Synthesis of new free‐radical initiators for polymerization

Synthesis and properties of new initiating systems formed from commercially available ketones, glycols, and hydrogen peroxide (60%) are presented. In preparation of free radical initiators methyl ethyl ketone, which was oxidized by hydrogen peroxide, was used. Reaction was carried out in etanodiol or 1,4‐butanodiol as diluent. The obtained initiators with cobalt octoate as a promotor were applied for crosslinking of the commercially available unsaturated polyester resin. Properties of the resin were compared with those obtained while it was hardened by the typical curing system containing methyl ethyl ketone hydroperoxide and cobalt octoate. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2238–2243, 2003     

Preparation of micrometer‐sized,multifunctional capsule particles for cosmetic by microsuspension polymerization utilizing the self‐assembling of phase separated polymer method

Micrometer‐sized polymer particles with encapsulated ultraviolet (UV) absorbent, fluorescent agent, and blue pigment were successfully prepared by microsuspension polymerization utilizing the Self‐assembling of Phase Separated Polymer method. The particles were characterized by optical microscope and particle size distribution analysis, and they were evaluated on their usefulness for cosmetic using UV spectrometry, colorimetry, VISIA? Evolution, and bioassay. The capsule particles had multifunctional properties, which are very attractive in the cosmetic field, especially in whitening, brightening, the improvement of face‐texture, and less noticeable pores in face, as well as the protection from UV. Moreover, bioactivities of the particles under the UV irradiation, which were examined with the films prepared from capsule components, revealed not only makeup effect but also the activation of human epidermal keratinocytes. The results suggest the importance of blue light in the field of cosmetics. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Temperature distribution effects during polymerization of methacrylate‐based monoliths

Monolithic stationary phases are becoming increasingly important in the field of liquid chromatography. Methacrylate‐based monoliths are produced via free‐radical bulk polymerization. The preparation of large‐volume monoliths is a major problem because the intensive heat released during polymerization causes distortion of the porous monolithic structure. This work presents experimental measurements of temperature distributions during polymerization in moulds of different sizes and at various experimental conditions. A mathematical model for the prediction of temporal and spatial temperature distribution during the polymerization of methacrylate‐based monolithic columns is introduced. The polymerization is described by an unsteady‐state heat conduction equation with the generation of heat related to the general kinetics of polymerization. Predictions from the mathematical model are in good agreement with the experimental measurements at different experimental conditions. A method for construction of large‐volume monolithic columns is presented and an attempt is made to adopt the developed mathematical model in annular geometry. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2326–2334, 2003     

Synthesis of ω‐functionalized poly(1,3‐cyclohexadiene): addition of fluorescent functional group to the polymer chain end

BACKGROUND: Poly(1,3‐cyclohexadiene) (PCHD) is of interest as a precursor for the synthesis of a new class of high‐performance hydrocarbon polymers. ω‐Functionalization of PCHD offers a new opportunity for the preparation of a variety of multifunctional PCHD derivatives. RESULTS: ω‐Functionalized PCHD containing a fluorenyl (or anthracenyl) group at the polymer chain end was successfully synthesized by post‐polymerization reaction of poly(1,3‐cyclohexadienyl)lithium (PCHDLi) with alkyl halides containing a fluorescent functional group. The degree of nucleophilicity of PCHDLi and the control of side reactions were very important factors to achieve a high conversion for the post‐polymerization reactions of PCHDLi. The ω‐functionalized PCHDs obtained exhibited strong photoluminescence and the wavelength of the fluorescence was adjustable by changing the structure of the ω‐functional group. CONCLUSION: ω‐Functionalized PCHD is a preferable precursor that can be utilized to obtain a new class of multifunctional hydrocarbon polymers containing six‐membered rings in the main chain. Copyright © 2007 Society of Chemical Industry     

Inhibition of radical polymerization in solvent‐based systems (security of solvent‐based radical polymerization of PSA‐acrylic in a plant reactor)

