Preparation and characterization of polystyrene‐grafted attapulgite via surface‐initiated redox polymerization

Polystyrene‐grafted attapulgite (ATP‐g‐PS) was prepared using surface‐initiated redox initiation via graft from approach. ATP was modified with (3‐ aminopropyl) triethoxysilane (APTES) to anchor amine on the surface (ATP‐NH₂), and then ATP‐NH₂ was further treated with 4‐(diethylamino) salicylaldehyde (DEAS) to give aromatic tertiary amine groups functional ATP (ATP‐ATA). Subsequently, the surface‐initiated redox polymerization of styrene in the presence of ATP‐ATA and benzoyl peroxide (BPO) was performed to afford ATP‐g‐PS . The chemical grafting of PS on the surface of ATP was confirmed by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and thermogravimetric analysis . The crystal structure of PS‐grafted ATP was characterized by X‐ray diffraction (XRD) analysis. The morphology of ATP‐g‐PS was observed by scanning electron microscopy (SEM) . POLYM. ENG. SCI., 55:889–895, 2015. © 2014 Society of Plastics Engineers     

Shape control synthesis of polymeric hybrid nanoparticles via surface‐initiated atom‐transfer radical polymerization

Polymeric hybrid nanoparticles were synthesized via surface‐initiated atom‐transfer radical polymerization (SI‐ATRP) method on the surface of gold nanoparticles in cyclohexanone. Tetraoctyl ammonium bromide (TOAB) as a phase transfer agent was used to transfer the gold nanoparticles into cyclohexanone, which will be replaced by disulfide initiator on the surface of gold nanoparticles. Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and UV–vis spectroscopy were utilized to characterize the product to make sure the experiment had been conducted. The results showed that the polymeric gold hybrid nanoparticles with different structures could be controlled by adjusting the ratio of initiator and gold nanoparticles in ATRP. If the ratio is very little, asymmetric polystyrene–gold hybrid nanoparticles were synthesized, and a single gold nanoparticle was attached with a polystyrene sphere. If the ratio becomes larger, core–shell polystyrene–gold nanocomposite particles were obtained resulting in gold nanoparticle encapsulated by a uniform polymer shell. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43584.     

Synthesis of polymer–inorganic hybrid nanoparticles via radical polymerization initiated by surface‐immobilized photoiniferter

Polymer–inorganic hybrid nanoparticles were prepared through radical photo‐polymerization of methyl methacrylate initiated by N,N‐diethyldithiocarbamyl surface functionalized silica nanoparticles under UV irradiation at ambient temperature. IR analysis and UV spectroscopy confirmed the occurrence of Et₂NCS₂—end groups on the resulting poly(methyl methacrylate), and the morphology of these hybrid nanoparticles was observed directly by means of tapping mode atomic force microscopy (AFM). Copyright © 2003 Society of Chemical Industry     

Preparation and characterization of polyhydroxyurethane/silica nanocomposites via in situ surface‐initiated polymerization

The polyhydroxyurethane/silica nanocomposite (PHU/SN) was prepared by the in situ surface‐initiated polymerization of a five‐membered cyclic carbonate, 2,2‐bis[p‐(1,3‐dioxolan‐2‐one‐4‐yl‐methoxy)phenyl]propane (B5CC) and hexamethylene diamine, from the surfaces of the aminopropyl silica nanoparticles (APSN) for the first time. The percentage of grafting (PG%) and the grafting efficiency (GE%) of 27% and 19% were calculated from the results of thermogravimetric analysis (TGA), respectively, after the free polyhydroxyurethane was washed off. The chemical grafting of the polymer was also confirmed using Fourier transform infrared (FTIR) and the morphology of the silica nanoparticles in the nanocomposite was characterized by transmission electron microscope (TEM). POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Grafting of water‐soluble sulfonated monomers onto functionalized fumed silica nanoparticles via surface‐initiated redox polymerization in aqueous medium

