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1.
The graft copolymerization of butyl acrylate (BA) onto chitosan was tried via a new protection‐graft‐deprotection procedure. About 6‐O‐maleoyl‐N‐phthaloyl‐chitosan was synthesized and characterized by Fourier transform infrared spectra analysis (FT‐IR) and 1H‐NMR. Because the intermediate 6‐O‐maleoyl‐N‐phthaloyl‐chitosan was soluble in organic solvents, the graft copolymerization was carried out in a homogeneous system. Grafting was initiated by γ‐irradiation. The graft extent was dependent on the irradiation dose and the concentration of BA monomer, and copolymers with grafting above 100% were readily prepared. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 489–493, 2006  相似文献   

2.
This article describes the synthesis and characterization of 2‐hydroxylethyl methacrylate‐coN‐vinylpyrrolidone copolymers, (HEMA‐co‐NVP), via free radical polymerization followed by grafting of poly(lactide) onto (HEMA‐co‐NVP) copolymers, via ring opening polymerization using tin octoate as a catalyst. The copolymers and the grafted copolymers (i.e., amphiphiles) were subjected to sustained release studies using salicylic acid, as a model drug. Characterization of the formed copolymers was performed using 1H‐NMR, 13C‐NMR, FTIR, TGA, DSC, and SEM techniques. Derivative of TGA thermogram was used to determine %hydrophilicity and %hydrophobicity in the grafted and ungrafted copolymers. The SEM morphology revealed porous layers with crispy structure that were most likely due to the presence of poly(lactide) chains. At lower content of poly(lactide) moiety, grafted copolymers showed non‐Fickian diffusion release rate, whereas Fickian diffusion release rate at higher content of poly(lactide) was observed. The increase of poly(lactide) content (i.e., larger %hydrophobicity) in the copolymer increased the drug‐sustainability, due to the consistent but porous amphiphilic degradable structures that allow controllable release of drug in time interval. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

3.
Poly(3‐hydroxy octanoate) (PHO), poly(3‐hydroxy butyrate‐co‐3‐hydroxyvalerate) (PHBV), and linoleic acid were grafted onto chitosan via condensation reactions between carboxylic acids and amine groups. Unreacted PHAs and linoleic acid were eliminated via chloroform extraction and for elimination of unreacted chitosan were used 2 wt % of HOAc solution. The pure chitosan graft copolymers were isolated and then characterized by FTIR, 13C‐NMR (in solid state), DSC, and TGA. Microbial polyester percentage grafted onto chitosan backbone was varying from 7 to 52 wt % as a function of molecular weight of PHAs, namely as a function of steric effect. Solubility tests were also performed. Graft copolymers were soluble, partially soluble or insoluble in 2 wt % of HOAc depending on the amount of free primary amine groups on chitosan backbone or degree of grafting percent. Thermal analysis of PHO‐g‐Chitosan graft copolymers indicated that the plastizer effect of PHO by means that they showed melting transitions Tms at 80, 100, and 113°C or a broad Tms between 60.5–124.5°C and 75–125°C while pure chitosan showed a sharp Tm at 123°C. In comparison of the solubility and thermal properties of graft copolymers, linoleic acid derivatives of chitosan were used. Thus, the grafting of poly(3‐hydroxyalkanoate) and linoleic acid onto chitosan decrease the thermal stability of chitosan backbone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:81–89, 2007  相似文献   

4.
Graft copolymers of chitosan and vinyl acetate were synthesized by free radical technique using cerium (IV) as the initiator. Under controlled conditions, as much as 92% grafting with a grafting yield of 30–40% could be achieved. Chitosan‐g‐poly(vinyl alcohol) copolymers were derived by the alkaline hydrolysis of the chitosan‐g‐poly(vinyl acetate) precursor. Thermogravimetric, FTIR, and X‐ray diffraction analyses of chitosan and the copolymers confirmed the grafting reaction between chitosan and vinyl acetate and also the subsequent hydrolysis. Both the copolymers possessed very good film‐forming properties. Grafting resulted in a significant increase in mechanical strength of both the copolymers in the dry condition. Chitosan‐g‐poly(vinyl acetate) (CH‐PVAc) proved more hydrophobic than did pure chitosan, whereas chitosan‐g‐poly(vinyl alcohol) (CH‐PVOH) exhibited enhanced hydrophilicity as evident from their swelling characteristics and contact angle measurements. The enhanced swelling of CH‐PVOH was ascribed to the presence of the pendant poly(vinyl alcohol) group. At pH 1.98, the CH‐PVAc copolymer films showed greater stability than do pure chitosan films, which is highly beneficial for specific biomedical applications. Both the copolymers showed lower glass transition temperature than do pure chitosan. Grafting did not affect the overall thermal stability, and the differential thermogram substantiated the grafting. The investigations indicate that the synthetic–natural hybrid copolymers having desirable mechanical properties and tailored hydrophilic/hydrophobic characteristics are realizable. These polymers could be exploited for varied biomedical applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1852–1859, 2007  相似文献   