This article shows the influence of some chain‐transfer agents as inhibitors for acrylic solvent‐based polymerization. These chain‐transfer agents can offer significant advantages, as outlined below. The following chain‐transfer agents were studied to stop or slow down the polymerization process in the case of a runaway: n‐dodecyl mercaptan, trimethylolpropane‐trimercaptoacetate, phenothiazine, diphenylphenylen diamine, cuprum oxide, isopropanol, toluene, and carbon tetrachloride. Synthesized pressure‐sensitive adhesive based on acrylic polymers and containing 2‐ethylhexyl acrylate, methyl acrylate, and acrylic acid were used for the production of self‐adhesives with high cohesion. The polymerization was accomplished in ethyl acetate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1354–1357, 2003     

Nano‐SiO2/PMMA‐PU composite particles with core‐shell structure via emulsion polymerization and their application in epoxy resin

A novel method of nano‐SiO₂/poly(methyl methacrylate)(PMMA)‐polyurethane(PU) composite particles modifying epoxy resin is reported. The composite particles with the obvious core‐shell structure were prepared by emulsion polymerization of PMMA and PU prepolymer on the surface of nano‐SiO₂. The diameter of the composite particles was 50–100 nm with dark core SiO₂ (30–60 nm) and light shell polymer of PMMA and PU (20–30 nm); moreover, PU was well distributed in PMMA with about 10 nm diameter. After nano‐SiO₂ was encapsulated by PMMA and PU, the Si content on the surface decreased rapidly to 2.08% and the N content introduced by PU was about 1.27%. The ratio of polymer to original nano‐SiO₂ (f_p), the grafting ratio of polymer to original nano‐SiO₂ (f_r) and the efficiency grafting ratio of polymer (f_e) were, respectively, about 116.7%, 104.4%, and 89.5%. The as‐prepared composite particles were an effective toughness agent to modify epoxy resin, and the impact strength of the modified epoxy resin increased to 46.64 kJ m^?2 from 19.12 kJ m^?2 of the neat epoxy resin. This research may enrich the field of inorganic nanoparticles with important advances toward the modification for polymer composite materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41919.     

Synthesis of fluorescent methoxy poly(ethylene glycol)‐b‐Poly(ethyl cyanoacrylate)–2‐(N‐carbazolyl) ethyl methacrylate copolymer via living oxyanion‐initiated polymerization

The fluorescent amphiphilic block copolymer methoxy poly(ethylene glycol) (mPEG)‐b‐poly(ethyl cyanoacrylate) (PECA)–2‐(N‐carbazolyl) ethyl methacrylate (CzEMA) was synthesized via living oxyanion‐initiated polymerization. mPEG‐b‐PECA–CzEMA was characterized by gel permeation chromatography, ¹H‐NMR, and Fourier transform infrared spectroscopy. The results indicate that the polymerization was well controlled with a narrow molecular weight distribution. The mPEG‐b‐PECA–CzEMA nanoparticles prepared by nanoprecipitation techniques showed a narrow size distribution with an average diameter of less than 100 nm. The mPEG‐b‐PECA–CzEMA exhibited a strong carbazole fluorescence. Furthermore, it was found that the fluorescence intensity of mPEG‐b‐PECA–CzEMA was sensitive to a change in solvent. The results indicate that a subtle change in the state of the polymer micellar association may have altered the state of carbazole groups, which was responsible for the fluorescence emission. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel comb‐structured‐polymer‐grafted carbon black by surface‐initiated atom transfer radical polymerization and ring‐opening polymerization

Novel comb‐structured‐polymer‐grafted carbon black (CB) was synthesized with a combination of surface‐initiated atom transfer radical polymerization and ring‐opening polymerization. First, poly(2‐hydroxyethyl methacrylate) (PHEMA) was grafted onto the CB surface by surface‐initiated atom transfer radical polymerization. The prepared CB‐g‐PHEMA contained 35.6–71.8% PHEMA, with the percentage depending on the molar ratio of the reagents and the reaction temperature. Then, with PHEMA in CB‐g‐PHEMA as the macroinitiator, poly(?‐caprolactone) (PCL) was grown from the CB‐g‐PHEMA surface by ring‐opening polymerization in the presence of stannous octoate. CB‐g‐PHEMA and CB‐g‐(PHEMA‐g‐PCL) were characterized with Fourier transform infrared, ¹H‐NMR, thermogravimetric analysis, dynamic light scattering, and transmission electron microscopy. The resultant grafted CB had a shell of PHEMA‐g‐PCL. On the whole, the CB nanoparticles were oriented in dendritic lamellae formed by these shells. This hopefully will result in applications in gas sensor materials and nanoparticle patterns. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel fluorescence method for cure monitoring of hydrosilation‐curable silicones