Sulfonated polymer/fumed silica hybrid nanoparticles were prepared via surface‐initiated free radical polymerization of 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (PAMPS‐g‐FSN), styrene sulfonic acid sodium salt (PSSA‐g‐FSN) and vinyl sulfonic acid sodium salt (PVSA‐g‐FSN) from the surface of aminopropyl‐functionalized fumed silica nanoparticles (AFSNs) dispersed in aqueous medium. Cerium(IV) ammonium nitrate/nitric acid and sodium dodecyl sulfate were used as redox initiator and stabilizer respectively. AFSNs were prepared by covalently attaching 3‐aminopropyltriethoxysilane onto the surface of fumed silica nanoparticles. Sulfonated monomers (AMPS, SSA or VSA) were then grafted onto the AFSNs ultrasonically dispersed in water via redox initiation at 40 °C. Structure, thermal properties, particle size and morphology of the AFSNs and PAMPS‐g‐FSN, PSSA‐g‐FSN and PVSA‐g‐FSN hybrid nanoparticles were characterized by Fourier transform infrared spectroscopy, TGA, SEM, transmission electron microscopy (TEM) and dynamic light scattering (DLS). The results indicated that the sulfonated monomers were successfully grafted onto the fumed silica nanoparticles. Grafting amounts of the sulfonated polymers onto the fumed silica nanoparticle surface were estimated from TGA thermograms to be 59%, 13% and 29% for the PAMPS, PSSA and PVSA, respectively. From SEM, TEM and DLS analysis, polymer‐grafted fumed silica nanoparticles with an average diameter smaller than 70 nm and a (semi‐) spherical shape were observed. A significant bimodal particle size distribution was observed only for the PAMPS‐g‐FSN with average diameters of 39.6 nm (84.1% per number) and 106 nm (15.9% per number). The hydrophilic sulfonated polymer/grafted fumed silica obtained from the redox graft polymerization gave a stable colloidal dispersion in acidic aqueous medium. Copyright © 2012 Society of Chemical Industry     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

Efficiencies of various metallocene/reducing agent catalyst systems in the hydrogenation of polystyrene‐b‐polybutadiene‐b‐polystyrene block copolymers

Various metallocenes, including bis(η⁵‐cyclopentadienyl)cobalt, bis(η⁵‐cyclopentadienyl)nickel, and bis(η⁵‐cyclopentadienyl)titanium dichloride, combined with various reducing agents, including n‐butyllithium, phenyllithium, and triethylaluminum, have been evaluated for their catalytic efficiencies in the hydrogenation of polystyrene‐b‐polybutadiene‐b‐polystyrene (SBS) block copolymer. The efficiencies were determined by monitoring the extent of saturation of double bonds on the polybutadiene segment of the copolymer using FTIR and ¹H‐NMR spectroscopy. The cobaltocene/n‐butyllithium catalyst system was found the most active. The effects of H₂ pressure and the ratio of n‐butyllithium to cobaltocene ratio on the hydrogenation efficiency were also investigated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1807–1815, 1999     

Preparation of monodispersed and lipophilic attapulgite and polystyrene nanorods via surface‐initiated atom transfer radical polymerization

A new kind of initiator, 3‐(2‐bromo‐2‐methylacryloxy)propyltriethysiliane (MPTS‐Br), was prepared with a simply hydrobrominated commercial silane coupling agent (3‐methacryloxy‐proplytriethysilane, MPTS). It has been one‐step self‐assemble onto the surface of attapulgite (ATP) nanorods in the dispersion system, and by using this initiator‐modified nanorod (MPTS‐Br‐modified ATP nanoparticles, ATP‐MPTS‐Br) as macroinitiator for atom transfer radical polymerization (ATRP). Structurally well‐defined homopolymer polystyrene (PS) and block polymer poly(styrene‐b‐methyl methacrylate) (PS‐b‐PMMA) chains were then grown from the needle‐shaped nanorods surface to yield monodispersed nanorods composed of ATP core and thick‐coated polymer shell (ATP and PS). The graft polymerization parameters exhibited the characteristics of a controlled/”living” polymerization. The PS‐grafted ATP nanorods could be dispersed well in organic solvent with nanoscale. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of copolymer grafted magnetic nanoparticles via surface‐initiated nitroxide‐mediated radical polymerization

