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1.
The thermodynamic miscibility and thermal and dynamic mechanical behaviour of semi‐interpenetrating polymer networks (semi‐IPNs) of crosslinked polyurethane (PU) and linear poly(hydroxyethyl methacrylate) (PHEMA) have been investigated. The free energies of mixing of the semi‐IPN components have been determined by the vapour sorption method and it was established that the parameters are positive and depend on the amount of PHEMA in the semi‐IPN samples. Thermal analyses glass transition temperatures evidenced two in the semi‐IPNs in accordance with the investigation of the thermodynamic miscibility of these systems. Dynamic mechanical analysis revealed a pronounced change in the viscoelastic properties of the PU‐based semi‐IPNs with different amounts of PHEMA in the samples. The semi‐IPNs have two distinct tan δ maxima related to the relaxations of the two polymers in their glass temperature domains. The temperature position of PU relaxation maximum tan δ is invariable but its amplitude decreases in the semi‐IPNs with increasing amount of PHEMA in the systems. The tan δ maximum of PHEMA is shifted to a lower temperature and its amplitude decreases with increasing amount of PU in the semi‐IPNs. The segregation degree of components α was calculated using the viscoelastic properties of semi‐IPNs. It was concluded that the studied semi‐IPNs are two‐phase systems with incomplete phase separation. The different levels of immiscibility lead to the different degree of phase separation in the semi‐IPNs with compositions. Copyright © 2004 Society of Chemical Industry  相似文献   

2.
Semi‐interpenetrating polymer networks (semi‐IPNs) composed of poly(dimethyl–aminoethyl methacrylate) (PDMAEMA) and poly(ethylene oxide) (PEO) were synthesized by γ‐radiation; three semi‐IPNs with 80 : 20, 90 : 10, and 95 : 5 weight ratios of DMAEMA/PEO were obtained by use of this technique. The gel–dose curves showed that the hydrogels were characterized by a structure typical of semi‐IPNs and the results of elemental analysis supported this point. The temperature‐induced phase transition of semi‐IPNs with the composition of 95 : 5 was still retained, with the lower critical solution temperature of PDMAEMA shifting from 40 to 27°C. The temperature sensitivity of the other two semi‐IPNs gradually disappeared. The pH sensitivity of three semi‐IPNs was still retained but the pH shifted slightly to lower values with increasing PEO content in the semi‐IPNs. The effect of PEO content in semi‐IPNs on their environmental responsiveness was discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2995–3001, 2004  相似文献   

3.
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   

4.
A range of semi‐interpenetrating polymer networks (semi‐IPNs) based on polyurethane (PU) and poly(vinyl pyrrolidone) (PVP) have been synthesized and characterized with respect to their thermodynamic characteristics, morphology, mechanical properties, surface properties, water sorption and bacterial adhesion. The free energies of mixing of PU and PVP in semi‐IPNs have been determined by the vapor sorption method and were shown to be positive for all compositions. The surface properties of semi‐IPNs were investigated using the dynamic contact angle analysis. It was shown that the advancing contact angle changes from 83.1° to 65.3° with increasing PVP from 7.05% to 57.38%. Scanning electron microscopy demonstrated that the semi‐IPNs are two‐phase systems with incomplete phase separation. The mechanical properties reflect the changes in structure of semi‐IPNs with increasing of amounts of PVP in the system. Incorporation of PVP into the semi‐IPN with PU restricts the ability of PVP to sorb water. As infection is likely to be caused by bacterial adherence to biomedical implants, the bacterial adhesion data suggests that the semi‐IPNs with PVP content below 22.52% may be useful for biomedical material applications. Polym. Eng. Sci. 44:940–947, 2004. © 2004 Society of Plastics Engineers.  相似文献   

