Synthesis and property study of UV-curable hyperbranched polyurethane acrylate/ZnO hybrid coatings

In the present work, the third generation hyperbranched polyester (HBPE-3G) based polyurethane acrylate (HBPUA-32)/ZnO hybrid coatings are prepared, by modifying 16 hydroxyl groups of HBPE-3G with an acrylic adduct. The HBPE-32 is prepared from the di-trimethylol propane and 2,2-bis(hydroxymethyl) propionic acid, converted into hybrid coatings by incorporating 1%, 3% and 5% nano ZnO powder into the polymer matrix. The ¹H, ¹³C NMR and FT-IR spectroscopy methods are used for structural characterization, degree of branching calculation and structure to property correlation study and various hybrid film properties are analyzed by TGA, DMTA, XRD and SEM instruments.     

Preparation of a monolith functionalized with zinc oxide nanoparticles and its application in the enrichment of fluoroquinolone antibiotics

This study describes the enrichment ability of ZnO‐modified methacrylic acid‐co‐ethylene dimethacrylate polymer monoliths as stationary phases for the simultaneous determination of antibiotics (ofloxacin, ciprofloxacin, enoxacin, and pefloxacin) combined with high‐performance liquid chromatography. The prepared monolith was characterized by scanning electron microscopy, X‐ray photoelectron spectroscopy, Fourier‐transformed infrared spectroscopy, and thermogravimetric analysis. The polymer monolith microextraction method has been applied to the enrichment of fluoroquinolone antibiotics and satisfactory results were obtained in the analysis of water samples. Compared with the conventional methacrylic acid based monolith, the developed monolith exhibited a higher enrichment capacity because of the introduction of zinc oxide into the preparation process.     

Modification of porous silica particles with poly(acrylic acid)

The surface of porous silica particles was modified with poly(acrylic acid) by reacting the carboxyl groups on poly(acrylic acid) with the amino groups of pregrafted aminopropyltriethoxysilane (APS). The chemical modifications by APS and polymer were characterized by infrared spectroscopy and the amount of APS and poly(acrylic acid) grafted to the surface were determined by thermal gravimetric analyses. The wettability of the modified silica particles, based on the rate of water penetration, was pH‐dependent with PAA; at pH 1.5 the wettability increased but at pH 5.5 it decreased dramatically. The pore size and size distribution of the silica particles decreased with APS and polymer grafting. Copyright © 2000 John Wiley & Sons, Ltd.     

聚砜与丙烯酸的紫外光辐射接枝共聚及其表征

在均相溶液体系下,运用紫外光辐射引发合成了聚砜与丙烯酸的接枝共聚物。用化学滴定、漫反射傅立叶变换红外光谱和热分析等技术对接枝聚合物进行了表征。结果表明:丙烯酸被接枝在聚砜链上;光照时间、单体浓度和光引发剂浓度对接枝率均有较大影响。膜表面接触角的研究表明,接枝共聚物膜的亲水性比改性前有所提高。     

A facile “graft from” method to prepare molecular‐level dispersed graphene–polymer composites

Graphene–polymer composites of positive‐charged poly(dimethyl aminoethyl acrylate), negative‐charged poly(acrylic acid), and neutral polystyrene were prepared by “graft from” methodology using reversible addition fragmentation chain transfer (RAFT) polymerization via a pyrene functional RAFT agent (PFRA) modified graphene precursor. Fluorescence spectroscopy and attenuated total reflection infrared (ATR‐IR) evidenced that the PFRA was attached on the graphene basal planes by π–π stacking interactions, which is strong enough to anti‐dissociation in the polymerization mixture up to 80°C. Atomic force microscopy (AFM) revealed that the thickness of a graphene–polymer sheet was about 4.0 nm. Graphene composites of different polymers with the same polymerization degree exhibited similar conductivity; however, when the polymer chain was designed as random copolymer the conductivity was significantly decreased. It was also observed that the longer the grafted polymer chains the lower the conductivity. ATR‐IR spectroscopy and thermogravimetric analysis were also performed to characterize the as‐prepared composites. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of the raspberry‐like PS/PAN particles with anisotropic properties via seeded emulsion polymerization initiated by γ‐ray radiation