“Grafting from” surface‐initiated nitroxide‐mediated radical polymerization (SI‐NMRP) techniques were used to synthesize poly[styrene‐co‐(maleic anhydride)] copolymer brushes from the Fe₃O₄ surfaces. Well‐defined polymer chains were grown from the Fe₃O₄ surfaces to yield particles with a Fe₃O₄ core and a polymer outer layer. The observed narrow molecular weight distributions (M_w/M_n), linear kinetic plots and linear plots of molecular weight (M_n) versus conversion for the free polymer indicated that the chain growth from the Fe₃O₄ surface was a controlled process by adding an excess of 2,2,6,6‐tetramethylpiperidinyloxy (TEMPO). The modified nanoparticles were subjected to detailed characterization using XRD, TEM, FT‐IR, and TGA. The analyses of vibration sample magnetometer (VSM) verified that the nanoparticles owned good magnetic property. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Study and comparison of interaction parameters and phase behavior of epoxy/polystyrene and epoxies copolymer polystyrene‐b‐poly(methyl methacrylate) blends

Thermodynamic studies in terms of phase separation behavior and interaction parameters, in mixtures of epoxy resins (thermoset materials) with thermoplastic additives, consisting of polystyrene (PS) or polystyrene‐b‐poly(methyl methacrylate) P(S‐MMA) (with small proportion of MMA), have been carried out. It can be confirmed that the solubility of P(S‐MMA) is an improvement on that of PS, with the prepolymer epoxy resins. Moreover, the interaction parameters are positive at temperatures in which phase separation is observed, but negative at temperatures in which the phase separation window disappears, in the corresponding phase diagram. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Grafting polymer from poly(ethylene terephthalate) films by surface‐initiated ATRP

Surface‐initiated atom transfer radical polymerization (ATRP) from poly(ethylene terephthalate) (PET) film was studied. Poly(methyl methacrylate) (PMMA), poly (acrylamide) (PAAM), and their diblock copolymer (PMMA/PAAM) on the surface of PET film were successfully prepared by surface‐initiated ATRP. The structures and properties of the modified PET film were characterized by FT‐IR/ATR, X‐ray photoelectron spectroscopy (XPS), measurements of contact angles, and scanning electronic microscopy (SEM). The results indicate that the surface properties of PET film were greatly improved by grafted polymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Comb‐like polymer‐graphene nanocomposites with improved adhesion properties via surface‐initiated atom transfer radical polymerization (SI‐ATRP)

The synthesis and properties of comb‐like polymer‐graphene nanocomposites via surface initiated atom transfer radical polymerization is reported. The crystallization temperature (T_c) and melt temperature (T_m) of the comb‐like homopolymer increases from −18 to −8 °C and 1 to 11 °C, respectively, in the nanocomposite synthesized with 0.6 wt % graphene initiator. The rheological properties like modulus and complex viscosity of the nanocomposite show a twofold increase. Transmission electron microscopy results of the nanocomposite show a well‐intercalated structure with nanoscale distribution of graphene domains and in scanning electron microscopy a sheet‐like structure with corrugations, and crumples are seen. The hydrophobicity, as measured by water contact angle, increases from 101° in the homopolymer to 118° in the nanocomposite. The nanocomposites exhibit substantial increase in adhesive strength on different substrates, with peel strength increasing by more than 1000 times, as compared to the homopolymer. The improved tack and adhesion properties of the nanocomposites suggest them as novel materials for adhesive applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45885.     

