheres prepared by miniemulsion polymerization

Hybrid microspheres with a polystyrene core coated with magnetite nanoparticles were prepared by miniemulsion polymerization. Acrylic acid was used as a comonomer to promote the anchoring of the magnetite nanoparticles onto the polymeric surface. The addition of a hydrophobic agent prevents effectively the monomer from diffusing into the aqueous phase. Magnetite was treated with a silane coupling agent in order to introduce some interactions with the polymers. The morphology and the structure of the hybrid microspheres were characterized using X‐ray diffraction, infrared spectroscopy, transmission electron microscopy and thermogravimetric analysis. The results show that the morphology of the hybrid microspheres was influenced by the concentrations of acrylic acid, hydrophobic agent and surfactant, and that the degree of coating can be tuned by changing these parameters. The miniemulsion polymerization technique is adaptable to the synthesis of magnetite‐coated polymer particles, and the synthesis can be scaled up. Copyright © 2008 Society of Chemical Industry     

Preparation of uniform hollow polystyrene particles with large voids by a glass‐membrane emulsification technique and a subsequent suspension polymerization

Hollow polymer particles with large voids were prepared with styrene (St) as the main component and in the presence of a small amount of N,N′‐dimethylaminoethyl methacrylate (DMAEMA) via a glass‐membrane emulsification technique and a subsequent suspension polymerization. A mixture of the monomer, hexadecane (HD), and N,N′‐azobis(2,4‐dimethylvaleronitrile) as an initiator was used as a dispersed phase (oil phase). By the careful pushing of the dispersed phase through the pores of the glass membrane into the aqueous phase, an emulsion of fairly monodisperse monomer droplets was formed. Then, the polymerization was performed by temperature being elevated to 70°C. The aqueous phase (continuous phase) contained poly(N‐vinyl pyrrolidone) as a stabilizer, sodium lauryl sulfate as a surfactant, Na₂SO₄ as an electrolyte, and sodium nitrite (NaNO₂) as a water‐soluble inhibitor. Results related to the effects of the HD content, DMAEMA, and the composition of the comonomer, including the crosslinker and flexible segment, on the features of the hollow particles were investigated. When the content of DMAEMA was higher than 1.0 wt % based on the total monomer, small, secondary particles were generated in the aqueous phase, but the generation was effectively prevented when DMAEMA was limited to 0.5 wt %. Hollow particles, with an average diameter of around 7 μm, were obtained with an St–DMAEMA system. The void size of the hollow particles was controlled by the HD content. When the HD content was lower (<25 wt % based on the oil phase), unbroken hollow particles were easily obtained. However, they tended to break into halves after drying when the HD content was increased to 50 wt %. A soft segment, lauryl acrylate, and a crosslinker, ethylene glycol dimethacrylate, were added to overcome this problem. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 244–251, 2003     

Synthesis and characterization of butan‐1‐ol modified toluene diisocyanate trimer

Butan‐1‐ol modified toluene diisocyanate tri mer (TDI‐trimer) was synthesized and characterized with Fourier transform infrared spectroscopy, gel permeation chromatography, and thermal gravimetry analysis techniques. The modified TDI‐trimer showed good dissolvable ability with hydroxy resin and can be used to produce paints with acrylic polyol resin. The thermal stability of the modified TDI‐trimer was improved by simply increasing both the amount of catalyst and the ratio of ? NCO/? OH, less depended on the kind of catalyst. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4958–4962, 2006     

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.     

Synthesis of monodisperse crosslinked polystyrene microspheres via dispersion copolymerization with the crosslinker‐postaddition method

Monodisperse crosslinked polystyrene microspheres were prepared by the dispersion copolymerization of styrene and divinylbenzene in a mixed solvent of ethanol and H₂O. 2,2′‐Azobisisobutyronitrile and poly(N‐vinyl pyrrolidone) were used as the initiator and steric stabilizer, respectively. The crosslinker‐postaddition method was adopted through a slow addition of a crosslinking agent into the dispersion system at a certain time after the beginning of the polymerization. The effects of the postaddition recipe, postaddition beginning time, postaddition velocity, and agitation rate on the particle size, size distribution, and morphology were discussed. The resulting polymer microspheres were characterized with scanning electron microscopy and laser particle analysis. Crosslinked polystyrene microspheres with a narrow size distribution and a 12.0% crosslinker level were obtained with a size of 1.0 μm through the crosslinker‐postaddition method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Hypercrosslinked polystyrene microspheres with bimodal pore size distribution and controllable macroporosity

