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1.
Poly(vinyl alcohol) (PVA) grafted with poly(lactide‐co‐glycolide) and cross‐linked as a material of increased hydrophobicity relative to PVA was produced. The properties were examined with respect to the mass loss, water uptake, hydrophilicity, and mechanical characteristics upon hydrolytical degradation. The hydrogels investigated display water uptake increasing with degradation time because of increasing hydrophilicity. The mass loss amounts up to 15% after eight weeks of degradation. The mechanical properties of the hydrogels are within the range of those of natural tissue, the E modulus is 18 MPa, or even 100–200 MPa, depending on the structure of material. The mechanical characteristic and their dependence degradation show the most recognizable correlation with the chemical structure. Studies of the topography of degraded samples (scanning electron microscopy) and IR measurements demonstrate the degradation to occur at slow rate due to the high degree of grafting. The mass loss is rather low and a bulk degradation mechanism takes place. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

2.
In this work, we present the synthesis and characterization of chemically crosslinked polyurethanes (PU) composed of poly(ethylene glycol) (PEG) and poly(caprolactone) diol (PCL‐diol), as hydrophilic and hydrophobic segments respectively, poly(caprolactone) triol (PCL‐triol), to induce hydrolysable crosslinks, and hexamethylene diisocyanate (HDI). The syntheses were performed at 45 °C, resulting in polyurethanes with different PEG/PCL‐diol/PCL‐triol mass fractions. All the PUs are able to crystallize and their thermal properties depend on the global composition. The water uptake capacities of the PU increase as the PEG amount increases. The water into hydrogels is present in different environments, as bounded, bulk and free water. The PU hydrogels are thermo‐responsive, presenting a negative dependence of the water uptake with the temperature for PEG rich networks, which gradually changes to a positive behavior as the amount of poly(caprolactone) (PCL) segments increases. However, the water uptake capacity changes continuously without an abrupt transition. Scanning electron microscopy (SEM) analyses of the hydrogel morphology after lyophilization revealed a porous structure. Mechanical compression tests revealed that the hydrogels present good resilience and low recovery hysteresis when they are subject to cycles of compression–decompression. In addition, the mechanical properties of the hydrogels varies with the composition and crosslinking density, and therefore with the water uptake capacity. The PU properties can be tuned to fit for different applications, such as biomedical applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43573.  相似文献   

3.
Polystyrene terminated with benzyl alcohol units was employed as a macroinitiator for ring‐opening polymerization of ε‐caprolactone and L ‐lactide to yield AB‐ and ABC‐type block copolymers. Even though there are many reports on the diblock copolymers of poly(styrene‐block‐lactide) and poly(styrene‐block‐lactone), this is the first report on the poly(styrene‐block‐lactone‐block‐lactide) triblock copolymer consisting of two semicrystalline and degradable segments. The triblock copolymers exhibited twin melting behavior in differential scanning calorimetry (DSC) analysis with thermal transitions corresponding to each of the lactone and lactide blocks. The block derived from ε‐caprolactone also showed crystallization transitions upon cooling from the melt. In the DSC analysis, one of the triblock copolymers showed an exothermic transition well above the melting temperature upon cooling. Thermogravimetric analysis of these block copolymers showed a two‐step degradation curve for the diblock copolymer and a three‐step degradation for the triblock copolymer with each of the degradation steps associated with each segment of the block copolymers. The present study shows that it is possible to make pure triblock copolymers with two semicrystalline segments which also consist of degradable blocks. Copyright © 2009 Society of Chemical Industry  相似文献   