We herein report a facile method to prepare the submicron‐sized raspberry‐like polystyrene/polyacrylonitrile particles with anisotropic properties and controllable structure via γ‐radiation‐induced seeded emulsion polymerization under ambient pressure and at room temperature, in which the monodisperse crosslinked styrene‐divinylbenzene‐acrylic acid terpolymer (P(S‐DVB‐AA)) particles were used as seed particles and acrylonitrile (AN) as the second monomer. The influence of the weight ratio of polymer/monomer, the absorbed dose rate, the absorbed dose, and the dispersion medium on the morphology of the as‐prepared particles was investigated. The final products were thoroughly characterized by Fourier transform infrared spectroscopy (FTIR), field‐emission scanning electron microscopy, and transmission electron microscopy. The results showed that the raspberry‐like particles could be fabricated in high yield. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Polymer crystalline structure and morphology changes in nylon‐6/ZnO nanocomposites

The influence of ZnO nanoparticles on the crystalline structures of nylon‐6 under different crystallization conditions (annealing at different temperatures from the amorphous solid, isothermal crystallization from the melt at different temperatures, and crystallization from the solution) has been examined with differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction, field emission scanning electron microscopy, and Fourier transform infrared. ZnO nanoparticles can induce the γ‐crystalline form in nylon‐6 when it is cooled from the melted state and annealed from the amorphous solid. This effect of ZnO nanoparticles increases with decreasing particle size and changes under different crystallization conditions. The effects of ZnO nanoparticles on the crystallization kinetics of nylon‐6 have also been studied with DSC. The results show that ZnO nanoparticles have two competing effects on the crystallization of nylon‐6: inducing the nucleation but retarding the mobility of polymer chains. Finally, the melting behavior of the composites has been investigated with DSC, and the multiple melting peaks of composites containing ZnO nanoparticles and pure nylon‐6 are ascribed to the reorganization of imperfect crystals. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1033–1050, 2003     

Preparation and application of polystyrene‐grafted ZnO nanoparticles

The precursor of ZnO was prepared by precipitation and ZnO nanoparticles were obtained by calcination afterwards. Poly(styrene) (PSt) was grafted onto the ZnO nanoparticles in a non‐aqueous suspension to reduce the aggregation among nanoparticles and to improve the compatibility between nanoparticles and the organic matter. The obtained samples were characterized by X‐ray powder diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT‐IR), zeta potential measurement, lipophilic degree (LD) test, photocatalytic experiments, sedimentation test, and contact angle measurement. The LD of composite particles after a high‐temperature treatment was stable. The photoluminescence of PSt‐grafted ZnO nanoparticles was observed by naked eyes and was recorded using a digital camera. The ZnO nanoparticles were used to reinforce poly(vinylidene fluoride) (PVDF) films and the mechanical and electric properties of the films were also measured. Copyright © 2007 John Wiley & Sons, Ltd.     

聚丙烯酸功能化多壁碳纳米管

Covalent functionalization of multiwalled carbon nanotubes （MWNT） with poly（acrylic acid） has been successfully achieved via grafting of poly（acryloyl chloride） on nanotube surface by esterification reaction of acyl chloride-bound polymer with hydroxyl functional groups present on acid-oxidized MWNT and hydrolysis of polymer attached to nanotubes. Polymer-functionalized MWNT could possess remarkably high solubility in water, and their aqueous solution was very stable without any observable black deposit for a long time. Characterizations of such functionalized MWNT samples using Fourier transform infrared spectrometer, transmission electron microscopy and nuclear magnetic resonance techniques indicated that poly（acrylic acid） was covalently attached to the surface of MWNT.     