A combination of suspension polymerization and postcrosslinking was used to prepare hypercrosslinked polystyrene (H‐PS) microspheres with controllably bimodal pore size distribution in the presence of toluene and polypropylene (PP) as a coporogen. The proportion of PP in the coporogen was changed to investigate the influence of the coporogen composition on the pore structure of the H‐PS microspheres. The addition of a small amount of PP achieved the aim of a clearly bimodal pore size distribution and the control of the macroporosity of the H‐PS microspheres, which have potential application in the preparation of catalyst supports. The specific surface area of the H‐PS microspheres could be adjusted in the range 380–790 m²/g by changes in the concentration of PP in the coporogen. Moreover, the H‐PS microspheres displayed all the characteristics of Davankov‐type resins by their ability to be swollen in both thermodynamically poor solvents such as water and good solvents such as toluene. Finally, the possible mechanism of porosity formation during polymerization and postcrosslinking was also examined by a combination of pore structure data and the appearance of the microspheres before and after postcrosslinking. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Radiational hardening of poly(vinylidene fluoride)–poly(methyl methacrylate)–polystyrene ternary blends

Specimens of poly(vinylidene fluoride) (PVDF)–poly(methyl methacrylate) (PMMA)–polystyrene (PS) polyblends with different weight percentage ratios of the three polymers were prepared with the solution cast technique. The effect of γ irradiation on the Vicker's microhardness was studied. Among the three pure polymers, PVDF, PMMA, and PS, the γ irradiation imparted crosslinking in PVDF, thereby causing radiational hardening. In the cases of PMMA and PS, the effect of irradiation exhibited a predominance of both the scissioning and crosslinking processes in different ranges of doses. Moreover, at a dose of 5 Mrad, in both PMMA and PS, maximum radiational crosslinking was observed. The effect of γ irradiation seemed to stabilize beyond 15 Mrad in PVDF and beyond 20 Mrad in PMMA and PS. Microhardness measurements on ternary blends of PVDF, PMMA, and PS revealed that the blend with low contents of PMMA, that is, up to 5 wt %, yielded softening, whereas increasing the content of PMMA beyond 5 wt % produced a hardened material because of radiational crosslinking, and a higher content of PMMA in the blend facilitated this crosslinking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3107–3111, 2004     

Synthesis and characterization of soluble hyperbranched polymer via initiator‐fragment incorporation radical polymerization of divinylbenzene with dimethyl 2,2′‐azobisisobutyrate

The homopolymerization of divinylbenzene (DVB) as an excellent crosslinker (0.20 mol/L) with dimethyl 2,2′‐azobisisobutyrate (MAIB) proceeded homogeneously without any gelation at 80°C in benzene when the MAIB concentrations as high as 0.30–0.50 mol/L were used, yielding soluble polymers. In the polymerization at the concentrations of [DVB] = 0.20 mol/L and [MAIB] = 0.50 mol/L, the polymer yield increased with time and leveled off over 90 min. The molecular weight and molecular weight distribution increased with polymer yield. The vinyl groups of DVB were observed to be almost completely consumed in about 80 min, by FT near‐IR spectroscopic analysis. The homogeneous polymerization system involved ESR‐observable polymer radical, the concentration of which increased with time up to 3.4 × 10^?5 mol/L. The polymer formed in the polymerization for 2 h consisted of 46 mol % of DVB unit and 54 mol % of the methoxycarbonylpropyl group as MAIB fragment, indicating that an initiator‐fragment incorporation radical polymerization proceeds in the present polymerization. The polymer was soluble in benzene, tetrahydrofuran, ethyl acetate, chloroform, acetone, and N,N‐dimethylformamide, while it was insoluble in n‐hexane, acetonitrile, dimethyl sulfoxide, methanol, and water. The results of the multiangle laser light scattering and viscometric measurements revealed that the individual polymer molecules were formed as hyperbranched polymer nanoparticles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 664–670, 2006     