5.
Semiinterpenetrating polymer networks (semi‐IPNs) based on polyurethane (PU) and polyvinylpyrrolidone (PVP) have been synthesized, and their thermodynamic characteristics, thermal properties, and dynamical mechanical properties have been studied to have an insight in their structure as a function of their composition. First, the free energies of mixing of the two polymers in semi‐IPNs based on crosslinked PU and PVP have been determined by the vapor sorption method. It was established that these constituent polymers are not miscible in the semi‐IPNs. The differential scanning calorimetry results evidence the Tg of polyurethane and two Tg for PVP. The dynamic mechanical behavior of the semi‐IPNs has been investigated and is in accordance with their thermal behavior. It was shown that the semi‐IPNs present three distinct relaxations. If the temperature position of PU maximum tan δ is invariable, on the contrary, the situation for the two maxima observed for PVP is more complex. Only the maximum of the highest temperature relaxation is shifted to lower temperature with changing of the semi‐IPNs composition. It was concluded that investigated semi‐IPNs are two‐phase systems with incomplete phase separation. The phase composition was calculated using viscoelastic properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 852–862, 2001  相似文献   

6.
Semi‐ and full‐interpenetrating polymer networks (IPNs) were prepared using polyurethane (PUR) produced from a canola oil‐based polyol with primary terminal functional groups and poly(methyl methacrylate) (PMMA). The properties of the material were studied and compared using dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and tensile measurements. The morphology of the IPNs was investigated using atomic force microscopy (AFM). Semi‐IPNs demonstrated different thermal mechanical properties, mechanical properties, phase behavior, and morphology from full IPNs. Both types of IPNs studied are two‐phase systems with incomplete phase separation. However, the extent of phase separation is significantly more advanced in the semi‐IPNs compared with the full IPNs. All the semi‐IPNs exhibited higher values of elongation at break for all proportions of acrylate to polyurethane compared with the corresponding full IPNs. These differences are mainly due to the fact that in the case of semi‐IPNs, one of the constituting polymers remains linear, so that it exhibits a loosely packed network and relatively high mobility, whereas in the case of full IPNs, there is a higher degree of crosslinking, which restricts the mobility of the chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

7.
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   

8.
Semi1 and semi2 interpenetrating polymer networks of poly(vinyl chloride) PVC and in situ formed poly(butyl acrylate) (PBA) have been synthesized and characterized using diallyl phthalate (DAP) and ethylene glycol dimethacrylate (EGDM) as the crosslinkers of PVC and PBA, respectively. These two types of IPNs have been compared with respect to their mechanical and thermal properties. The semi1 IPNs displayed a decrease in their mechanical parameters and the physical properties as well, while in contrast, the semi2 IPNs exhibited a marginal increase in the corresponding values when compared to the crosslinked PVC in the case of semi1 IPN and linear PVC in case of semi2 IPN. The representative samples of semi1 and semi2 IPNs revealed a two‐stage‐degradation typical of PVC while confirming the increased stability of the samples with higher onset temperature of degradation. The softening characteristics as detected by thermomechanical analysis are in conformity with their mechanicals. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

9.
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   

10.
Semi1 and semi2 interpenetrating polymer networks (IPNs) of PVC and in situ formed PMMA have been synthesized using diallyl phthalate and ethylene glycol dimethacrylate as the crosslinkers of PVC and PMMA, respectively. These two types of IPNs have been compared w.r.t their physical, mechanical, and thermal properties and an endeavor has been made to find a correlation of these properties with the morphology generated in these systems. The semi1 IPNs displayed a decrease in their mechanical parameters and the physical properties as well, while in contrast, the semi2 IPNs exhibited a marginal increase in the corresponding values after an initial drop upto about 15% of crosslinked PMMA incorporation when compared to the crosslinked PVC in the case of semi1 IPN and linear PVC in the case of semi2 IPN. The various samples of semi1 and semi2 IPNs showed a two‐stage degradation typical of PVC, while confirming the increased stability with the samples having higher percentages of PMMA. The influence of crosslinking of the major matrix in semi1 IPN was almost counterbalanced by the influence of crosslinking in the dispersed PMMA phase in the case of semi2 IPN. The softening characteristics as detected by the extent of penetration of the probe, as has been detected by thermomechanical analysis, are in conformity with their mechanicals. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1725–1735, 2005  相似文献   