Instability of styrene/polystyrene/polybutadiene/polystyrene‐b‐polybutadiene emulsions that emulate styrene polymerization in the presence of polybutadiene

This article investigates the room temperature demixing of oil‐in‐oil emulsions containing styrene (St), polybutadiene (PB), a St‐butadiene star block copolymer (BC), and two polystyrene (PS) samples of different molecular weights and is a contribution toward a better understanding of the stability/instability of the reaction mixture in a bulk high‐impact polystyrene (HIPS) process close to the phase inversion. Twelve bulk prepolymerizations of St in the presence of PB were emulated, at 10%, 15%, and 20% conversion; and with constant grafting efficiencies. All the blends contained 6% in weight of butadiene units. After stirring the blends for 24 h, the decantation demixing process was monitored along 30 days, with daily measurement of the interface levels after appearance of a clear interface. For some of the isolated phases, their unswollen morphologies were observed by transmission electron microscopy. All the isolated phases exhibited macrophase separation into homopolymer‐ and copolymer‐rich macrodomains with lamellar microdomains. The BC showed a greater affinity toward the PS‐rich phase. The separation of an independent BC‐rich phase in the blends containing the high molar mass PS and at high grafting efficiencies, modifies the idea of the graft‐ or BC molecules located at the interface of large PS‐rich and PB‐rich phases. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Synthesis and characterization of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers by atom‐transfer radical polymerization

Well‐defined polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐PS triblock copolymers were synthesized by atom‐transfer radical polymerization (ATRP), using C—X‐end‐group PEO as macroinitiators. The triblock copolymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The experimental results showed that the polymerization was controlled/living. It was found that when the number‐average molecular weight of the macroinititors increased from 2000 to 10,000, the molecular weight distribution of the triblock copolymers decreased roughly from 1.49 to 1.07 and the rate of polymerization became much slower. The possible polymerization mechanism is discussed. According to the Cu content measured with atomic absorption spectrometry, the removal of catalysts, with CHCl₃ as the solvent and kaolin as the in situ absorption agent, was effective. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2882–2888, 2000     

Syndiotactic polystyrene‐b‐atactic polypropylene block copolymer alloy as a compatibilizer for syndiotactic polystyrene/isotactic polypropylene blends

A polymeric alloy (SP–A) containing syndiotactic polystyrene (sPS), atactic polypropylene (aPP), and about 66 wt % sPS‐b‐aPP diblock copolymer, was prepared by the sequential feed of monomers in the presence of the half‐titanocene Cp*Ti(OBz)₃ (where Cp* is C₅Me₅ and Bz is PhCH₂), modified methylaluminoxane, and external triisobutylaluminum. The effects of the SP–A alloy as a compatibilizer for sPS and isotactic polypropylene (iPP) blends were evaluated. The blending of sPS and iPP, with and without SP–A, was performed in a single‐screw miniextruder with a side channel that allowed the continuous recycling of materials. The influence of SP–A on the mechanical and thermal properties of the immiscible sPS/iPP blends was investigated over a range of composition. The presence of the SP–A alloy resulted in a significant improvement of the impact strength of the blends compared with that of pure sPS and their pure blends. This improvement was particularly obvious in the sPS/iPP (90/10 wt %) blend containing 5 wt % SP–A. Morphological analysis of the impact‐fractured surface of the ternary blends indicated that the sPS‐b‐aPP diblock copolymer contained in the SP–A alloy acted as an efficient compatibilizer by decreasing the dispersed‐phase iPP particle size, improving the interfacial adhesion, and generating a stable microphase‐separated state. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1596–1605, 2003     

Surface‐initiated atom transfer radical polymerization (ATRP) of styrene from silica nanoparticles under UV irradiation

Diethyldithiocarbamyl‐modified silica nanoparticles were prepared and used as macroinitiator for the surface‐initiated atom transfer radical polymerization (SI‐ATRP) of styrene under UV irradiation. Well‐defined polymer chains were grown from the nanoparticle surfaces to yield particles composed of a silica core and a well‐defined, densely grafted outer PS layer with a mass ratio of styrene to silica, or percentage grafting, of 276.3% after an UV irradiation time of 5 h. Copyright © 2004 Society of Chemical Industry     

Modification of polysulfone membranes via surface‐initiated atom transfer radical polymerization and their antifouling properties