This study aimed to evaluate a reactive fluorescent probe, 9,10‐bis‐(phenylethynyl) anthracene (BPEA), for cure monitoring of hydrosilation‐curable silicones. The hydrosilation‐curable silicones consisted of a vinyl‐terminated polydimethylsiloxane prepolymer, a methylhydrosiloxane‐dimethylsiloxane copolymer, and an inhibitor, 1,3‐divinyltetramethyldisiloxane. The hydrosilation reaction was catalyzed with the solution of a platinum catalyst in the prepolymer. The catalyst solution also contained a trace amount of the reactive fluorescent probe. Three hydrosilation‐curable silicones, with the prepolymer of varying molar mass, were investigated. Each of the hydrosilation‐curable silicones was mixed with the catalyst solution at the mass ratio of 1 : 1 to initiate the cure. During the cure of each mixture at 22°C, the elastic modulus of the mixture and the fluorescence spectrum of the probe at the excitation wavelength of 360 nm were measured. Initially, the elastic modulus changed slowly, but then increased rapidly as a result of the increase in molar mass. The elastic modulus leveled off and reached a plateau value at the setting time. The ratio of the fluorescence intensities at 422 and 466 nm increased steadily, and then leveled off and reached a plateau value at the setting time, in agreement with the setting time determined from the change in elastic modulus. The reactive fluorescent probe, BPEA, can therefore be used for nondestructive fluorescence monitoring of hydrosilation‐curable silicones. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electrochemical polymerization of β‐naphthalene sulfonic acid

β‐Naphthalene sulfonic acid (β‐NSA) has been electrochemically polymerized in a mixed electrolyte of boron trifluoride diethyl etherate (BFEE) solution mixed with a certain amount of trifluoroacetic acid (TFA) or concentrated sulfuric acid (SA). The poly(β‐naphthalene sulfonic acid) (PNSA) film prepared from the medium of BFEE+TFA was partly soluble in methanol. On the other hand, the polymer obtained from the system of BFEE+SA was soluble in water and general polar organic solvents such as methanol, alcohol, and acetone. The structure of PNSA was examined by infrared and UV spectra. Fluorescent spectral studies indicate that the polymer is a blue light emitter with fluorescence quantum efficiency of ～ 4%. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1939–1944, 2004     

Properties of amine‐containing coatings prepared by plasma polymerization

Two monomers, ethylenediamine (EDA) and diaminocyclohexane (DACH), were plasma‐polymerized in continuous‐wave (CW) and pulse modes. The influence of different plasma parameters on the deposition rate and film composition were investigated in detail and the changes in aminofunctionalization with varying pulse parameters were examined by FTIR, ESCA, and chemical‐derivatization techniques. It was shown that a varying duty cycle does not produce a considerable effect on the retention of amine groups into the film, while power and t_on play a significant role in the polymerization process. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 979–990, 2004     

Two‐stage grafting onto polyethylene fiber by radiation‐induced graft polymerization and atom transfer radical polymerization

Two‐stage graft polymerization onto polyethylene (PE) fiber was demonstrated. The graft side chain was formed by radiation‐induced graft polymerization. A PE fiber was irradiated with an electron beam and immersed in a vinyl monomer solution. The terminal of the formed graft chain was halogenated using N‐bromosuccinimide. The halogenated graft chain was then extended by atom transfer radical polymerization to obtain block‐copolymer grafted PE fibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

反相微乳液聚合荧光高分子F-PAM

通过Span80-Tween80/异辛烷/FM(4-甲氧基-N-（2-N′,N′-二甲基氨基乙基）萘二甲酰亚胺烯丙基氯化铵）-AM（丙烯酰胺）-H₂O反相微乳液聚合,制备了AM和FM的荧光高分子聚合物（F-PAM）.采用透射电镜（TEM）、原子力显微镜（AFM）、激光纳米粒度仪、荧光分光光度计等测试手段,测定了荧光高分子聚合物（F-PAM）的粒子形态、粒径和粒径分布等微观结构及其荧光性能.试验结果表明：所制备的F-PAM为单分散、球形的纳米材料,平均粒径（D）在60～145 nm之间;F-PAM的激发波长和发射波长分别为381 nm和462 nm.F-PAM激发光谱与发射光谱呈较好的镜像对称关系;F-PAM的相对荧光强度随着其质量浓度的增加而增加,且F-PAM的浓度与其荧光强度呈很好的线性关系,其线性相关系数（R）为0.9953,F-PAM的检测下限为1.83 mg·L^-1.     

