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1.
Semi‐interpenetrating polymer networks (semi‐IPNs) composed of a dicyanate resin and a poly(ether sulfone) (PES) were prepared, and their curing behavior and mechanical properties were investigated. The curing behavior of the dicyanate/PES semi‐IPN systems catalyzed by an organic metal salt was analyzed. Differential scanning calorimetry was used to study the curing behavior of the semi‐IPN systems. The curing rate of the semi‐IPN systems decreased as the PES content increased. An autocatalytic reaction mechanism was used to analyze the curing reaction of the semi‐IPN systems. The glass‐transition temperature of the semi‐IPNs decreased with increasing PES content. The thermal decomposition behavior of the semi‐IPNs was investigated. The morphology of the semi‐IPNs was investigated with scanning electron microscopy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1079–1084, 2003  相似文献   

2.
A series of novel semi‐2‐interpenetrating polymeric networks (semi‐2‐IPNs) were prepared through blending in solution using two different polyimides, biscitraconamic acid as a precursor of biscitraconimide (MBMI) with various proportions of polyetherimide (PEI) to achieve optimum properties. Biscitraconamic acid was prepared by reacting citraconic anhydride (CA), 3,3',4,4'‐benzophenone tetracarboxylic dianhydride (BTDA) and bis(3‐aminopropyl)phenyl phosphine (BAPPP) and it was characterized by differential scanning calorimetry (DSC), FTIR, and 1H‐NMR spectroscopy. Both biscitraconamic acid and PEI were blended in N,N‐dimethylacetamide (DMAc) solution, casted and thermally cured up to 300°C to give semi‐2‐IPNs. The MBMI/PEI semi‐IPN systems were characterized by UV‐Vis spectroscopy, FTIR spectroscopy and thermal techniques. The phase morphology, isothermal aging, and water uptake of semi‐IPN systems have also been studied. The morphological studies on phase distribution were investigated by scanning electron microscopy (SEM). Thermal performance of MBMI/PEI semi‐IPN systems were evaluated by DSC and thermo gravimetric analysis (TGA). All the compositions of semi‐IPN polyimide system were stable up to 400°C and their thermal stability increased with increase in the content of PEI. Isothermal aging studies done at 300°C for various time periods showed good thermo‐oxidative stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

3.
Norman R. Horn 《Polymer》2011,52(7):1619-5594
Recent studies have shown that thin glassy polymer films undergo physical aging more rapidly than thick films. This suggests that thickness may also play a role in the plasticization and conditioning responses of thin glassy films in the presence of highly-sorbing penetrants such as CO2. In this paper, a carefully designed systematic study explores the effect of thickness on the CO2 plasticization and conditioning phenomena in Matrimid®, a polyimide commonly used in commercial gas separation membranes. Thin films are found to be more sensitive than thick films to CO2 exposure, undergoing more extensive and rapid plasticization at any pressure. The response of glassy polymers films to CO2 is not only dependent on thickness, but also on aging time, CO2 pressure, exposure time, and prior history. Finally, thin films experiencing constant CO2 exposure for longer periods of time exhibit an initial large increase in CO2 permeability, which eventually reaches a maximum, followed by a significant decrease in permeability for the duration of the experiment. Thick films, in contrast, do not seem to exhibit this trend for the range of conditions explored.  相似文献   

4.
Semi‐interpenetrating polymer networks (semi‐IPN) formed with commercial polyether imide (ULTEM®, PEI) and poly (ethylene glycol) diacrylate (PEGDA) were used to make asymmetric membranes. The effect of increasing amount of PEGDA on the bulk and the gas separation properties of semi‐IPN membranes were studied. The formation of IPNs was confirmed by Fourier Transform Infra Red (FT‐IR) spectroscopy. The 5% weight loss temperature decreased and the percent weight loss of the first step increased with increase in the PEGDA content, which indicated the incorporation of more poly (ethylene glycol) (PEG) segments to the semi‐IPNs. The microscopic experiments revealed the change in morphology with change in PEGDA content. The Scanning electron micrographs exhibited typical finger‐like voids in the sub layer, which is characteristic morphology of asymmetric membranes. The increase in PEGDA content up to 5.7 wt % increased the CO2/N2 selectivity of the semi‐IPN after which the selectivity decreased and permeance increased. Although, the increase in the polar poly (ethylene glycol) molecules is expected to render better CO2 selectivity, the performance of the membrane was found to decrease as PEGDA content exceeded 5.7% for the given ratio. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