4.
Methoxy poly(ethylene glycol)‐b‐poly(ε‐caprolactone) (MPEG‐PCL) or MPEG‐b‐poly(L ‐lactide) (MPEG‐PLLA) diblock copolymers were prepared by the polymerization of CL or LA, using MPEG as an initiator in the presence of stannous octoate. MPEG‐b‐poly(ε‐caprolactone‐ran‐L ‐lactide) (MPEG‐PCLA) diblock copolymers with different chemical composition of PCL and PLLA were also prepared by adjusting the amount of CL and LA from MPEG in the presence of stannous octoate. In degradation study, the degradation of the MPEG‐PCLA diblock copolymers mainly depends on the PCL and PLLA segments present in their structure. MPEG‐PCLA, with intermediate ratio of PCL and PLLA segment, completely degraded after 14 weeks. Meanwhile, partially degraded MPEG‐PCLA segments and parent MPEG segments were observed at higher PCL or PLLA segment contents. Introduction of PLLA into the PCL segments caused a lowering of the crystallinity of the diblock copolymers, thus, inducing a faster incoming of water into the copolymers. We confirmed that the diblock copolymers, with lower degree of crystallinity, have degraded more rapidly. POLYM. ENG. SCI., 46: 1242–1249, 2006. © 2006 Society of Plastics Engineers  相似文献   

5.
Novel pH‐sensitive chitosan‐poly(acrylamide‐co‐itaconic acid) hydrogels were prepared by free radical copolymerization of acrylamide and itaconic acid (IA) in chitosan solution. The hydrogels were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry and the swelling ratios of the hydrogels in water (pH 6.8) and pH 1.2. The influence of composition on the thermal properties of the hydrogels was assessed. The glass transition temperatures of the samples increased with IA content, ranging from 110 to 136 °C. Swelling of the hydrogels was found to obey second‐order kinetics with respect to the remnant swelling, indicating that diffusion is controlled by the relaxation of chains. The equilibrium swelling degree was strongly dependent on pH and composition. At both pH values the highest water uptake was obtained for the IA‐free sample M1. From the equilibrium swelling results the average molar mass between crosslinks, Mc, and the crosslink density of the chitosan‐poly(acrylamide‐co‐itaconic acid) samples were calculated. The results evidenced the reinforcing effect of IA on the hydrogel structure. It is concluded that these highly swellable pH‐sensitive hydrogels can be useful for applications in biomedicine and pharmacy. © 2013 Society of Chemical Industry  相似文献   

6.
Tetraphenyl porphyrin metal compound (TPPMCl) (where the TPPMCl was TPPCrCl, TPPCoCl, TPPAlCl), in combination with cocatalyst PPNCl (bis(triphenylphosphine)iminium chloride, the molar ratio of TPPMCl to PPNCl was 1:0.5), was used to catalyze the polymerization of racemic lactide (rac‐LA) in racemic propylene oxide (rac‐PO) medium and the terpolymerization of rac‐LA, CO2 and rac‐PO. It was found that these TPPMCl/PPNCl binary catalysts could initiate the stereoselective polymerization of rac‐LA in rac‐PO medium to form enriched isotactic polylactide (PLA) (Pi ≥ 68.0%) and terpolymerization of CO2, rac‐LA, rac‐PO to form PPC‐PLA‐PPO (PPC, poly(propylene carbonate); PPO, poly(propylene oxide)) multiblock copolymer. In particular the PPC‐PLA‐PPO multiblock copolymer thus formed displayed high regioregularity and stereoregularity, and has high head‐to‐tail structure content in the PPC block (H‐T% ≥ 63.6%) and high isotacticity in the PLA block (Pi ≥ 64.0%). The influence of catalyst formula, the monomer feeding ratio, reaction temperature, carbon dioxide pressure and reaction time on the terpolymerization was investigated by 1H NMR, 13C NMR, gel permeation chromatography, DSC and TGA. © 2018 Society of Chemical Industry  相似文献   

