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1.
The physical properties of poly(vinyl chloride) (PVC) and poly(N‐isopropylacrylamide) [poly(NIPAAm)] blend systems, and their corresponding graft copolymers such as PVC‐g‐NIPAAm, were investigated in this work. The compatible range for PVC–poly(NIPAAm) blend systems is less than 15 wt % poly(NIPAAm). The water absorbencies for the grafted films increase with increase in graft percentage. The water absorbencies for the blend systems increase with increase in poly(NIPAAm) content within the compatible range for the blends, but the absorbencies decrease when the amount of poly(NIPAAm) is more than the compatible range in the blend system. The tensile strengths for the graft copolymers are larger than the corresponding blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 170–178, 2000  相似文献   

2.
Polysaccharide‐based hydrogels, such as xanthan maleate/poly(N‐isopropylacrylamide) (PNIPAAm) interpenetrated polymer networks, are thermostimulable materials of interest for the controlled release of biologically active components due to conformation changes at the low critical‐solution temperature (LCST) PNIPAAm phase transition. The phase transition of these interpenetrated polymer network hydrogels, where PNIPAAm is in a ‘confined’ environment, was examined by high resolution magic angle spinning nuclear magnetic resonance and differential scanning calorimetry. High resolution magic angle spinning nuclear magnetic resonance spectroscopy allows the accurate determination of LCST and an evaluation of the corresponding thermodynamic data. More particularly, the evolution of these data as a function of the composition of the hydrogel, and of the external parameters such as pH and ionic strength, was considered. LCST shows a minimal value with increasing xanthan content. Moreover, it was possible to calculate, as a function of temperature, the fraction of NIPAAm which remains uncollapsed. The data obtained for pure PNIPAAm hydrogels are in good agreement with recently published results. The phase transition of PNIPAAm in a diphasic hydrogel is broader when PNIPAAm is ‘confined’ within an interpenetrated polymer network than in a pure PNIPAAm crosslinked network. The widening of the transition with increasing xanthan content indicates a reduction of the PNIPAAm interchain aggregation in a network structure. Copyright © 2011 Society of Chemical Industry  相似文献   

3.
Stimuli‐responsive biocompatible and biodegradable materials can be obtained by combining polysaccharides with polymers exhibiting lower critical solution temperature (LCST) phase behavior, such as poly(N‐isopropylacrylamide) (PNIPAAm). The behavior of aqueous solutions of sodium alginate (NaAl) grafted with PNIPAAm (NaAl‐g‐PNIPAAm) copolymers as a function of composition and temperature is presented. The products obtained exhibit a remarkable thermothickening behavior in aqueous solutions if the degree of grafting, the concentration, and the temperature are higher than some critical values. The sol–gel‐phase transition temperatures have been determined. It was found that at temperatures below LCST the systems behave like a solution, whereas at temperatures above LCST, the solutions behave like a stiff gel, because of PNIPAAm segregation. This behavior is reversible and could find applications in tissue engineering and drug delivery systems. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

4.
The synthesis of a thermoresponsive graft copolymer consisting of a maleic acid/vinyl acetate alternating copolymer backbone (MAc‐alt‐VA) and poly(N‐isopropylacrylamide) (PNIPAM) side chains is reported. Turbidimetric measurements in dilute aqueous solutions showed that no macroscopic phase separation takes place when the temperature is raised above the lower critical solution temperature (LCST) of PNIPAM, even at pH = 2. Moreover, in semi‐dilute aqueous solutions, a pronounced thermally induced viscosity increase (thermothickening) was observed. This thermoresponsive behaviour has been attributed to the interconnection of the hydrophilic MAc‐alt‐VA graft copolymer backbones by means of the hydrophobic PNIPAM side chain aggregates formed as the temperature increases above the LCST of this polymer. Copyright © 2004 Society of Chemical Industry  相似文献   