Uniform star‐polystyrene nanoparticles prepared by emulsion atom transfer radical polymerization

Pentaerythritol (PT) was converted into four‐arm initiator pentaerythritol tetrakis(2‐chloropropionyl) (PT‐Cl) via reaction with 2‐chloropropionyl chloride. Uniform (monodisperse) star‐polystyrene nanoparticles were prepared by emulsion atom transfer radical polymerization of styrene, using PT‐Cl/CuCl/bpy (bpy is 2,2′‐dipyridyl) as the initiating system. The structures of PT‐Cl and polymer were characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance. The morphology, size and size distribution of the star‐polystyrene nanoparticles were characterized by transmission electron microscopy, atomic force microscopy and photon correlation spectroscopy. It was found that the average diameters of star‐polystyrene nanoparticles were smaller than 100 nm (30–90 nm) and monodisperse; moreover, the particle size could be controlled by the monomer/initiator ratio and the surfactant concentration. The average hydrodynamic diameter (D_h) of the nanoparticles increased gradually on increasing the ratio of styrene to PT‐Cl and decreased on enhancing the surfactant concentration or increasing the catalyst concentration. Copyright © 2011 Society of Chemical Industry     

Facile preparation and potential application of water‐soluble polymeric temperature/pH probes bearing fluorescein

An unsaturated monomer bearing xanthene groups and allyloxyfluorescein (Al‐Flu), was synthesized from fluorescein and allyl bromide by etherification. The structure of the monomer was confirmed by IR and mass spectroscopy and ¹H‐NMR, and ¹³C‐NMR spectroscopy. With azobisisobutyronitrile as a thermal initiator in tetrahydrofuran under 65–70°C, a copolymer of allyloxyfluorescein and acrylamide [poly(Al‐Flu‐co‐AM)] was obtained and was characterized by the methods of IR spectroscopy, ultraviolet–visible spectroscopy, and differential scanning calorimetry. The experimental results show that the fluorescence spectra of water‐soluble poly(Al‐Flu‐co‐AM) was dependent on the pH and temperature in the solution. Moreover, poly(Al‐Flu‐co‐AM) had an excellent linear response between the relative fluorescence intensity and temperature in the range 0–60°C and had a nonlinear response from pH 0.00 to 12.85 between the relative fluorescence intensity and pH. The pH and temperature sensitivities of the fluorescence could be advantageous for it as a multifunctional material to probe pH and temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Multi‐responsive microgel of a water‐soluble monomer via emulsion polymerization

Microgel of a water‐soluble monomer [2‐(N‐morpholino)ethyl methacrylate (MEMA)] was successfully prepared in aqueous media via emulsion polymerization by using a novel water‐soluble block copolymer as stabilizer. Characterization studies confirmed monodisperse spherical morphologies of microgels with a diameter of 280 nm at neutral pH. These microgels exhibited multi‐responsive behavior by responding solution pH, temperature, ionic strength, type of dispersing media, and magnetic particles. It swells well at low pH (<6.0) and at low temperature, but shrinks above pH 6.0, or even more shrinks with salt addition at neutral and basic conditions. In addition, the hydrodynamic diameter of PMEMA microgel was decreased gradually at basic and neutral pH when solution temperature was increased up to the lower critical solution temperature of PMEMA (LCST, 35°C), but microgel diameter did not change much above LCST. Multi‐responsive behavior of PMEMA microgel was investigated by using dynamic light scattering, UV‐Vis spectrophotometer and zeta potentiometer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42072.     