7.
Poly‐DL ‐lactide (PLA) and poly‐DL ‐lactide‐poly(ethylene glycol) (PELA) were produced by bulk ring‐opening polymerization using stannous chloride as initiator. PLA, PELA microspheres, and PELA microspheres containing the outer membrane protein (OMP) of Leptospira interrogans with the size of 1.5–2 μm were prepared by a solvent evaporation process. In vitro degradation and release tests of PLA, PELA, and OMP‐loaded PELA microspheres were performed in pH 7.4 buffer solution at 37°C. Quantitatively, the degree of degradation was monitored by detecting the molecular weight reduction, by evaluating the mass loss and the apparent degradation rate constant, and by determining the intrinsic viscosity and poly(ethylene glycol) content of retrieved polymer, while the release profile was assessed by measuring the amount of protein presented in the release medium at various intervals. Qualitatively, the morphological changes of microspheres were observed with scanning electron micrography. The observed relative rates of mass loss versus molecular weight reduction are consistent with a bulk erosion process rather than surface erosion for PELA microspheres. The introduction of hydrophilic poly(ethylene glycol) domains in copolymer PELA and the presence of OMP within microspheres show critical influences on the degradation profile. The OMP‐loaded PELA microspheres present triphasic release profile and a close correlation is observed between the polymer degradation and the OMP release profiles. It is suggested that the polymer degradation rate, protein diffusion coefficient, and the water‐swollen structure of microspheres matrix commonly contribute to the OMP release from PELA microspheres. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 140–148, 2000  相似文献   

8.
In this work, biocompatible hydrogel matrices for wound‐dressing materials and controlled drug‐release systems were prepared from poly[hydroxyethyl methacrylate‐co‐poly(ethylene glycol)–methacrylate] [p(HEMA‐co‐PEG–MA] films via UV‐initiated photopolymerization. The characterization of the hydrogels was conducted with swelling experiments, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis (differential scanning calorimetry), and contact‐angle studies. The water absorbency of the hydrogel films significantly changed with the change of the medium pH from 4.0 to 7.4. The thermal stability of the copolymer was lowered by an increase in the ratio of poly(ethylene glycol) (PEG) to methacrylate (MA) in the film structure. Contact‐angle measurements on the surface of the p(HEMA‐co‐PEG–MA) films demonstrated that the copolymer gave rise to a significant hydrophilic surface in comparison with the homopolymer of 2‐hydroxyethyl methacrylate (HEMA). The blood protein adsorption was significantly reduced on the surface of the copolymer hydrogels in comparison with the control homopolymer of HEMA. Model antibiotic (i.e., minocycline) release experiments were performed in physiological buffer saline solutions with a continuous flow release system. The amount of minocycline release was shown to be dependent on the HEMA/PEG–MA ratio. The hydrogels have good antifouling properties and therefore are suitable candidates for wound dressing and other tissue engineering applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

9.
Three series of novel semi‐interpenetrating polymer networks, based on crosslinked poly(N‐isopropylacrylamide), PNIPA, and different amounts of the linear poly(N‐vinylpyrrolidone), PVP, were synthesized to improve the mechanical properties and thermal response of PNIPA gels. The effect of the incorporation of the linear PVP into the temperature responsive networks on the temperature‐induced transition, swelling/deswelling behavior, and mechanical properties was studied. Polymer networks with four different crosslinking densities were prepared with varying molar ratios (25/1 to 100/1) of the monomer (N‐isopropylacrylamide) to the crosslinker (N,N′‐methylenebisacrylamide). The hydrogels were characterized by determination of the equilibrium degree of swelling, the dynamic shear modulus and the effective crosslinking density, as well as tensile strength and elongation at break. Furthermore, the deswelling kinetics of the hydrogels was studied by measuring their water retention capacity. The inclusion of the linear hydrophilic PVP in the PNIPA networks increased the equilibrium degree of swelling. The tensile strength of the semi‐interpenetrating networks (SIPNs) reinforced with linear PVP was higher than that of the PNIPA networks. The elongation at break of these SIPNs varied between 22% and 55%, which are 22 – 41% larger than those for pure PNIPA networks. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