5.
A novel fluorine‐containing telechelic polyimide end‐capped with acetylene group which derived from 4,4‐(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 3,4‐diaminodiphenyl ether (DADE), and 4‐(2‐phenylethynyl) phthalic anhydride (PEPA) was synthesized using polycondensation. The physical and CO2 permeation properties of its crosslinked membranes prepared by the cyclotrimerization reaction of the acetylene groups at the polymer chain end using tantalum (V) chloride (TaCl5) as a catalyst under thermal treatment was investigated in terms of CO2‐induced membrane plasticization. The crosslinked membranes showed a gel content in organic solvent, which was good solvent of noncrosslinked membranes, and improved their thermal stability. Based on the measurement of the high‐pressure time dependence on CO2 permeation, the crosslinked 6FDA–DADE–PEPA membranes exhibited more resistance to CO2‐induced plasticization than noncrosslinked 6FDA–DADE and thermal treated 6FDA–DADE–PEPA. Furthermore, the increase in TaCl5 content resulted in more resistance to plasticization. The cyclotrimerization reaction of the acetylene groups at the polymer chain ends using a transition metal catalyst under thermal treatment was found to be more effective than conventional thermal treatments for suppressing membrane plasticization without the membrane densification. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers  相似文献   

6.
The curing behavior and physical properties of dicyanate/polyetherimide (PEI) semi‐interpenetrating polymer network (IPN) systems were investigated. Differential scanning calorimetry (DSC) was used to study the curing behavior of the dicyanate/PEI semi‐IPN systems. The curing rate of the semi‐IPN system decreased as the PEI content increased. An autocatalytic reaction mechanism can describe well the curing kinetics of the semi‐IPN systems. The reaction kinetic parameters were determined by fitting DSC conversion data to the kinetic equation. The glass transition temperature of the semi‐IPNs decreased with increasing PEI content. Two glass transitions due to phase‐separated morphology were observed for the semi‐IPN containing over 15 phr (parts per hundred parts of dicyanate resin) PEI. The thermal stability and dynamic mechanical properties of the semi‐IPNs were measured by thermal analysis.  相似文献   

7.
A series of novel sulfonated polyimide (SPI)/crosslinked poly(N‐isopropylacrylamide) (cPNIPAm) semi‐interpenetrating polymer networks (semi‐IPNs) were synthesized as the proton exchange membranes for direct methanol fuel cells via in situ polymerization. The micromorphology and properties of the semi‐IPN membranes were characterized. The results indicated that the hydrogen bonds between cPNIPAm and SPI in the semi‐IPN structure were a crucial factor for regulating the micromorphology, proton conductivity and other properties of the semi‐IPN membranes. A more uniform sulfonic ionic cluster distribution was observed in the membrane of SPI‐20‐cPNIPAm with equimolar ratio of sulfonic acid groups and amido bonds, which could provide effective proton transport channels. The SPI‐20‐cPNIPAm exhibited a maximum proton conductivity of 0.331 S cm?1 at 80 oC (relative humidity 100%), an optimal selectivity of 8.01 × 105 S s cm?3 and an improved fuel cell performance of 72 mW cm?2 compared with both pristine SPI and other semi‐IPN membranes. The SPI‐20‐cPNIPAm semi‐IPN membranes also retained good mechanical properties and thermal stabilities on the whole. © 2014 Society of Chemical Industry  相似文献   

8.
A novel semi‐interpenetrating polymer networks (semi‐IPNs) porous salt‐resistant superabsorbent composite was prepared by copolymerization of partially neutralized acrylic acid and acrylamide using polyethylene glycol as semi‐IPNs composite, N,N′‐methylenebisacrylamide, triene propanol phosphate, and trihydroxymethyl propane glycidol ether as crosslinking agents, methanol, propanol, and butanol as foaming agents, and L ‐ascorbic acid and peroxide hydrogen as initiators. To improve the properties of swollen hydrogel, such as strength, resilience, permeabilities, and dispersion, the copolymer was surface‐crosslinked, and then blended with aluminum sulfate, sodium carbonate, and sodium 1‐octadecanol phosphate in the course of post treatment. The influences of reaction conditions on properties of superabsorbent composite were investigated and optimized, and the water absorbency of superabsorbent composite prepared at optimal conditions in 0.9 wt% NaCl aqueous solution under atmospheric pressure and certain load (P ≈ 2 × 103 Pa) were 61 g g?1 and 16.7 g g?1, respectively. Moreover, the swelling rate reached 22.003 × 10?3 g (g s)?1. And the excellent hydrogel properties, such as hydrogel strength, resilience, permeabilities, and dispersion were also obtained. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers  相似文献   