5.
The in‐vitro hydrolytic behavior of diblock copolymer films consisting of poly(ε‐caprolactone) (PCL) and poly(ethylene glycol) (PEG) was studied at pH 7.4 and pH 9.5 at 37°C. The degradation of these films was characterized at various time intervals by mass loss measurements, GPC, 1H‐NMR, DSC, FTIR, XRD, and SEM. A faster rate of degradation took place at pH 9.5 than at pH 7.4. Analysis of the molecular weight profile during the course of degradation revealed that random chain scission of the ester bonds in PCL predominates at the initial induction phase of polymer degradation. There was also an insignificant mass loss of the films observed. Mass spectroscopy was used to determine the nature of the water soluble products of degradation. At pH 7.4, a variety of oligomers with different numbers of repeating units were present whereas the harsher degradation conditions at pH 9.5 resulted in the formation of dimers. From the results, it can be proposed that a more complete understanding of the degradation behavior of the PCL‐b‐PEG copolymer can be monitored using a combination of physiological and accelerated hydrolytic degradation conditions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

6.
pH and thermo‐responsive graft copolymers are reported where thermo‐responsive poly(N‐isopropylacrylamide) [poly(NIPAAm), poly A ], poly(N‐isopropylacrylamide‐co‐2‐(diethylamino) ethyl methacrylate) [poly(NIPAAm‐co‐DEA), poly B ], and poly(N‐isopropylacrylamide‐co‐methacrylic acid) [poly(NIPAAm‐co‐MAA), poly C ] have been installed to benzaldehyde grafted polyethylene glycol (PEG) back bone following introducing a pH responsive benzoic‐imine bond. All the prepared graft copolymers for PEG‐g‐poly(NIPAAm) [ P‐N1 ], PEG‐g‐poly(NIPAAm‐co‐DEA) [ P‐N2 ], and PEG‐g‐poly(NIPAAm‐co‐MAA) [ P‐N3 ] were characterized by 1H‐NMR to assure the successful synthesis of the expected polymers. Molecular weight of all synthesized polymers was evaluated following gel permeation chromatography. The lower critical solution temperature of graft copolymers varied significantly when grafted to benzaldehyde containing PEG and after further functionalization of copolymer based poly(NIPAAm). The contact angle experiment showed the changes in hydrophilic/hydrophobic behavior when the polymers were exposed to different pH and temperature. Particle size measurement investigation by dynamic light scattering was performed to rectify thermo and pH responsiveness of all prepared polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

7.
Amphiphilic thermally sensitive poly(N‐isopropylacrylamide)‐block‐poly(tetramethylene carbonate) block copolymers were synthesized by ring‐opening polymerization of tetramethylene carbonate with hydroxyl‐terminated poly(N‐isopropylacrylamide) (PNiPAAm) as macro‐initiator in the presence of stannous octoate as catalyst. The synthesis involved PNiPAAm bearing a single terminal hydroxyl group prepared by telomerization using 2‐hydroxyethanethiol as a chain‐transfer agent. The copolymers were characterized using 1H NMR and Fourier transform infrared spectroscopy and gel permeation chromatography. Their solutions show reversible changes in optical properties: transparent below the lower critical solution temperature (LCST) and opaque above the LCST. The LCST depends on the polymer composition and the media. Owing to their amphiphilic characteristics, the block copolymers form micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range 1.11–22.9 mg L?1. Increasing the hydrophobic segment length or decreasing the hydrophilic segment length in the amphiphilic diblock copolymers produces lower CMCs. A core‐shell structure of the micelles is evident from 1H NMR analyses of the micelles in D2O. Transmission electron microscopic analyses of micelle morphology show a spherical structure of both blank and drug‐loaded micelles. The blank and drug‐loaded micelles have an average size of less than 130 nm. Observations show high drug‐entrapment efficiency and drug‐loading content for the drug‐loaded micelles. Copyright © 2010 Society of Chemical Industry  相似文献   