Environmentally responsive amphiphilic cationic block copolymers synthesized by 2,2,6,6‐Tetramethylpiperidinyloxy mediated living free‐radical polymerization

Polychloromethylstyrene (PCMS)‐block‐polystyrene (PS) copolymers were prepared by controlled free‐radical polymerization in the presence of 2,2,6,6‐tetramethylpiperidinooxy and 2,2′‐azobisisobutyronitrile (AIBN) initiator. The PCMS‐b‐PS copolymers had narrow molecular weight distributions, and the block lengths were controlled by the reaction time and the molar ratios of chloromethylstyrene/AIBN and styrene/PCMS macroinitiator. The block copolymers were further quaternized with triethylamine. The amphiphilic cationic block copolymers formed colloidal particles; the effects of the pH value, salt concentration, and solvent polarity on the particle size were investigated with a dynamic light scattering analyzer. The average colloid size increased with increasing pH value and salt concentration. This implied that the colloid formed a protonated hydrophilic shell and hydrophobic styrene core in water. Furthermore, with the addition of tetrahydrofuran to the aqueous solution, the styrene segments in the core could be inverted to the outside of the colloid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and fluorescence of polymeric triphenylamine obtained by oxidative‐coupling polymerization

We prepared triphenylamine (TPA)‐containing polymers by a direct oxidative‐coupling method, which showed high thermostability, good solubility, high quantum efficiency, and blue light emission. The polymers are characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, ultraviolet–visible spectroscopy, thermogravimetric analysis, elemental analysis, and fluorescence spectra. The homopolymeric TPA (PTPA) was fairly soluble in CCl₄ and toluene, with a quantum yield of 0.38 relative to Rhodamine B in toluene solution, and showed blue light emission in solid‐state film. The TPA–stilbene copolymers were more soluble than the PTPA and showed violet to green light emission in solid‐state film, depending on the TPA moiety contents, from which a pure blue light emission could be obtained. The emitting quantum efficiency of the copolymers measured in toluene solution was from 0.57 to 0.78 relative to Rhodamine B. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2718–2724, 2002     

Inverted emulsion polymerization route to polyaniline‐3D nanofiber network using sulfonated‐p‐cresol as novel dopant

Sulfonated‐p‐cresol (SPC) was used as novel dopant for the first time in the synthesis of polyaniline in 3D nanofiber networks (PANI‐3D). Polyaniline in 3D nanofiber network was prepared using organic solvent soluble benzoyl peroxide as oxidizing agent in presence of SPC and sodium lauryl sulfate (SLS) surfactant via inverted emulsion polymerization pathway. The influence of synthesis conditions such as the concentration of the reactants, stirring/static condition, and temperature etc., on the properties and formation of polyaniline nanofiber network were investigated. Polyaniline in 3D nanofiber network with 40–160 nm (diameter), high yield (134 wt % with respect to aniline used), and reasonably good conductivity (0.1 S/cm) was obtained in 24 h time. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Different dispersion polymerization strategies influence the quality of fluorescent poly (St‐co‐GMA) microspheres

The polymerization strategy plays a vital role in the preparation of functional microspheres. In this work, fluorescent poly (styrene‐co‐glycidyl methacrylate) (PSt‐GMA) microspheres were synthesized via one‐stage and two‐stage dispersion polymerization with 4‐Bis(5‐phenyl‐1,3‐oxazol‐2‐yl)benzene (POPOP) as fluorescence agent. SEM and DLS were adopted to characterize the properties of prepared microspheres. The UV‐vis and fluorescence spectroscopy were used to analyze the mechanisms of two‐stage dispersion polymerization. The experimental results showed that the size distribution and fluorescence intensity of prepared microspheres could be improved by two‐stage dispersion polymerization compared to one‐stage dispersion polymerization. In addition, according to UV‐vis, the interactions between POPOP and Poly (N‐vinyl pyrrolidone) (PVP) as well as POPOP and Glycidyl methacrylate (GMA) could affect the particle size and its distribution. UV‐vis and fluorescence spectra implied that the POPOP existed outside of the particle's core via two‐stage strategy. The monomer conversion of styrene was similar at the beginning of reaction; however, the monomer conversion of styrene by two‐stage strategy was higher than that of by one‐stage strategy. In a word, two‐stage dispersion polymerization could prepare fluorescent microspheres with the monodispersion micrometer‐size and high quality. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41927.