Synthesis and pyrolysis of a novel preceramic polymer PZMS from PMS to fabricate high‐temperature‐resistant ZrC/SiC ceramic composite

As a valuable ultra‐high‐temperature ceramic (UHTC), ZrC was introduced to SiC ceramic for the preparation of high‐temperature‐resistant ZrC/SiC composite by a polymer‐derived method through the reaction between Cp₂Zr(CH=CH₂)₂ and polymethylsilane (PMS). The composition, structure, element distribution and pyrolysis process of the preceramic polymer polyzirconomethylsilane (PZMS) were investigated by nuclear magnetic resonance, infrared, gel permeation chromatography, X‐ray photoelectron spectroscopy, energy‐dispersive X‐ray spectroscopy, scanning electron microscopy and thermogravimetric analysis. The obtained ZrC/SiC ceramic composites had very good high‐temperature resistance with a weight loss of 7.1% after being subjected to temperatures ranging from 1200 to 2200°C, as the introduction of ZrC prevented the fast growth of crystalline β‐SiC. The ceramic composites prepared by this method were homogeneous with well‐distributed element components, and the ceramic yield reached as high as 78.4%. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation of bow tie–type methacrylated poly(caprolactone‐co‐lactic acid) scaffolds: effect of collagen modification on cell growth

A branched methacrylated poly(caprolactone‐co‐lactic acid) and methacrylated poly(tetramethylene ether glycol) (PTMG‐IEM) resins were synthesized. ¹H‐NMR spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR) spectroscopy, and gel permeation chromatography confirmed the chemical structures of copolymers. The photoinitiated polymerization of formulation composed of various amounts of methacrylated poly(caprolactone‐co‐lactic acid), PTMG‐IEM, poly(ethylene glycol) diacrylate, water, and photoinitiator were performed. The curing reactions were followed by photo‐DSC (Differential scanning calorimetry). Gel fraction was calculated from the insoluble part and found as ≥93%. Swelling and contact angles were measured, and all increased with the increasing amount of PTMG‐IEM in network formulations. In vitro degradation studies were performed at 37 °C in phosphate‐buffered saline (pH 7.4). Collagen‐modified polymers were also prepared and introduced as a bioactive moiety to modify the polymer to enhance cell affinity. To compare the cell adhesion affinity to the polymer with and without collagen, cell growth experiments were performed. The results showed that collagen improves the cell adhesion onto the polymer surface. With the increasing amount of collagen, cell viability increases 86% (ECV304, p < 0.05) and 83% (3 T3, p < 0.05). Copyright © 2011 John Wiley & Sons, Ltd.     

Graft Copolymerization of Artemisia Seed Gum with Acrylic Acid under Microwave and its Water Absorbency

A super‐absorbent polymer was prepared by grafting copolymerization of acrylic acid onto Artemisia seed gum, using microwave irradiation and ammonium persulfate as an initiator. The effect of various preparation conditions on its water absorbency, such as the ratio of acrylic acid to Artemisia seed gum, degree of acrylic acid neutralization, amount of initiator and microwave irradiation time, was investigated by orthogonal tests. The optimal reaction conditions were 3 min (irradiation time), 70% neutralization degree of acrylic acid and 2% initiator on the basis of the mass of acrylic acid used. When the mass ratio of acrylic acid to Artemisia seed gum is 5:0.5, the product has a water absorbency close to 400 times at room temperature in distilled water, this indicated that is has a high water absorbency. The structure of the graft copolymer was confirmed by Fourier transform infrared spectrometer (FT‐IR) and thermogravimetric analysis (TGA). Further more, this microwave irradiation processing method to prepare water absorbent materials has no industrial cast off produced, that is to say, this method is environmentally friendly.     

Towards Organized Hybrid Nanomaterials at the Air/Water Interface Based on Liquid‐Crystal/ZnO Nanocrystals

The ability to self‐assemble nanosized ligand‐stabilized metal oxide or semiconductor materials offers an intriguing route to engineer nanomaterials with new tailored properties from the disparate components. We describe a novel one‐pot two‐step organometallic approach to prepare ZnO nanocrystals (NCs) coated with deprotonated 4‐(dodecyloxy)benzoic acid (i.e., an X‐type liquid‐crystalline ligand) as a model LC system (termed ZnO‐LC1 NCs ). Langmuir and Langmuir–Blodgett films of the resulting hybrids are investigated. The observed behavior of the ZnO NCs at the air/water interface is rationalized by invoking a ZnO‐interdigitation process mediated by the anchored liquid‐crystalline shell. The ordered superstructures form according to mechanism based on a Z nO‐ i nterdigitation p rocess mediated by l iquid c rystals (termed ZIP‐LC). The external and directed force applied upon compression at the air/water interface and the packing of the ligands that stabilize the ZnO cores drives the formation of nanorods of ordered internal structure. To study the process in detail, we follow a nontraditional protocol of thin‐film investigation. We collect the films from the air/water interface in powder form ( ZnO‐LC1 LB ), resuspend the powder in organic solvents and utilize otherwise unavailable experimental techniques. The structural and physical properties of the resulting superlattices were studied by using electron microscopy, atomic force microscopy, X‐ray studies, dynamic light scattering, thermogravimetric analysis, UV/Vis absorption, and photoluminescence spectroscopy.     