10.
A copolymer, poly(L ‐lactide)‐g‐poly(N‐vinyl pyrrolidone) (PLLA‐g‐PVP) was prepared with poly(L ‐lactide) (PLLA) and N‐vinyl pyrrolidone in the presence of methanol as a solvent by γ‐ray irradiation. The structure of PLLA‐g‐PVP was characterized by 1H‐NMR and Fourier transform infrared spectroscopy. The PLLA‐g‐PVP graft ratio calculated by the percentage increase in weight increased with the increase of absorbed dose, and the percentage crystallinity of PLLA‐g‐PVP decreased with increasing graft ratio. The introduction of the poly(N‐vinyl pyrrolidone) chain into PLLA resulted in a decrease in the contact angle of PLLA‐g‐PVP with increasing graft ratio. In vitro degradation testing showed that PLLA‐g‐PVP had a higher degradation rate both in the weight‐loss test and molecular weight measurement because of a lower crystalline percentage and higher hydrophilicity compared to PLLA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

11.
Grafting of poly(ε‐caprolactone) (PCL) and poly(lactide) (PLA) chains on poly(vinyl alcohol) backbone (PVA degree of hydrolysis 99%) was investigated using MgH2 environmental catalyst and melt‐grown ring‐opening polymerization (ROP) of ε‐caprolactone (CL) and L ‐lactide (LA), that avoiding undesirable toxic catalyst and solvent. The ability of MgH2 as catalyst as well as yield of reaction were discussed according to various PVA/CL/MgH2 and PVA/LA/MgH2 ratio. PVA‐g‐PCL and PVA‐g‐PLA were characterized by 1H‐ and 13C‐NMR, DSC, SEC, IR. For graft copolymers easily soluble in tetrahydrofuran (THF) or chloroform, wettability and surface energy of cast film varied in relation with the length and number of hydrophobic chains. Aqueous solution of micelle‐like particles was realized by dissolution in THF then addition of water. Critical micelle concentration (CMC) decreased with hydrophobic chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

12.
Biodegradable poly[(2‐methacryloyloxyethyl phosphorylcholine)‐block‐(D ,L ‐lactide)] (PMPC‐b‐PLA) diblock copolymers with various hydrophilic PMPC weight fractions (fPC) will spontaneously self‐assemble into well‐defined vesicles and large compound micelles (LCMs) in water. Transmission electron microscopy, scanning electron microscopy, dynamic light scattering and fluorescence microscopy were used to observe their aggregate morphologies. The degradation of the LCMs was investigated and the loss of molecular weight of PLA blocks was confirmed using 1H NMR analysis. The hydrolysis of PLA increases fPC and consequently shifts the preferred morphology from LCMs to vesicles. Such degradation‐induced morphological transitions mean that the biocompatible and biodegradable LCMs have great application potential in drug delivery. Copyright © 2010 Society of Chemical Industry  相似文献   

13.
Ring‐opening polymerization of L ‐ or D ‐lactide was realized at 140 °C for a period of 7 days in the presence of dihydroxyl poly(ethylene glycol) (PEG), with M?n = 4000 g mol?1, using zinc lactate as initiator. The resulting poly(L ‐lactide)–PEG–poly(L ‐lactide) and poly(D ‐lactide)–PEG–poly(D ‐lactide) triblock copolymers are water soluble with polylactide (PLA) block length ranging from 11 to 17 units. Both the tube inverting method and rheological measurements were used to evaluate the gelation properties of aqueous solutions containing single copolymers or L /D copolymer pairs. Stereocomplexation between poly(L ‐lactide) and poly(D ‐lactide) blocks is observed for mixed solutions. Hydrogel formation is detected in the case of relatively long PLA blocks (DP PLA = 17), but not for copolymers with shorter PLA blocks (DP PLA = 11–13) due to partial racemization of L ‐lactyl units. Racemization is largely reduced when the reaction time is shortened to 1 day. Under these conditions, DP PLA of 8 is sufficient for the stereocomplexation of PLA–PEG block copolymers, and DP PLA above 10 leads to the formation of hydrogels of PLA–PEG block copolymers. On the other hand, racemization appears as a general phenomenon in the (co)polymerization of L ‐lactide with Zn(Lac)2 as initiator, although it is negligible or undetectable in the case of high molar mass polymers. Therefore, racemization is the limiting factor for the stereocomplexation‐induced gelation of water‐soluble PLA–PEG block copolymers where the PLA block length generally ranges from 10 to 30. Reaction conditions including initiator, time and temperature should be strictly controlled to minimize racemization. Copyright © 2010 Society of Chemical Industry  相似文献   