One‐pot synthesis of monodispersed phosphazene‐containing microspheres with active amino groups

An amine‐terminated nucleophile Hexakis (4‐aminophenoxy) cyclotriphosphazene (HACP) was synthesized. Its chemical structure was identified by ¹H NMR and ³¹P NMR. Novel monodispersed phosphazene‐containing microspheres with active amino groups on the surface have been successfully prepared through a one‐pot precipitation polymerization of hexachlorocyclotriphosphazene with HACP. Just by single step, the microspheres were synthesized without stirring, surfactant and ultrasonic irradiation. The diameter of the obtained microspheres ranged from 0.1 to 0.5 μm with the rough surface. And, the onset of the thermal‐degradation temperature was 460°C, which is attributed to the highly cross‐linked structure and the introduced of the cyclotriphosphazene rings. Moreover, the products at variable stages of polymerization were measured by TEM. The formation mechanism was proposed which is corresponding with an oligomeric species absorbing mechanism. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43336.     

pH and organic solvent‐sensitive properties of crosslinked polymeric spheres formed by a soap‐free emulsion polymerization

Narrowly distributed poly (styrene‐co‐(4‐vinylpyridine)) microspheres are facilely prepared by a soap‐free emulsion polymerization, and their structures and properties are investigated by TEM, FTIR spectra, DSC, and DLS, respectively. The sizes and glass transition temperatures of the polymeric spheres increase with an increase of 4‐vinylpyridine in the reactive system. In addition, these polymeric spheres show good stability in water and a series of organic solvents due to their crosslinked structures. When poly(styrene‐co‐(4‐vinylpyridine)) microspheres are obtained in the reactive system where the weight ratio of 4‐vinyl pyridine to styrene is less than 4/6, they can be well dispersed in water as well as in organic solvents such as ethanol, toluene and DMF, and show obvious pH sensitive and organic solvent‐sensitive characteristics. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dispersion polymerization of n‐butyl acrylate

The dispersion polymerization of n‐butyl acrylate (BA) was investigated using alcohol/water mixtures as the dispersion medium, 4,4′ ‐azobis‐(4‐cyanopentanoic acid) as the initiator, and polyvinylpyrrolidone (PVP) as the stabilizer. The effects of polymerization parameters, such as the alcohol/water ratio in the medium and the type and concentration of the polymeric stabilizer, on the resulting particle size and size distribution were studied. The final particle size and the stability of the dispersion system were found to be greatly influenced by the type of alcohol used in the mixture; that is, methanol or ethanol, even though the apparent solubility parameters are almost the same for the two types of mixtures. Poly(butyl acrylate) particles with controlled size and size distribution (monodisperse), and gel content were successfully prepared in a 90/10 methanol/water medium. It was found that the particle size decreased with increasing initiator concentration. This is the opposite of what was previously reported in the dispersion polymerizations of styrene and methyl methacrylate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2692–2709, 2002     

Novel cross‐linked sericin films: Characterization and properties

In the present study, an attempt has been made to convert sericin into film form and further make it insoluble by forming sericin–aluminum metal complex using alum salt, which may lead to some extent of cross‐linking. After complex formation sericin becomes insoluble in warm water as well as thermal stability and tensile strength improves significantly with increasing alum content. Metal complexed sericin films show good antimicrobial property and both the pure and alum modified sericin (AM‐Sericin) films show a very good oil barrier property. But after complex formation moisture content and swelling percentage of sericin film decreases quite significantly with increasing aluminum concentration. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41400.     