9.
Poly(N‐isopropylacrylamide) (PNIPAAm)/poly(ethylene oxide) (PEO) semi‐interpenetrating polymer networks (semi‐IPNs) synthesized by radical polymerization of N‐isopropylacrylamide (NIPAAm) in the presence of PEO. The thermal characterizations of the semi‐IPNs were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). The melting temperature (Tm) of semi‐IPNs appeared at around 60°C using DSC. DEA was employed to ascertain the glass transition temperature (Tg) and determine the activation energy (Ea) of semi‐IPNs. From the results of DEA, semi‐IPNs exhibited one Tg indicating the presence of phase separation in the semi‐IPN, and Tgs of semi‐IPNs were observed with increasing PNIPAAm content. The thermal decomposition of semi‐IPNa was investigated using TGA and appeared at around 370°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3922–3927, 2003  相似文献   

10.
Temperature‐ and pH‐sensitive interpenetrating polymer networks (IPNs) and semi‐interpenetrating polymer networks (s‐IPNs) were γ‐ray grafted onto polyurethane (Tecoflex®; TFX) to obtain vancomycin‐eluting implantable medical devices with minimized risk of infections. N‐isopropylacrylamide (NIPAAm) was grafted onto TFX catheters and films via a preirradiation oxidative method (method P) or via a direct method (method D). The PNIPAAm network facilitated acrylic acid (AAc) inclusion and subsequent polymerization/crosslinking, under specific reaction conditions. IPNs and s‐IPNs systems were characterized regarding the amount of grafted polymers, surface properties (FTIR‐ATR, ESEM, EDX), thermal behavior (DSC), and their temperature‐ and pH‐responsiveness. Loading and release of vancomycin for preventing in vitro growth of Staphylococcus aureus were also evaluated. Antimicrobial activity tests and hemo‐ (hemolysis, protein adsorption, thrombogenicity) and cyto‐compatibility (cell viability and production of cytokines and NO) assays indicated that the modification of TFX by γ‐radiation may improve the performance of polyurethanes for biomedical applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39992.  相似文献   

11.
A new series of semi‐conducting interpenetrating polymer networks (IPNs) based on pyridine and poly(antimony acrylate) were synthesized. Structural evidence for IPNs come from the infrared spectra indicating characteristic frequencies of (>C = O) of poly(antimony acrylate) at 1680 cm?1. Properties such as percentage swelling, average molecular weight between crosslinks (Mc) and Young's modulus are direct functions of the concentration of linear polymer and initiator (benzoyl peroxide), whereas inverse relationships with concentration of monomer (pyridine) and crosslinker (divinyl benzene) are observed. The presence of antimony in the IPNs is determined by SEM and elementac analysis. The DSC curve shows two glass transition temperatures (Tg), at 110 and 150 °C. The IPNs formed with a low content of pyridine exhibited processability, mechanical properties and conductivity. © 2003 Society of Chemical Industry  相似文献   

12.
We investigated the stress–strain behavior of low molecular weight polycarbonate for optical disc grade (OD‐PC) under carbon dioxide (CO2) at various pressures, and compared the results with that under ambient pressure at various temperatures. Elongation at break decreased sharply with increased CO2 pressure at around 2 MPa, while the elastic modulus decreased gradually up to 6 MPa. These results indicate that the tensile property changed from ductile to brittle with increased CO2 pressure, although the molecular motion is accelerated due to the plasticization effect of CO2. Such ductile‐to‐brittle transition is similar to that observed under elevated temperatures caused by chain disentanglement due to accelerated molecular motion. Although the changes of tensile properties were similar, the craze structure obtained by the brittle behavior was different, i.e., a filamented‐craze structure was obtained under high‐pressure CO2, while a lace‐like one was obtained under elevated temperatures. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers  相似文献   

13.
Hydrogels with environment‐sensitive properties have great potential applications in the controlled drug release field. In this paper, hybrid hydrogels with semi‐interpenetrating polymer networks (semi‐IPNs), composed of poly(N‐isopropylacrylamide) (PNIPAM) as the thermo‐sensitive component by in situ polymerization and self‐assembled collagen nanofibrils as the pH‐sensitive framework, were prepared for controlled release of methyl violet as a model drug. From Fourier transform infrared spectroscopy and scanning electron microscopy, it was indicated that the crosslinking of PNIPAM in the presence of collagen nanofibrils led to the formation of semi‐IPNs with homogeneous porous structure, and the semi‐IPNs showed improved thermal stability and elastic properties compared with the native collagen as determined using differential scanning calorimetry and rheologic measurements. Furthermore, the semi‐IPNs possessed swelling behaviors quite different from those of neat collagen or PNIPAM hydrogel under various pH values and temperatures. Correspondingly, as expected, the drug release behavior in vitro for semi‐IPNs performed variously compared with that for single‐component semi‐IPNs, which revealed the tunable performance of semi‐IPNs for release ability. Finally the thermo‐ and pH‐responsive mechanism of the semi‐IPNs was illuminated to provide guidance for the application of the thermo‐ and pH‐sensitive collagen‐based hybrid hydrogels in controlled drug delivery systems. © 2019 Society of Chemical Industry  相似文献   