5.
The polycarbonate copolymers poly[trimethylene carbonate‐co‐2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate] [P(TMC‐co‐PTC)] were synthesized by the ring‐opening polymerization of trimethylene carbonate (TMC) and 2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate (PTC) with tin(II) 2‐ethylhexanoate and aluminum isopropoxide as the catalysts. These copolymers were further reduced by a palladium/carbonate (Pd/C; 10%) catalyst to produce partly deprotected copolymers. These two types of copolymers were characterized by 1H‐NMR, Fourier transform infrared spectroscopy, UV spectroscopy, gel permeation chromatography, differential scanning calorimetry, and an automatic contact angle meter. The influences of the feed molar ratio of the monomers, the catalyst concentration, the reaction time, and the reaction temperature on the copolymerization process were also studied. The copolymerization of the TMC and PTC monomers was a nonideal copolymerization, and the copolymerization reactivity ratio of TMC was higher than that of PTC. In vitro degradation tests indicated that the partly deprotected copolymers possessed faster degradation rates and more hydrophilicity than the corresponding unreduced copolymers. Moreover, the degradation of these two type copolymers increased when the pH value of the buffer solutions decreased. In vitro drug‐release experiments showed that these two types of copolymers had steady drug‐release rates and good controlled release properties. Moreover, the partly deprotected copolymers had faster drug‐release rates than the corresponding unreduced copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

6.
Water‐soluble copolymers of N‐acryloyl‐N‐methylpiperazine and N‐acetyl‐α‐aminoacrylic acid were synthesized by radical polymerization. The copolymerization yield ranged between 60 and 97%. The FTIR and NMR spectra demonstrated that the copolymerization occurred. The copolymer composition was determined from 1H‐NMR spectra by comparison of methyl groups from both moieties. The copolymers were richest in AAA units. The metal ion retention properties were investigated by the liquid‐phase polymer‐based retention (LPR) technique at different pH and filtration factors. The affinity for the metal ions depended on the copolymer composition, pH, and filtration factor. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2556–2561, 2002  相似文献   

7.
A novel cyclic‐amine monomer, 3‐allyl‐5,5‐dimethylhydantoin (ADMH) was synthesized with good yield by the reaction of allyl bromide with 5,5‐dimethylhydantoin (DMH), and was characterized by FTIR and 1H‐NMR spectra. ADMH alone cannot be grafted onto other polymers. However, the presence of acrylonitrile markedly enhanced the ADMH graft yield onto cotton cellulose. The influence of reaction conditions on the graft copolymerization was investigated. After chlorine bleach treatment, hydantoin units in the grafted copolymers were easily transformed into N‐halamine structures. Grafted samples exhibited potent antibacterial activity against Escherichia coli, and the functional properties were shown to be durable and regenerable. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 617–624, 2001  相似文献   

8.
The grafting of acrylamide onto a chitosan backbone was carried out at three acrylamide concentrations (polymer/monomer ratio = 1:1, 1:2, and 1:3). The synthesis of the grafted polymer was achieved by K2S2O8‐induced free‐radical polymerization. Microspheres of polyacrylamide‐g‐chitosan crosslinked with glutaraldehyde were prepared to encapsulate nifedipine (NFD), a calcium channel blocker and an antihypertensive drug. The microspheres of polyacrylamide‐g‐chitosan were produced by a water‐in‐oil emulsion technique with three different concentrations of glutaraldehyde as the crosslinking agent. Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC) were used to characterize the grafted copolymers, and the microspheres were prepared from them. FTIR and DSC were also used to analyze the extent of crosslinking. The microspheres were characterized by the particle size; the water transport into these microspheres, as well as the equilibrium water uptake, were studied. Scanning electron microscopy confirmed the spherical nature of the particles, which had a mean particle size of 450 μm. Individual particle dynamic swelling experiments suggested that with an increase in crosslinking, the transport became case II. The release of NFD depended on the crosslinking of the network and on the amount of drug loading. Calculating the drug diffusion coefficients with the initial time and later time approximation method further supported this. The drug release in all 27 formulations followed case II transport, and this suggested that the time dependence of the NFD release followed zero‐order kinetics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2940–2949, 2003  相似文献   