无皂乳液聚合法合成单分散性阴离子聚苯乙烯微球

采用无皂乳液聚合法制备了粒径大小可控且均一的聚苯乙烯微球,研究了反应过程中SDS加入量、反应温度、引发剂加入量及反应介质对聚苯乙烯微球粒径大小及分布的影响。利用傅立叶变换红外光谱仪对微球结构进行了表征。     

Solvothermal synthesis of organically modified α‐zirconium phosphate‐based polystyrene nanocomposites and thermal stability

Polystyrene/α‐zirconium phosphate (PS/OZrP) nanocomposites were prepared based on the organically modified α‐ZrP(OZrP) with hexadecyltrimethyl ammonium bromide (C16) by solvothermal technique and solution refluxing. The structure of the PS/OZrP composites was characterized by X‐ray diffraction and high‐resolution electronic microscopy. The thermal behaviors of the composites obtained were investigated by thermogravimetric analysis. The maximum decomposition temperatures (T_max) of PS/OZrP nanocomposites prepared by solvothermal method increased gradually from 431 to 458°C with the increase of the OZrP loading from 0 to 20 wt %, and the amounts of the charred residue at 600°C (char wt %) had a remarkable increase from 1.6 to 17.1 wt %, respectively. Moreover, the TG results of the nanocomposites prepared by solvothermal method have more obvious enhancement in the thermal stabilities and especially in the amount of charred residue at 600°C (char wt %), which has a double increase from 4.2 to 8.5 wt % at the content of 10 wt % OZrP than by solution refluxing. All results suggested that the solvothermal method is an effective way for the preparation of PS/OZrP nanocomposites with the intercalated nanostructure, which led to the obviously improved thermal stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 122:593–598, 2011     

Analysis of chain‐scission and crosslinking rates in the photo‐oxidation of polystyrene

A study of the chain‐scission and crosslinking rates in polystyrene photodegraded in the laboratory with fluorescent tubes (UVA‐340) was made using GPC molecular weight distributions. The analysis was based on the assumption that scission and crosslinking occur randomly and employed a Monte Carlo procedure to compute the changes in molecular weight distribution for chosen values of scission and crosslinking rates and compared the computed profiles with measurements made on the photodegraded samples. Results were obtained for three different exposures and at various depths within 3.2‐mm‐thick bars. The scission/crosslinking ratio, λ, was between 3 and 8 for all samples measured in this study. The lowest values of λ were found near the exposed surface and the highest near the bar center. Both scission and crosslinking rates were much lower in the interior, presumably the result of oxygen starvation. Some bars were exposed while loaded to 10 MNm⁻² in uniaxial tension. The stress appeared to increase the reaction rates somewhat near the surface and to depress the rates in the interior correspondingly. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3015–3023, 2000     

Properties of high‐impact polystyrene/organoclay nanocomposites synthesized via in situ polymerization

High‐impact polystyrene (HIPS)/organically modified montmorillonite (organoclay) nanocomposites were synthesized via in situ polymerization. The effects of the organoclay on the morphology and material properties of HIPS/organoclay nanocomposites were investigated. X‐ray diffraction and transmission electron microscopy experiments revealed that intercalation of polymer chains into silicate layers was achieved, and the addition of nanoclay led to an increase in the size of the rubber domain in the composites. In comparison with neat HIPS, the HIPS/organoclay nanocomposites exhibited improved thermal stability as well as an increase in both the complex viscosity and storage modulus. The presence of intercalated organoclay drastically enhanced the gas‐barrier properties because of the increase in the tortuosity of the diffusive path for a penetrating gas molecule. Some mechanical properties, including the tensile modulus, were superior to those of conventional HIPS. Finally, the preparation of the nanocomposites with a minimal loss of impact properties was proposed through changes in the synthetic procedure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of a three‐dimensional ordered macroporous titanium dioxide material with polystyrene colloid crystal as a template

Polystyrene (PS) photonic colloid crystals were assembled from PS spheres prepared by emulsion‐free polymerization through an improved vertical deposition method that could shorten the assembly time efficiently. The monodispersity of the spheres was appraised according to the standard deviation. The results showed that the PS spheres had a high monodispersity with a standard deviation of 3.7% and a dispersion coefficient of 0.02. The morphology and bandgap structure were observed with scanning electron microscopy images and transmission spectra, respectively. The mechanism of vertical deposition was analyzed simply. As an application of PS colloid crystals, ordered macroporous TiO₂ photonic crystals were prepared, and the structure and properties of macroporous TiO₂ were also studied with various analytical methods, which provided some values for the fabrication of photonic crystals with a complete bandgap. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008