8.
The ring‐opening polymerization of ε‐caprolactone was carried out with poly(ethylene‐co‐vinyl alcohol) as a macroinitiator to synthesize poly(ethylene‐co‐vinyl alcohol)‐graft‐polycaprolactone (EVOH‐g‐PCL). A simple low‐density polyethylene (LDPE)/polycaprolactone (PCL) (64/36) blend lost 5.3 wt % of its original weight after 90 days of a soil burial test. However, the elongation at break of the LDPE/PCL blend remained almost invariable even after the solid burial test because the tensile properties depended mostly on the LDPE phase on account of the poor interaction between the continuous LDPE matrix and the dispersed PCL phase. For EVOH‐g‐PCL, the elongation at break decreased drastically as a result of the soil burial test, and the reduction of the elongation at break was more pronounced for EVOH‐g‐PCL with a higher PCL concentration, even though the weight loss of EVOH‐g‐PCL after the soil burial test was as low as 1.2–1.3% and was nearly independent of the PCL concentration. Few holes were observed in EVOH‐g‐PCL when the PCL concentration was less than 26 wt % after an accelerated hydrolysis experiment at 60°C for 7 days in a 0.1M KOH solution. In contrast, the hydrolysis formed small holes in EVOH‐g‐PCL with a PCL concentration of 36 wt %. The LDPE/PCL blend was much better percolated, as a result of the hydrolysis, than EVOH‐g‐PCL with the same PCL concentration; the soil burial test showed the same results. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1064–1071, 2005  相似文献   

9.
BACKGROUND: A series of novel biodegradable poly[(sebacic anhydride)‐co‐caprolactone] (PSA‐co‐PCL) triblock copolymers were prepared by melt condensation of acylated PSA and monofunctional hydroxyl‐terminated PCL prepolymers. These copolymers could be used as novel drug delivery carriers with expected good drug permeability due to the PCL component. The degradation rate and mode can be modulated by varying the ratio of monomers in the copolymer. RESULTS: The homopolymers and copolymers were characterized using 1H NMR, gel permeation chromatography and differential scanning calorimetry (DSC). 1H NMR confirmed the formation of triblock copolymers that comprise a middle PSA block and two side PCL blocks. DSC revealed that the melting temperature and degree of crystallinity for both sebacic anhydride (SA) and caprolactone (CL) components are strongly composition dependent, implying the hindrance effect of the two components on the crystallinity. In vitro degradation experiments showed that the mass loss is significantly accelerated for samples in base buffer solution and more rapid for the copolymers with a higher SA content. Scanning electron microscopy revealed that for SA‐rich copolymer, PSA(80 wt%)‐co‐PCL, surface erosion dominated the degradation mode of the sample. In contrast, for CL‐rich copolymer, PSA(20 wt%)‐co‐PCL, a micropore structure developed at a degradation time of 155 h along the edges of the sample, owing to the hydrolysis of SA. CONCLUSION: It is concluded that the rate and mode of degradation of these copolymers can be tuned by varying the composition of the copolymers. Copyright © 2007 Society of Chemical Industry  相似文献   

10.
Thermal analysis of EVOH copolymers with different ethylene content, were performed by TGA/DTGA under dynamic conditions. Apparent kinetic parameters were determined using different classical kinetic approaches. The apparent activation energy values obtained confirm that thermal stability of EVOH increases with ethylene content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3157–3163, 2003  相似文献   

11.
Thermoresponsive graft copolymers of ε‐caprolactone and N‐isopropylacrylamide were synthesized by a combination of ring‐opening polymerization and the sequential atom transfer radical polymerization (ATRP). The copolymer composition, chemical structure, and the self‐assembled structure were characterized. The graft length and density of the copolymers were well controlled by varying the feed ratio of monomer to initiator and the fraction of chlorides along PCL backbone, which is acting as the macroinitiator for ATRP. In aqueous solution, PCL‐g‐PNIPAAm can assemble into the spherical micelles which comprise of the biodegradable hydrophobic PCL core and thermoresponsive hydrophilic PNIPAAm corona. The critical micelle concentrations of PCL‐g‐PNIPAAm were determined under the range of 6.4–23.4 mg/L, which increases with the PNIPAAm content increasing. The mean hydrodynamic diameters of PCL‐g‐PNIPAAm micelles depend strongly on the graft length and density of the PNIPAAm segment, allowing to tune the particle size within a wide range. Additionally, the PCL‐g‐PNIPAAm micelles exhibit thermosensitive properties and aggregate when the temperature is above the lower critical solution temperature. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41115.  相似文献   