Surface‐initiated atom transfer radical polymerization (ATRP) was used to tailor the functionality of polysulfone (PSF) membranes. A simple one‐step method for the chloromethylation of PSF under mild conditions was used to introduce surface benzyl chloride groups as active ATRP initiators. Covalently tethered hydrophilic polymer brushes of poly(ethylene glycol)monomethacrylate and 2‐hydroxyethyl methacrylate and their block copolymer brushes were prepared via surface‐initiated ATRP from the chloromethylated PSF surfaces. A kinetic study revealed that the chain growth from the membranes was consistent with a controlled process. X‐ray photoelectron spectroscopy was used to characterize the surface‐modified membrane after each modification stage. Protein adsorption experiments revealed substantial antifouling properties of the grafted PSF membranes in comparison with the those of the pristine PSF surface. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation magnetite core/coated with polystyrene shell hybrid materials via redox interfacial‐initiated emulsion polymerization

In this article, we describe a novel redox interfacial‐initiated micro‐emulsion polymerization (RIEP) to prepare hollow polystyrene microspheres with magnetite nanoparticles (MPs) core and polystyrene (PS) shell (MPs‐PS) under ambient pressure. The emulsion was constituted water‐based magnetic ferro‐fluid as dispersing phase and organic solvent and styrene (St) as continuous phase. Cumene hydroperoxide (CHPO)/iron (II) sulfates (FS) as the redox initiation system, the water‐soluble FS acted as the reducing component and the oil‐soluble CHPO as the oxidant component of the redox initiation system. Therefore, the primary radicals are produced mainly at the oil/water interface to initiate the polymerization of styrene to form polymer shell. The final products thoroughly characterized by X‐ray powder diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, field‐emission scanning electron microscopy, thermogravimetric analysis, dynamic light scattering, and X‐ray photoelectron spectroscopy, which showed the formation of hollow magnetite/polystyrene nanocomposite microspheres. Magnetic measurements were carried out at room temperature using a vibrating sample magnetometer. The saturation magnetization (M_s), remanent magnetization (M_r) and coercivity (H_c) is 30 emu/g, 15 emu/g and 370 Oe, respectively. The results revealed that the hybrid materials microspheres were super‐paramagnetic. POLYM. COMPOS., 31:1846–1852, 2010. © 2010 Society of Plastics Engineers     

Synthesis and characterization of poly(γ‐methacryloxypropyltrimethoxysilane)‐grafted silica hybrid nanoparticles prepared by surface‐initiated atom transfer radical polymerization

Poly(γ‐methacryloxypropyltrimethoxysilane) (PMPTS)‐grafted silica hybrid nanoparticles were prepared by surface‐initiated atom transfer radical polymerization (SI‐ATRP). The resulting PMPTS‐grafted silica hybrid nanoparticles were characterized using Fourier transform infrared spectroscopy (FTIRS), nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), X‐ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM), static water contact angle (WCA) measurement, and thermogravimetric analysis (TGA). Combined FTIRS, NMR, XPS, SEM, and TGA studies confirmed that these hybrid nanoparticles were successfully prepared by surface‐initiated ATRP. SEM and AFM studies revealed that the surfaces of the nanoparticles were rough at the nanoscale. In addition, the results of the static WCA measurements showed that the nanoparticles are of low surface energy and their surface energy reaches as low as 6.10 mN m^?1. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Poly(N‐hydroxyethyl acrylamide)‐b‐polystyrene by combination of ATRP and aminolysis processes

Block copolymers of very hydrophilic poly(N‐hydroxyethyl acrylamide) (PHEAA) with polystyrene (PS) were successfully synthesized by sequential atom transfer radical polymerization of ethyl acrylate (EA) and styrene monomers and subsequent aminolysis of the acrylic block with ethanolamine. Quantitative aminolysis of poly(ethyl acrylate) (PEA) block yielded poly(N‐hydroxyethyl acrylamide)‐b‐polystyrene in well‐defined structures, as evidenced by Fourier transform infrared spectroscopy (FTIR) and ¹H‐NMR spectroscopy techniques. Three copolymers with constant chain length of PHEAA (degree of polymerization: 80) and PS blocks with 21, 74, and 121 repeating units were prepared by this method. Among those, the block copolymer with 21 styrene repeating units showed excellent micellation behavior in water without phase inversion below 100°C, as inferred from dynamical light scattering, environmental scanning electron microscopy, and fluorescence measurements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013