Study on luminescence characteristic of the ZnO/polymer hybrid films

The cyclohexane solution of PS (polystyrene) and the ethyl acetate solution of PMMA (polymethyl methacrylate) were used as flowing liquid; the ZnO/polymer hybrid colloids were successively produced by focused pulsed laser ablation of ZnO target in interface of solid and flowing liquid. As solvent in the hybrid colloids has volatized, the ZnO/polymer hybrid films were obtained. The hybrid colloids were characterized by high-resolution transmission electron microscopy (HRTEM) and select-area electron diffraction (SEAD). The results show a good dispersion of the ZnO nanoparticles in the polymer matrix. The hybrid films were characterized by fluorescence spectrum, Fourier transform infrared spectroscopy (FTIR) spectroscopy, thermogravimetry with FTIR (TG/FTIR), and X-ray photoelectron spectrum. The results show the ZnO/polymer hybrid films can radiate strong blue light under ultraviolet. Meanwhile, the ZnO/polymer hybrid films have higher chemical stability than ZnO nanoparticles because nano-ZnO nanoparticles were enwrapped by polymers. In addition, the ZnO hybrid films have higher thermal stability then the related pure polymers because of strong interaction among ZnO nanoparticles and polymers.     

Stimuli-responsive polyelectrolyte polymer brushes prepared via atom-transfer radical polymerization

We present an account of our research into polyelectrolyte polymer brushes that are capable of acting as stimuli-responsive films. We first detail the synthesis of poly(acrylic acid) polymer brushes using ATRP in a "grafting from" strategy. Significantly, we employed a chemical-free deprotection step that should leave the anchoring ester groups intact. We have demonstrated how these polymer assemblies respond to stimuli such as pH and electrolyte concentration. We have used poly(acrylic acid) polymer brushes for the synthesis of metallic nanoparticles and review this work. We have used XPS, ATR-FTIR, and AFM spectroscopy to show the presence of silver and palladium nanoparticles within polymer brushes. Finally, we report the synthesis of AB diblock polyampholyte polymer brushes that represent an extension of polyelectrolyte polymer brushes.     

Organic–inorganic polymeric nanocomposites involving novel titanium tetraisopropylate in polyethylene–octene elastomer

The new nanocomposites, by means of an in situ sol–gel process consisting of metallocene polyethylene–octene elastomer (POE) and titanium tetraisopropylate (TTIP), were investigated. In addition, the acrylic acid grafted POE (POE‐g‐AA) was studied as an alternative to POE. Fourier transform infrared (FTIR) spectroscopy, a dynamic mechanical analyzer (DMA) spectrometer, an X‐ray diffractometer (XRD), differential scanning calorimetry (DSC), a thermogravimetric analyzer (TGA), an Instron mechanical tester, and a scanning electron microscope (SEM) were used to characterize and examine the samples. The results indicate that the POE‐g‐AA/TiO₂ hybrid could have a positive effect on the properties of the POE/TiO₂ hybrid because the carboxylic acid groups of acrylic acid should act as coordination sites for the titania phase to form a Ti? O? C chemical bond. The strength of interfacial bonding between the polymer chains and the ceramic phase depended on the amount of TiO₂, as shown by the change in glass‐transition temperature (T_g) with TiO₂ content. The result of mechanical and thermal tests showed that both the tensile strength and the T_g increased to a maximum value and then decreased with an increasing of TiO₂ because excess particles (e.g., greater than 10 wt % TiO₂) might cause separation or segregation between the organic and inorganic phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4272–4280, 2004     