14.
The commercially available linear polyimide Matrimid® 9725 was crosslinked with amino groups containing both high‐molecular‐weight and low‐molecular‐weight compounds. The multi‐functional amine‐terminated hyperbranched polyimide precursor (hyperbranched polyamic acid), based on 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride and 4,4′,4″‐triaminotriphenylmethane, and its fully imidized form (amine‐terminated hyperbranched polyimide), bifunctional amine, 4,4′‐diaminodiphenylamine and trifunctional amine, 4,4′,4″‐triaminotriphenylamine, were used as the crosslinkers. Theoretically, 10% or 20% of the Matrimid imide groups was reacted with the amino groups of the crosslinking agent during the formation of the amide groups. The insoluble content (gel) in the final materials was very low at the crosslinking temperature of 80°C and was in the 55–90% range at the crosslinking temperature of 200°. The permeability coefficients of hydrogen, carbon dioxide and methane in the self‐standing, mechanically tough film (membrane) based on the combination of Matrimid and hyperbranched polyimide were approximately 30–45% higher compared with those in the membrane made of pure Matrimid at a comparable separating ability (selectivity). POLYM. ENG. SCI., 57:1367–1373, 2017. © 2017 Society of Plastics Engineers  相似文献   

15.
A novel semi‐interpenetrating poly(2‐hydroxyethyl methacrylate) (pHEMA) based polyelectrolyte hydrogel [p(HEMA‐co‐METAC)/PEG] was prepared by copolymerizing HEMA with the cationic monomer 2‐methacryloyloxyethyltrimethyl ammonium chloride (METAC) in the presence of polyethylene glycol (PEG) with different content and molecular weight (MW 4000 and 400). The chemical structure of the gels was confirmed by FT‐IR spectroscopy, morphology study was performed by scanning electron microscope (SEM), thermal stability was revealed by thermogravimetric analysis (TGA), and the mechanical properties were determined by electronic universal testing machine. Swelling studies showed introduction of cationic monomer METAC led to high water content, and the obvious salt and pH sensitive properties were observed which proved the smart behavior of the semi‐interpenetrating polymer networks (IPNs) gels. In addition, the effect of temperature and some important biological solution on swelling behavior were reported. Cytotoxicity test demonstrated that synthesized gels owned satisfactory cytocompatibility and were convenient for the application as biomaterials. Finally, the weak bovine serum albumin (BSA) adsorption on semi‐IPNs by introducing METAC and controlling the content of PEG in gels demonstrated that they were of good protein resistance effect in biomedical applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41537.  相似文献   

16.
Semi‐interpenetrating polymer networks (semi‐IPNs) based on crosslinked polyurethane (PU) and linear polyvinylpyrrolidone (PVP) were synthezised, and their thermal and dynamic mechanical properties and dielectric relaxation behavior were studied to provide insight into their structure, especially according to their composition. The differential scanning calorimetry results showed the glass transitions of the pure components: one glass‐transition temperature (Tg) for PU and two transitions for PVP. Such glass transitions were also present in the semi‐IPNs, whatever their composition. The viscoelastic properties of the semi‐IPNs reflected their thermal behavior; it was shown that the semi‐IPNs presented three distinct dynamic mechanical relaxations related to these three Tg values. Although the temperature position of the PU maximum tan δ of the α‐relaxation was invariable, on the contrary the situation for the two maxima observed for PVP was more complex. Only the maximum of the highest temperature relaxation was shifted to lower temperatures with decreasing PVP content in the semi‐IPNs. In this study, we investigated the molecular mobility of the IPNs by means of dielectric relaxation spectroscopy; six relaxation processes were observed and indexed according the increase in the temperature range: the secondary β‐relaxations related to PU and PVP chains, an α‐relaxation due to the glass–rubber transition of the PU component, two α‐relaxations associated to the glass–rubber transitions of the PVP material, and an ionic conductivity relaxation due to the space charge polarization of PU. The temperature position of the α‐relaxation of PU was invariable in semi‐IPNs, as observed dynamic mechanical analysis measurements. However, the upper α‐relaxation process of PVP shifted to higher temperatures with increasing PVP content in the semi‐IPNs. We concluded that the investigated semi‐IPNs were two‐phase systems with incomplete phase separation and that the content of PVP in the IPNs governed the structure and corresponding properties of such systems through physical interactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1191–1201, 2003  相似文献   

