Enhanced osteogenic activities of polyetheretherketone surface modified by poly(sodium p‐styrene sulfonate) via ultraviolet‐induced polymerization
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Abstract Polyetheretherketone (PEEK) is a promising bone and dental tissue engineering material with excellent mechanical properties and biocompatibility, but its biological inertness deficiency limits its clinical applications. In this study, poly(sodium p‐styrene sulfonate) (pNaSS) was grafted onto PEEK surface by ultraviolet (UV) induced polymerization to enhance its osteogenic activities. Attenuated total reflectance Fourier transformed Infrared (ATR‐FTIR) spectroscopy, scanning electron microscopy (SEM), and contact angle (CA) analysis were carried out to prove the success of grafting polymerization. Toluidine blue O (TBO) colorimetric assay was utilized to quantify the graft amounts of pNaSS. Results showed that the amounts of grafted pNaSS on the PEEK surface could be well‐controlled from 0.59 ± 0.07 mmol/cm 2 to 5.08 ± 0.20 mmol/cm 2 , through adjusting the UV irradiation time and monomer concentration. The hydrophilicity of PEEK surface was increased and the in vitro mineralization ability was promoted with the introduction of pNaSS. Besides, this surface modification method did not influence the intrinsic mechanical properties of PEEK. in vitro biological studies revealed that cell adhesion, proliferation, and osteogenic differentiation of MC3T3‐E1 cells were enhanced with the increase of graft amounts.Keywords:
Biocompatibility
Surface Modification
Attenuated total reflection
Biomaterial
Abstract Graft copolymerization of acrylonitrile and acrylonitrile‐styrene onto carbon fibers containing unsaturated groups was studied. Graft copolymerization of acrylonitrile was found to result in a very low grafting yield in comparison with styrene, and it remained nearly constant in the latter stage of the reaction. The effects of monomer concentrations, initiators, solvents, and reaction temperature on the monomer reactivity ratios were studied by using Hayes's equation to calculate the reactivity ratio. For graft copolymerization of acrylonitrile‐styrene were studied the rate of graft polymerization and the grafting yield with varying monomer compositions, both of which were found to be very low in the range of monomer compositions containing acrylonitrile at a level more than 8%. The monomer reactivity ratios for each monomer were calculated by use of the Fineman‐Ross method after the analytical determination of compositions of both grafted copolymer and ungrafted copolymer, and it was found that the monomer reactivity ratios for the grafted copolymer were very different from those for the ungrafted copolymer.
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Abstract The anionic copolymerization of 5‐( N , N ‐diisopropylamino)isoprene ( N , N ‐diisopropyl‐2‐vinylallylamine) and styrene initiated with alkyllithium compounds is studied. Copolymers obtained from different compositions are characterized by size‐exclusion chromatography (SEC), differential scanning calorimetry and by 1 H NMR and 13 C NMR spectroscopy. Under these conditions the dialkylaminoisoprene, similar to butadiene and isoprene, is more reactive than styrene and is incorporated faster into the polymer backbone. The incomplete conversion of the monomers has been attributed to the formation of intra‐or intermolecular complexes between the Li + counterion at the chain end and amino groups. Because of the polarity of the aminoisoprene, no tapered copolymer is obtained, contrary to the isoprene/styrene system. The reactivity ratios of the monomers calculated according to Kelen‐Tudos show that the styryl anion reacts preferably with an aminoisoprene monomer, while the aminoisoprenyl anion tends to homopolymerize.
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Abstract The synthesis and polymerization of N ‐[1‐(1‐substituted‐2‐oxopropyl)]acrylamides and ‐methacrylamides are described. Seven new monomers were prepared by two kinds of synthetic procedure. The polymerization of these monomers was carried out. Monomer reactivity ratios in the polymerization of these monomers with styrene were determined and the Alfrey‐Price Q and e values calculated. The effects of substituents on the reactivities in copolymerization were observed, and an interpretation of the results is given.