12.
Several different composition temperature‐ and pH‐sensitive poly(acrylic acid‐gN‐isopropylacrylamide) (P(AA‐g‐NIPAM)) graft copolymers were synthesized by free‐radical copolymerization utilizing macromonomer technique. The phase behavior and conformation change of P(AA‐g‐NIPAM) in aqueous solutions were investigated by UV–vis transmittance measurements, fluorescence probe, and fluorescence quenching techniques. The results demonstrate that the P(AA‐g‐NIPAM) copolymers have temperature‐ and pH‐sensitivities, and these different composition graft copolymers have different lower critical solution temperature (LCST) and critical phase transition pH values. The LCST of graft copolymer decreases with increasing PNIPAM content, and the critical phase transition pH value increases with increasing Poly(N‐isopropylacrylamide) (PNIPAM) content. At room temperature (20°C), different composition of P(AA‐g‐NIPAM) graft copolymers in dilute aqueous solutions (0.001 wt %) have a loose conformation, and there is no hydrophobic microdomain formation within researching pH range (pH 3 ~ 10). In addition, for the P(AA‐g‐NIPAM) aqueous solutions, transition from coil to globular is an incomplete reversible process in heating and cooling cycles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

13.
Unreported graft copolymer of 2‐acrylamido‐2‐methyl‐1‐propanesulphonic acid (AMPS) with sodium carboxymethylcellulose (Na‐CMC) was synthesized and reaction conditions were optimized using a bromate/thiourea redox pair under an inert atmosphere at 40°C. Grafting ratio, add on, and conversion increase as the concentration of thiourea and [H+] increases up to 3.6 × 10?3 and 0.6 × 10?2 mol dm?3, respectively, while on increasing the concentration of bromate ion and Na‐CMC, grafting ratio, add on, and conversion decrease. The samples of Na‐CMC and grafted Na‐CMC with AMPS were subjected to thermogravimetric analysis, with the objective of studying the effect of grafting of AMPS on the thermal stability of graft copolymer. The graft copolymer was found to be more thermally stable than pure Na‐CMC. Comparing the IR spectra of pure with grafted Na‐CMC confirm the evidence of grafting. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 100: 26–34, 2006  相似文献   

14.
Beads composed of alginate, poly(N‐isopropylacrylamide) (PNIPAM), the copolymers of N‐isopropylacrylamide and methacrylic acid (P(NIPAM‐co‐MAA)), and the copolymers of N‐isopropylacrylamide, methacrylic acid, and octadecyl acrylate (P(NIPAM‐co‐MAA‐co‐ODA)), were prepared by dropping the polymer solutions into CaCl2 solution. The beads were freeze‐dried and the release of blue dextran entrapped in the beads was observed in distilled water with time and pH. The degree of release was in the order of alginate bead < alginate/PNIPAM bead ≈ alginate/P(NIPAM‐co‐MAA) bead < alginate/P(NIPAM‐co‐MAA‐co‐ODA) bead. On the other hand, swelling ratios reached steady state within 20 min, and the values were 200–800 depending on the bead composition. The degree of swelling showed the same order as that of release. Among the beads, only alginate/P(NIPAM‐co‐MAA‐co‐ODA) bead exhibited pH‐dependent release. At acidic condition, inter‐ and intraelectrostatic repulsion is weak and P(NIPAM‐co‐MAA‐co‐ODA) could readily be assembled into an aggregate due to the prevailing hydrophobic interaction of ODA. Thus, it could block the pore of bead matrix, leading to a suppressed release. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