Complexation of poly(acrylic acid) and poly(ethylene oxide) investigated by enhanced Rayleigh scattering method

The method of enhanced Rayleigh scattering spectroscopy (ERS) was developed to investigate the complexation of poly(acrylic acid) (PAA) and poly(ethylene oxide) (PEO) in semidilute polymer solutions. Based on the Ornstein‐Zernike equation, the relationship between macromolecular static correlation length and ERS intensity was presented. Moreover, the ERS spectra were calculated by the moving window two‐dimensional (MW2D) correlation spectroscopy to get detailed information of the polymer complexation. The results indicated that the ERS spectroscopy characteristics of the polymer mixtures have similar trend, and the ERS intensity promptly increases as the macromolecular chains contract. The increase of ERS intensity showed that the degree of complexation between PAA and PEO increases when the pH value decreases. The complexation results from the collapse of macromolecular chains, which is induced by the PAA chains contracting and the enhanced association between PAA and PEO chains because of the hydrogen bond formation. In addition, the association resulting from the complexation of PAA and PEO in solution was demonstrated by the MW2D correlation spectroscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1847–1852, 2010     

Preparation of novel curcumin‐imprinted polymers based on magnetic multi‐walled carbon nanotubes for the rapid extraction of curcumin from ginger powder and kiwi fruit root

A novel molecularly imprinted polymer based on magnetic phenyl‐modified multi‐walled carbon nanotubes was synthesized using curcumin as the template molecule, methacrylic acid as the functional monomer and ethylene glycol dimethacrylate as the cross‐linker. The phenyl groups contained in the magnetic imprinted polymers acted as the assisting functional monomer. The magnetic imprinted polymers were characterized by scanning electron microscopy, Fourier‐transform infrared spectroscopy and vibrating sample magnetometry. Adsorption studies demonstrated that the magnetic imprinted polymers possessed excellent selectivity toward curcumin with a maximum capacity of 16.80 mg/g. Combining magnetic extraction and high‐performance liquid chromatography technology, the magnetic imprinted polymer based on magnetic phenyl‐modified multi‐walled carbon nanotubes was applied for the rapid separation and enrichment of curcumin from ginger powder and kiwi fruit root successfully.     

Molecular‐level structures at poly(4‐vinyl pyridine)/acid interfaces probed by nonlinear vibrational spectroscopy

The molecular structures of the interfaces between a solid poly(4‐vinyl pyridine) (P4VP) surface and poly(acrylic acid) (PAA) as well as hydrochloric acid (HCl) solutions were probed using sum frequency generation (SFG) vibrational spectroscopy in situ in real time. Spectroscopic results clearly reveal that the PAA molecules are adsorbed onto the P4VP surface via hydrogen bonding at the P4VP/PAA solution interface while the P4VP surface is protonated at the P4VP/HCl solution interface. Consequently, the water molecules near the interfaces are strongly perturbed by these two interactions, exhibiting different orderings at the two interfaces. This work clearly demonstrates the power of studying the interfacial molecular‐level structures via nonlinear vibrational spectroscopy when molecular adsorption happens at the solid–liquid interface and paves a way for our future study on tracing the adsorption dynamics of polymer chains onto solid surfaces. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 848–852     

Spherical Zinc Oxide Nano Particles from Zinc Acetate in the Precipitation Method

The liquid precipitation method using zinc acetate dihydrate was applied for the synthesis of uniform and spherical ZnO nanoparticles. The ultrafine zinc oxid was prepared in a water‐ethanol mixture solution. The solution containing zinc cation was soluble in water. The surface‐active agent triethanolamine (TEA) was soluble in ethanol. Then alkali precipitated by adding n‐propylamine. The spherical zinc oxide particle morphology was found to be highly dependent on the zinc salt concentration, ethanol‐water ratio, and the surface‐active agent additive. The process can produce white ZnO powder of 50–90 nm in size. The morphology of zinc oxide showed a powder shape by transmission electron microscopy (TEM), the crystallization phase structure of zinc oxide by X‐ray diffraction (XRD), and the zinc oxide remaining by using an organic analysis by infrared spectroscopy (IR).