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Abstract BACKGROUND: The synthesis of poly[styrene‐ co ‐(sodium styrene sulfonate)], poly(S‐ co ‐NaSS), with a high loading of sulfonate groups is of current interest owing to its potential use in numerous areas. A series of these copolymers with various sulfonate loads were synthesized using the emulsion polymerization technique with a study of the copolymerization kinetics, monomer reactivity ratio and copolymer properties. RESULTS: The copolymerization kinetics are significantly enhanced with an increase of NaSS feed in the polymerization. Monomer reactivity ratios were determined from NMR data by employing the Fineman–Ross and Kelen–T ü d ö s methods. Styrene ( r 1 ) and NaSS ( r 2 ) reactivity ratios are 0.5 and 10, respectively. The colloidal particle size of the copolymers depends upon the NaSS composition. The thermal stability of the copolymers is greatly enhanced with higher NaSS content in the copolymer backbone. Higher glass transition temperatures are observed for the copolymers with higher NaSS content. CONCLUSION: The reactivity ratio values suggest that styrene prefers to form copolymers whereas NaSS produces homopolymers. It is also found that styrene copolymerization with NaSS is only twice as fast as homopolymerization. In contrast, NaSS homopolymerization is ten times faster than NaSS copolymerization with styrene. The NaSS content in the copolymer backbone affects the thermal stability and the glass transition of the copolymers. Copyright © 2008 Society of Chemical Industry
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Butyl acrylate
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Abstract The diblock copolymer poly(styrene-b-trimethylvinylsilane) was made anionically by sequential addition of the monomers. The copolymer is amphipathic and will stabilize foams consisting of nitrogen and polymer hydrocarbon solutions. The foam stabilization properties of poly(sty-rene-b-trimethylvinylsilane) are dependent upon molecular weight, composition, and concentration. The optimum diblock copolymer has M n in the range of 9 000-30 000, contains about 0.10 mole fraction trimethylvinylsilane, and is used at about 0.3 wt% concentration for foams consisting of nitrogen dispersed in a solution of polystyrene in styrene monomer. The diblock copolymer poly(styrene-b-trimethylvinylsilane) is readily made by sequentially and anionically polymerizing styrene and trimethylvinylsilane. Kinetics place limitations upon the length of the poly(trimethylvinylsilane) segment and conversion of trimethylvinylsilane monomer due to a termination reaction. Two transitions are observed in DSC thermograms indicating that the poly(styrene) and poly(trimethylvinylsilane) segments reside in separate domains. The amphipathic nature of the diblock copolymer is revealed from molecular weight and GPC data, which show that the polystyrene) segment is more lyophilic in tetrahydrofuran than the poly(trimethylvinylsilane) segment. The foaming properties of the diblock copolymer were found to depend upon composition, molecular weight, and concentration. Typically, concentrations of 0.3 wt% of a diblock copolymer having M n in the range 9 000-30 000 and 0.10 mole fraction styrene stabilized fine-celled foams of nitrogen and polystyrene-styrene solutions. Both the foaming properties and inertness to carbanions make poly(styrene-b-trimethylvinylsilane) a good candidate as a foaming agent in an anionic poly(styrene) RIM process.
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Abstract Gelatin was graft copolymerized with poly(butyl acrylate) using potassium peroxy disulfate in aqueous medium. Effects of temperature, time, monomer concentration, and backbone concentration were studied. The percent grafting was found to increase initially and then decreased in all cases. Infrared, viscosity, and thermal analysis were carried out on the graft copolymers, and the mechanism of the graft copolymerization reaction was discussed.
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Abstract Sulfonated polystyrene (S–PS), which is of considerable scientific and technological interest, has been traditionally prepared by the sulfonation of preformed polystyrene. This report describes the preparation and properties of S–PS prepared by emulsion copolymerization of styrene and sodium styrene sulfonate. S–PS prepared by copolymerization gave solubility, solution behavior and thermal characteristics that are consistent with an ionomeric structure. The solubility characteristics indicated some chain‐to‐chain sulfonate heterogeneity. Thermal analysis studies indicated that the glass transition does not increase with increasing sulfonate content. This is contrary to what has been observed for S–PS prepared by sulfonation and suggests that the S–PS prepared by copolymerization is fundamentally different in structure than S–PS prepared by sulfonation of polystyrene.
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mined by analysis of 1 H NMR spectra. The reactivity ratios of D-120 and BA were determined using the meth- ods of Kelen-Tds (K-T), Fineman-Ross (F-R) and Yezrielev-Brokhina-Roskin (YBR), respectively. Graft copolymers were obtained by the grafting of styrene onto the copolymers during the decompositon of peroxy bonds of the copolymers.
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