9.
To develop cost effective and eco friendly polymeric materials for enrichment and separation technologies, 1‐vinyl‐2‐pyrrolidone (N‐VP) was graft copolymerized onto cellulose, extracted from pine needles. Optimum conditions have been evaluated for the grafting of N‐VP onto cellulose and at these conditions it was also grafted onto cellulose phosphate, hydroxypropyl cellulose, cyanoethyl cellulose, and deoxyhydrazino cellulose. At the optimum grafting conditions for N‐VP, it was also cografted with maleic anhydride. Kinetics of radiochemical graft copolymerization has been studied and evaluation of the polymerization and grafting parameters as percent grafting, percent grafting efficiency, rate of polymerization, homopolymerization, and graft copolymerization have been evaluated. Graft copolymers have been characterized by elemental analysis, FTIR, and swelling studies. An attempt has been made to study sorption of some metal ions such as Fe2+ and Cu2+ and iodine on select graft copolymers to investigate selectivity in metal ion sorption and iodine sorption as a function of structural aspects of the functionalized graft copolymers to find their end uses in separation and enrichment technologies. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 373–382, 2005  相似文献   

10.
Chitosan‐g‐poly(vinyl alcohol) (PVA) copolymers with different grafting percent were prepared by grafting water‐soluble PVA onto chitosan. The drug‐release behavior was studied using the chitosan‐g‐PVA copolymer matrix containing prednisolone in a drug‐delivery system under various conditions. The relationship between the amount of the released drug and the square root of time was linear. From this result, the drug‐release behavior through the chitosan‐g‐PVA copolymer matrix is shown to be consistent with Higuchi's diffusion model. The drug‐release apparent constant (KH) was slightly decreased at pH 1.2, but increased at pH 7.4 and 10 according to the increasing PVA grafting percent. Also, KH was decreased by heat treatment and crosslinking. The drug release behavior of the chitosan‐g‐PVA copolymer matrix was able to be controlled by the PVA grafting percent, heat treatment, or crosslinking and was also less affected by the pH values than was the chitosan matrix. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 458–464, 1999  相似文献   

11.
2‐Hydroxyethyl methacrylate was copolymerized with acrylamide, N‐vinyl‐2‐pyrrolidone, and n‐butyl methacrylate by free‐radical solution polymerization with α,α′‐azobisisobutyronitrile as an initiator at 70 ± 1°C. The average molecular weights and molar compositions of the resultant copolymers were determined with gel permeation chromatography and 1H‐NMR spectroscopy data, respectively. Diclofenac or 2‐[(2,6‐dichlorophenyl)amino]benzene acetic acid, a nonsteroidal anti‐inflammatory drug, was chemically attached to the copolymers by transesterification reaction in the presence of N,N′‐dicyclohexylcarbodiimide to give macromolecular prodrugs. All the synthesized polymers were characterized with Fourier transform infrared, 1H‐, and 13C‐NMR spectroscopy techniques. The polymer–drug conjugates were hydrolyzed in cellophane member dialysis bags containing aqueous buffered solutions (pH 8) at 37°C, and the hydrolysis solutions were detected by UV spectrophotometer at selected intervals. The results showed that the drug could be released by selective hydrolysis of the ester bond from the side chain of the drug moiety. The release profiles of the drug indicated that the hydrolytic behavior of polymeric prodrugs strongly depends on the hydrophilicity of the polymer. The results suggest that the synthesized copolymers could be useful carriers for the release of diclofenac in controlled‐release systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2403–2409, 2007  相似文献   

12.
Solvothermal process was successfully developed to graft dibutylmaleate (DBM) onto poly(ethylene‐co‐1‐octene) (POE) with dicumyl peroxide (DCP) as free radical‐initiator. FTIR spectra demonstrate that DBM is successfully grafted onto the backbone of POE by this novel method. The influences of DBM content, DCP concentration, POE concentration, reaction temperature and reaction time on the grafting copolymerization have been investigated in detail through grafting degree (GD). It is worthy to indicate that high grafting degree (above 15%) can be achieved through the one‐pot way when the graft reaction is carried out in 40 mL toluene at 150°C for 5 h with 1.6 g DBM, 6–8 g POE and 0.35 g DCP. This developed solvothermal process is becoming an effective way to prepare POE‐g‐DBM graft copolymers, and can be extended to other systems. In addition, TGA results show that the thermal properties of POE are enhanced after the grafting reaction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