14.
A novel amphiphilic hydrogel based on poly(2‐methyl‐2‐oxazoline)‐b‐poly(dimethyl siloxane) (PMeOx–PDMS) block copolymer was developed. First of all, PMeOx–PDMS macromonomer was synthesized by coupling mono‐hydroxylated PMeOx with PDMS followed by end‐capping with methacrylate group. The structures of each step were characterized by NMR and titration. After that, silicone hydrogels were prepared by UV‐initiated copolymerization of PMeOx–PDMS macromonomer with monomers such as 2‐hydroxyethyl methacrylate in the presence of a crosslinker. Measurements of the hydrogels' water contact angle, equilibrium water content, and tensile properties showed that the hydrogels possessed better hydrophilic surface, higher water content, and better ion permeability with the increase of the content of the macromonomer PMeOx–PDMS. Meanwhile, the tensile strength and Young's modulus of the hydrogels decreased slightly. Protein adsorption tests showed that the hydrogels had strong antifouling ability after the incorporation of PMeOx. This newly described hydrogel demonstrated attractive properties to serve as ophthalmic biomaterial. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39867.  相似文献   

15.
A new mathematical model for the prediction of the heterogeneous hydrolytic degradation of poly(D,L‐lactide‐co‐glycolide) (PLGA)‐based microspheres was developed. The model takes into account the autocatalytic effect of carboxylic groups and polymer composition on the degradation rate. It is based on mass balances for the different species, considering the kinetic and mass transport phenomena involved. The model estimates the evolution of average molecular weight, mass loss, and morphological change of the particles during degradation, and it was validated with novel experimental data. Theoretical predictions are in agreement with the hydrolysis data of PLGA microspheres (error values less than 5%). The model is able to predict the effect of particle size and molecular weight on the degradation of PLGA‐based microspheres and estimates the morphological changes of the particles due to the autocatalytic effect. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45464.  相似文献   

16.
To reach sustained drug release, a new composite drug‐delivery system consisting of poly(d,l ‐lactide‐co‐glycolide) (PLGA) nanoparticles (NPs) embedded in thermosensitive poly(N‐isopropyl acrylamide) (PNIPAAm) hydrogels was developed. The PNIPAAm hydrogels were synthesized by free‐radical polymerization and were crosslinked with poly(ethylene glycol) diacrylate, and the PLGA NPs were prepared by a water‐in‐oil‐in‐water double‐emulsion solvent‐evaporation method. The release behavior of the composite hydrogels loaded with albumin–fluorescein isothiocyanate conjugate was studied and compared with that of the drug‐loaded neat hydrogel and PLGA NPs. The results indicate that we could best control the release rate of the drug by loading it to the PLGA NPs and then embedding the whole system in the PNIPAAm hydrogels. The developed composite hydrogel systems showed near zero‐order drug‐release kinetics along with a reduction or omission of initial burst release. The differential scanning calorimetry results reveal that the lower critical solution temperature of the developed composite systems remained almost unchanged (<1°C increase only). Such a characteristic indicated that the thermosensitivity of the PNIPAAm hydrogel was not distinctively affected by the addition of PLGA NPs. In conclusion, an approach was demonstrated for the successful preparation of a new hybrid hydrogel system having improved drug‐release behavior with retained thermosensitivity. The developed systems have enormous potential for many biotechnological applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40625.  相似文献   