17.
Superabsorbent resins prepared by ultraviolet radiation‐inducing polymerization techniques with acrylic acid/acrylamide were treated with supercritical carbon dioxide (SC‐CO2). The water‐absorbing properties of the treated resins were greatly improved. The water‐absorbing properties of resins treated with SC‐CO2 in the pressure range of 10–35 MPa and the temperature range of 40–60°C were studied. The effects of the treatment time and depressurizing speed of CO2 after treatment were also examined. Obviously, different results were found for particles of different sizes. Smaller particles were more efficient under the same treatment conditions. Samples were tested with differential scanning calorimetry. The results showed that the plasticizing effect of CO2 reduced the glass‐transition temperature of the polymer, and it was proposed that the plasticization effect might have led to polymer chain redistribution and better flexibility. Minor changes in the surface morphology of the particles were observed with scanning electron microscopy. The extraction of the unpolymerized monomers by SC‐CO2 was also studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2272–2278, 2002  相似文献   

18.
To suppress undesirable plasticization effects of condensable gas (CO2) in high pressure gas‐separation process, a surface‐modified poly(methyl methacrylate) (PMMA) membrane prepared by a plasma treatment was synthesized in this study. The pressure dependencies of permeability were analyzed to characterize the plasticization phenomenon and how it can be controlled by the plasma modification. FTIR‐ATR and TGA results suggest that the plasma treatment leads to surface crosslinking of PMMA membrane. Thus, the plasticization effect resulting from sorbed CO2 on the Ar‐plasma–treated PMMA membrane was significantly reduced, but the reduction in permeability was lower than that of other crosslinking modification methods. The reduction of the CO2 permeability contributes to a major part to the selectivity of He/CO2 for the Ar‐plasma–treated PMMA membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 395–401, 2004  相似文献   

19.
The thermal, dynamic mechanical analysis, morphology and mechanical properties of semi‐interpenetrating polymer networks based on crosslinked polyurethane (PU) and poly(2‐hydroxyethyl methacrylate) (PHEMA) synthesized by photopolymerization and by thermopolymerization have been investigated. The thermal analysis has evidenced the two glass temperature transitions in the semi‐IPNs and this is confirmed by the thermodynamic miscibility investigation of the systems. The Dynamic Mechanical Analysis spectra have shown that the phase separation is more significant in the thermopolymerized semi‐IPNs: the tan δ peaks of constituent polymers are more distinct and the minimum between the two peaks is deeper. The calculated segregation degree values of semi‐IPN's components are significantly higher for thermopolymerized semi‐IPNs, thereby the process of phase separation in the thermopolymerized semi‐IPNs is more developed. The structures of two series of samples investigated by SEM are completely different. The mechanical properties reflect these changes in structure of semi‐IPNs with increasing amount of PHEMA and with the changing of the method of synthesis. The results suggest that the studied semi‐IPNs are two‐phase systems with incomplete phase separation. The semi‐IPN samples with early stage of phase separation demonstrate higher mechanical characteristics. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers  相似文献   

20.
The aim of the work reported here was to investigate temperature‐ and pH‐sensitive hydrogels of N‐isopropylacrylamide (NIPAM) and itaconic acid (IA) and their semi‐interpenetrating polymer networks (semi‐IPNs) with varying contents of poly(ethylene glycol) (PEG). The stimuli responsiveness, swelling behaviour and mechanical properties of the hydrogels and semi‐IPNs were studied in order to investigate the effect of various amounts of PEG. Pulsed‐gradient spin‐echo NMR experiments were carried out to investigate the diffusion process. The pH sensitivity increased with an increasing amount of PEG in the semi‐IPNs, while the overall rate of water uptake was diffusion‐controlled (n < 0.5). For certain PEG contents (5 and 10 wt%), the semi‐IPNs exhibited better mechanical properties than the poly(NIPAM‐co‐IA) copolymer. The calculated values of the self‐diffusion coefficients of water indicated facilitated diffusion of water through the system with increased amounts of PEG, while the self‐diffusion coefficients of a model compound, metoprolol tartrate, showed no significant dependence on the amount of PEG. According to the results obtained and compared to results reported in the literature, the investigated semi‐IPNs may have potential applications in the controlled release of macromolecular active agents such as proteins and peptides. Copyright © 2009 Society of Chemical Industry  相似文献   

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