13.
Modification of chitosan by grafting with 4‐vinylpyridine (VP) was carried out both in homogeneous and heterogeneous phases, using potassium persulfate (K2S2O8) and sodium bisulfite (NaHSO3) as redox initiators. The effect of monomer concentration, initiator concentration and redox ratio, time and temperature on the extent of grafting (G%), homopolymer formation, and the efficiency of grafting were studied. Values of grafting percentages up to 96% were reached in heterogeneous conditions and up to 130% in homogeneous conditions (in 5% acetic acid). The grafting was confirmed by FTIR and 1H NMR spectroscopy. The grafted samples were characterized by scanning electron microscopy, X‐ray diffraction, and thermogravimetric analysis. The crystallinity of the used chitosan was not affected by grafting, it even increased slightly. Dye uptake of the grafted samples towards the different types of dyes (acidic and basic) was investigated and was found to improve profoundly over the native chitosan with a higher uptake for the acidic dye. The grafted samples showed an increased swelling in water, which increased further upon quaternization of the graft copolymers. The extent of swelling is higher in acidic and basic media more than in neutral pH. The grafted copolymers are soluble with difficulty in warm acetic acid solution. The quaternized graft copolymer was found to be soluble in water. The biological activity of the quaternized graft copolymers (G = 130 and 80%) was investigated and was found to have an inhibition effect on both the Azotobacter fungus and the bacterium Fusarium oxysporium. The effect on the micro organisms is proportional to the amount of VP in the graft copolymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3308–3317, 2006  相似文献   

14.
A series of poly(5,5‐dimethyl‐1,3‐dioxan‐2‐one)‐block‐methoxy poly(ethylene glycol) (PDTC‐b‐mPEG) copolymers were synthesized by the ring‐opening polymerization of 5,5‐dimethyl‐1,3‐dioxan‐2‐one (DTC) in bulk, using methoxy poly(ethylene glycol) (mPEG) as initiator without adding any catalysts. The resulting copolymers were characterized by Fourier transform infrared spectra, 1H NMR and gel permeation chromatography. The influences of some factors such as the DTC/mPEG molar feed ratio, reaction time and reaction temperature on the copolymerization were investigated. The experimental results showed that mPEG could effectively initiate the ring‐opening polymerization of DTC in the absence of catalyst, and that the copolymerization conditions had a significant effect on the molecular weight of PDTC‐b‐mPEG copolymer. In vitro drug release study demonstrated that the amount of indomethacin released from PDTC‐b‐mPEG copolymer decreased with increase in the DTC content in the copolymer. © 2013 Society of Chemical Industry  相似文献   

15.
Superabsorbent composites based on chitosan‐g‐poly(acrylamide) and montorillonite (CTS‐g‐PAAm/MMT) were synthesized through in situ radical polymerization by grafting of crosslinked acrylamide onto chitosan backbone in presence of MMT at different contents. The formation of the grafted network was confirmed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetery (DSC). The obtained porous structure was observed by scanning electron microscope (SEM). The presence of clay and its interaction with chitosan‐g‐poly(acrylamide) (CTS‐g‐PAAm) matrix was evidenced by ATR‐FTIR analysis. The morphology was investigated by both X‐ray diffraction (XRD) and SEM analyses. It was suggested the formation of mostly exfoliated structures with more porous structures. Besides, the thermal stability of these composites, observed by TGA analysis, was slightly affected by the clay loading as compared to the matrix. These hydrogel composites were also hydrolyzed to achieve anionic hydrogels with ampholytic properties. Swelling behaviors were examined in doubly distilled water, 0.9 wt % NaCl solution and buffer solutions. The water absorbency of all superabsorbent composites was enhanced by adding clay, where the maximum was reached at 5 wt % of MMT. Their hydrolysis has not only greatly optimized their absorption capacity but also improved their swelling rate and salt‐resistant ability. The hydrolyzed superabsorbent showed better pH‐sensitivity than the unhydrolyzed counterparts. The results of the antibacterial activity of these superabsorbents composites against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli), assayed by the inhibitory zone tests, have showed moderate inhibition of the bacteria growth. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39747.  相似文献   