15.
The thermoresponsive properties in aqueous solution of the graft copolymer poly(acrylic acid‐co‐2‐acrylamido‐2‐methyl propane sulfonic acid)‐g‐poly(N‐isopropylacrylamide) [P(AA‐co‐AMPSA)‐g‐PNIPAM] were studied and compared to the corresponding behavior of the poly(acrylic acid)‐g‐poly(N‐isopropylacrylamide) (PAA‐g‐PNIPAM) graft product. Both products contain about 40% (w/w) of PNIPAM, whereas the backbone, P(AA‐co‐AMPSA), of the first copolymer contains about 40% of AMPSA mole units. The strongly charged P(AA‐co‐AMPSA)‐g‐PNIPAM graft copolymer was water soluble over the whole pH range, whereas the PAA‐g‐PNIPAM copolymer precipitated out from water at pH < 4. As a result, the first product exhibited a temperature‐sensitive behavior in a wide pH range, extended in the acidic region, whereas in semidilute aqueous solutions, an important thermothickening behavior was observed, even at low pH (pH = 3.0). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3466–3470, 2004  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.
It is indispensable to investigate hydrolytic degradation behavior to develop novel (bio)degradable polyesters. Biobased and biodegradable copolyesters poly(butylene adipate‐co ‐butylene furandicarboxylate) (PBAF) and poly(butylene succinate‐co ‐butylene furandicarboxylate) (PBSF) with BF molar fraction (?BF) between 40 and 60% were synthesized in this study. The hydrolytic degradation of film samples was conducted in a pH 7.0 PBS buffer solution at 25 °C. Slight mass loss (1–2%) but significant decrease in intrinsic viscosity (35–44%) was observed after 22 weeks. The apparent hydrolytic degradation rate decreased with increasing ?BF and initial crystallinity. Meanwhile, PBAFs degraded slightly faster than PBSFs with the same composition. The ?BF and crystallinity increased slowly with degradation time, suggesting the aliphatic moiety and the amorphous region are more susceptible to hydrolysis. And high enough tensile properties were retained after hydrolysis degradation, indicating PBAF and PBSF copolyesters are hydrolytically degradable, with tunable hydrolytic degradation rate and good balance between hydrolytic degradability and durability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44674.  相似文献   

18.
Poly(butylene terephthalate)‐co‐poly(butylene succinate)‐block‐poly(ethylene glycol) segmented random copolymers, with poly(butylene succinate) (PBS) molar fraction (MPBS) varying from 10 to 60 %, were synthesized through a melt polycondensation process and characterized by means of GPC, NMR, DSC and mechanical testing. The number‐average relative molecular mass of the copolymers was higher than 4 × 104 g mol?1 with polydispersity below 1.9. Sequence distribution analysis on the two types of hard segments by means of 1H NMR revealed that the number‐average sequence length of PBT decreased from 2.80 to 1.23, while that of PBS increased from 1.27 to 4.76 with increasing MPBS. The random distribution of hard segments was also justified because of the degree of randomness around 1.0. Micro‐phase separation structure was verified for the appearance of two glass transition temperatures and two melting points, respectively, in DSC thermograms of most samples. The crystallinity of hard segments changed with the crystallizability controlled by the average sequence length and reached the minimum value at an MPBS of about 50–60 mol%. The results can also be ascribed to the co‐crystallization between two structurally analogous hard segments. Mechanical testing results demonstrated that incorporating a certain amount of PBS moieties (less than 30 mol%), at the expense of a minute depression of the elastic modulus, that higher relative elongation and more flexibility of polymer chain could be expected. Maximum equilibrium water absorption and faster degradation rates were observed on samples with higher MPBS values and lower crystallinity of hard segments were better hydrophilicity of the polymer chain, through in vitro degradation experiments. Copyright © 2003 Society of Chemical Industry  相似文献   

19.
Mixed‐interpenetrated polymeric networks based on sodium alginate (ALG) and poly(N‐isopropylacryl amide) (PNIPAAm) covalently cross‐linked with N,N'‐methylenebisacrylamide are studied for their biocompatibility, nontoxicity, and biodegradability aiming their application in drug delivery. The presence of drug‐polymeric matrix interactions and the distribution of the drug in the polymeric network for theophylline‐loaded ALG/PNIPAAm hydrogels are also investigated by spectroscopic and microscopic methods. The quantitative evaluation of theophylline loaded hydrogels performed by NIR‐CI technique shows a better drug entrapment and a higher homogeneity of the samples with increased alginate content. The thermal behavior of the hydrogels is significantly modified by theophylline presence. The application of the ALG/PNIPAAm hydrogels as carriers for sustained drug release formulations was assessed by the theophylline release tests performed both by in vitro and in vivo studies. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40733.  相似文献   

20.
In the present work, we report on the synthesis and characterization of poly(vinylidene fluoride) (PVDF) with N‐isopropylacrylamide (NIPAAM) polymer side chains from molecular graft copolymerization in solution. The copolymer can be readily cast into temperature‐sensitive microfiltration (MF) membranes by the phase inversion technique. The copolymer approach to membrane fabrication allows a much better control of the physicochemical nature of the membrane pores through the variation in graft concentration, membrane casting temperature and concentration of the membrane casting solution.

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