17.
Supramolecular poly(?‐capolactone)/poly(lactide) alternating multiblock copolymers were prepared by UPy‐functionalized poly(lactide)‐b‐ poly(?‐capolactone)‐b‐ poly(lactide) copolymers. The prepared supramolecular polymers (SMPs) exhibit the characteristic properties of thermoplastic elastomers. The stereo multiblock SMPs (sc‐SMPs) were formed by blending UPy‐functionalized poly(l ‐lactide)‐b‐ PCL‐b‐ poly(l ‐lactide) (l ‐SMPs) and UPy‐functionalized poly(d ‐lactide)‐b‐ PCL‐b‐ poly(d ‐lactide) (d ‐SMPs) due to stereocomplexation of the PLLA and PDLA blocks. Sc‐SMPs with low content of d ‐SMPs (≤20%) are transparent, elastic solids, while those having high d ‐SMPs content are opaque, brittle solids. The effects of l ‐SMPs/d ‐SMPs mixing ratios on thermal, crystallization behaviors, crystal structure, mechanical and hydrophilic properties of sc‐SMPs were deeply investigated. The incorporation of UPy groups depresses the crystallization of polymer, and the stereocomplex formation accelerates the crystallization rate. The used initiator functionalized polyhedral oligomeric silsesquioxanes causes a different effect on the crystallization of PLA and PCL blocks. The tensile strength and elongation at break of l d /d d ‐SMPs (d represents the initiator diethylene glycol) are significantly larger than that of l p /d p ‐SMPs (p represents the initiator polyhedral oligomeric silsesquioxanes), and their heat resistance and hydrophilicity can be also modulated by the l ‐SMPs/d ‐SMPs mixing ratios and the different initiators. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45575.  相似文献   

18.
In this work, we report the synthesis and characterization of poly(butyl monoitaconate‐co‐acrylamide) hydrogels to be used as drug release agents. Four isomers of butanol were used to synthesize the hydrogels. The influence of butyl monoitaconate isomery on swelling behavior, Young's and compression moduli, cross‐linking density and molar mass between cross‐links are reported. It was found that by increasing butyl ramification, equilibrium degree of swelling, and the time for reaching swelling equilibrium decreases. Cross‐linking density, Young's and compression moduli increases as butyl ramification increases. The release of theophylline and aminophylline drugs used in therapy for respiratory diseases were studied and it was found that theophylline was released faster than aminophylline © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

19.
In this study, N‐vinylpyrrolidone(VP)/methacrylic acid (MAA) mixtures have been prepared at three different mole percents which the methacrylic acid composition around 5, 10, and 15%. Poly(N‐vinylpyrrolidone‐co‐methacrylicacid) P(VP/MAA) hydrogels irradiated at 3.4 kGy have been used for swelling and diffusion studies in water and uranyl ion solutions. The influence of dose, pH, relative amounts of monomers in MAA/VP monomer mixtures on the swelling properties have been investigated. P(VP/MAA) hydrogels were swollen in distilled water at pH 7.0. P(VP/MAA)1 hydrogel containing 36% (mole percent) methacrylic acid showed the maximum percent swelling in water. Adsorption isotherms were constructed for uranyl ions and P(VP/MAA) hydrogel systems. It has been found that P(VP/MAA) hydrogels have very high uptake of the uranyl ions succesfully in water containing uranyl ions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

20.
The effect of the mixing condition in a mill‐type mixer on the thermal property and the crystal formation of the poly(l ‐lactide)/poly(d ‐lactide) blends is investigated. The blends melt‐mixed at 200 and 210 °C under application of a high shear flow tend to show a single melting peak of the stereocomplex crystal (SC) in the differential scanning calorimetry first and second heating processes without indicating the trace of the melting of homo‐chiral crystal. The mixing at an elevated temperature causes a serious thermal degradation. Further kneading of the blends at an elevated temperature higher than Tm of SC causes the transesterification between the same enatiomeric chains forming block copolymers of l ‐ and d ‐chains. This block copolymer acts as a nucleating agent of SC and the compatibilizing agent between poly(l ‐lactide) and poly(d ‐lactide) and promotes the formation of SC. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45489.  相似文献   

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