16.
Graft copolymers of sodium alginate (NaAlg) with N‐vinyl‐2‐pyrrolidone were prepared using azobisisobutyronitrile as initiator. The graft copolymers (NaAlg‐g‐PVP) were characterized with Fourier transform infrared spectroscopy, elemental analysis, and differential scanning calorimetry. Polymeric hydrogel beads of NaAlg and NaAlg‐g‐PVP were prepared by crosslinking method using glutaraldehyde (GA) as a crosslinker in the hydrochloric acid catalyst (HCl) and these beads were used to deliver anti‐inflammatory drug, indomethacin (IM). Chemical stability of the IM after encapsulation into beads was confirmed by FTIR. Preparation conditions of the NaAlg‐g‐PVP beads were optimized by considering the percentage entrapment efficiency, particle size, swelling capacity and their release data. In vitro release studies were performed in simulated gastric fluid (pH 1.2) for the initial 2 h, followed by simulated intestinal fluid (pH 7.4) for 4 h. Effects of GA concentration, exposure time to GA, drug/polymer (d/p) ratio, and concentration of HCl on the release of IM were discussed. It was observed that IM release from the beads decreased with increasing GA concentration and exposure time. IM release also decreases with increasing d/p ratio and HCl concentration. The highest IM release was obtained to be 77% for beads crosslinked with 0.027M GA. Swelling experiments were also performed to compute molecular mass between crosslinks of the beads. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

17.
Two new kinds of amphiphilic copolymers were synthesized in this work. Poly(1‐octene‐co‐acrylic acid) copolymers were prepared through the copolymerization of 1‐octene and tert‐butyl acrylate, and the hydrolysis of tert‐butyl acrylate units. Poly(1‐octene‐co‐acrylic acid)‐g‐poly (ethylene glycol) copolymers were obtained from the esterification reaction between poly(1‐octene‐co‐acrylic acid) and poly(ethylene glycol) monomethyl ether. They were characterized by means of 1H‐NMR, 13C‐NMR, GPC, and FTIR. These amphiphilic copolymers can form stable micelles in aqueous solutions. The critical micelle concentration was determined by fluorescence spectroscopy. The micellar morphology and size distribution were investigated by transmission electron microscopy and dynamic light scattering. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

18.
Graft copolymerization of starch has been carried out onto preirradiated polypropylene (PP) in an aqueous medium using benzoyl peroxide (BPO) as the radical initiator. The maximum percentage of grafting (115%) of starch onto PP was obtained at optimum conditions of BPO concentration, 1.239 × 10−3 moles; temperature, 65°C; in 120 min. using 30 mL of water. Swelling studies were carried out in pure, binary, ternary and quaternary solvent systems comprising of water, ethanol (EtOH), dimethylsulphoxide (DMSO), and N,N‐dimethylformamide (DMF) in different ratios. Maximum swelling is observed in DMSO and DMF, followed by EtOH and least in water for true graft. Water retention studies of pristine PP and PP‐g‐Starch (both composite and true graft) were investigated at different time periods, temperature and pH. The composite contains grafted PP, unreacted starch and unreacted PP whereas true graft is the product from which both unreacted polymers have been removed. Maximum % water retention of PP‐g‐Starch (composite) (110%) was observed in 8 h at 50°C in neutral medium (pH = 7). The graft copolymers were characterized by FTIR, DTG, DTA, TGA, and SEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

19.
A series of polycarbonate copolymers were synthesized by the ring‐opening bulk polymerization of 2‐phenyl‐5,5‐bis(hydroxymethyl) trimethylene carbonate (PTC) and 5,5‐dimethyl trimethylene carbonate (DTC) with tin(II) 2‐ethylhexanoate and aluminum isopropoxide as initiators. The copolymers obtained were characterized by 1H‐NMR, Fourier transform infrared, and ultraviolet. The influence of the molar ratio of the monomers, the initiators, and their concentrations, the reaction time, and the reaction temperature on the copolymerization was also studied. The copolymerization of monomers DTC and PTC was a nonideal copolymerization, and the copolymerization reactivity ratio of the monomer DTC was higher than that of PTC in the copolymerization process. In vitro release profiles of fluorouracil from the copolymers showed that the copolymer had a steady drug‐release rate and good controlled‐release property. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008  相似文献   

20.
Electrochemical copolymerization of o‐dihydroxybenzene (oDHB) and 3‐methylthiophene (3MeT) was successfully achieved in boron trifluoride diethyl etherate by direct anodic oxidation of the monomer mixtures, although the oxidation potentials of oDHB and 3MeT were quite different. The influence of the applied polymerization potential on the synthesis of the copolymers was investigated. The higher applied potential favored the incorporation of 3MeT units into the copolymers. The structure and properties of the copolymers were investigated with UV‐vis spectroscopy, fluorescence spectroscopy, FTIR spectroscopy, and thermal analysis. The novel copolymers had many advantages, including good redox activity, good thermal stability, and high electrical conductivity. Additionally, the copolymers fluorescence properties that were tunable through changes in the feed ratio of the monomer mixtures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

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