11.
Semi‐1 and semi‐2 interpenetrating polymer networks (IPNs) of poly(vinyl chloride) (PVC) and in situ formed poly(ethyl acrylate) (PEA) have been synthesized using diallyl phthalate and ethylene glycol dimethacrylate as the crosslinkers of PVC and PEA, respectively. These two types of IPNs have been compared with respect to their physical, mechanical, and thermal properties and an endeavor has been made to find a correlation of these properties with the morphology generated in these systems. The semi‐1 IPNs displayed a decrease in their tensile strength and modulus while in contrast; the semi‐2 IPNs exhibited a marginal increase with increasing crosslinked PEA incorporation. The semi‐1 and semi‐2 IPNs containing 10 and 30 wt % of PEA displayed a two‐stage degradation typical of PVC in their thermogravimetric and DSC studies while confirming the increased stability of the samples with higher percentages of PEA. The softening characteristics as detected by the extent of penetration of the thermomechanical probe as has been detected by thermomechanical analysis are in conformity with their mechanicals. The biphasic cocontinuous systems as explicit from the morphological studies reveal fibrillar characteristics in both the systems. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

12.
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   

13.
Here, a novel ternary semi interpenetrating polymer networks (semi IPNs) have been synthesized. An effective role to develop mechanically strong polymeric materials has been through the preparation of interpenetrating polymer networks (IPNs). The highly swelling superabsorbent semi IPNs were prepared by introducing poly(ethylene glycol), (PEG) into an acrylamide/sodium acrylate, (AAm/SA) hydrogels. For swelling characterization, swelling experiments were performed in water at 25 °C, gravimetrically. Water uptake and dye sorption properties of AAm/SA hydrogels and AAm/SA/PEG semi IPNs were investigated as a function of chemical composition of the hydrogels. AAm/SA hydrogels and AAm/SA/PEG semi IPNs were used in experiments on sorption of water-soluble cationic dye such as “Janus Green B” (JGB). For sorption of JGB into AAm/SA hydrogels and AAm/SA/PEG semi IPNs were studied by batch sorption technique at 25 °C. For the analysis of sorption mechanism and for calculation of some binding parameters of JGB from aqueous solutions, some linearization methods such as Klotz, Scatchard, and Langmuir linearization methods have been used.  相似文献   

14.
Semi‐interpenetrating networks (semi‐IPNs) were prepared from natural rubber (NR) and polystyrene (PS) by the sequential method. In these semi‐IPNs the NR phase was crosslinked while the PS phase was uncrosslinked. Different initiating systems such as dicumyl peroxide (DCP), benzoyl peroxide (BPO), and the azobisisobutyronitrile (AIBN) system were used for polymerizing the PS phase. The blend ratio was varied by controlling the swelling of NR in the styrene monomer. The mechanical properties of the semi‐IPNs, namely, density, tensile strength, tear strength, elongation at break, tension set, tensile set, impact strength, and hardness, were determined. The morphology of different IPNs was studied using scanning electron microscopy. A compact morphology with a homogeneous phase distribution was observed in the semi‐IPNs. The properties of the semi‐IPN do not change much with the initiating system. However, in most cases, the DCP initiating system showed slightly superior performance. The tensile and tear‐strength values of the IPNs were found to increase with increasing plastomer content. The crosslink density of the semi‐IPNs also increased with increase in the polystyrene content. The experimental values were compared with theoretical models such as series, parallel, Halpin Tsai, Coran, Takayanaki, Kerner, and Kunori. The tensile and tear‐fracture surfaces were examined using a scanning electron microscope. The fracture patterns were correlated with the strength and nature of the failure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2327–2344, 2000  相似文献   

15.
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   

16.
Semi‐1 and semi‐2 interpenetrating polymer networks (IPNs) of poly(vinyl chloride) (PVC) and in situ formed poly(butyl methacrylate) (PBMA) have been synthesized using diallyl phthalate and ethylene glycol dimethacrylate as the crosslinkers of PVC and PBMA, respectively. These were then characterized with reference to their mechanical, thermal, and morphological properties. The mechanical and thermal characteristics revealed modification over the unmodified polymeric systems in relation to their phase morphologies. The semi‐1 IPNs displayed a decrease in their mechanical parameters of modulus and UTS while semi‐2 IPNs exhibited a marginal increase in these two values. The semi‐1 IPNs, however, also revealed a decrease in the elongation and toughness values away from the normal behavior. The thermomechanical behavior of both the systems is in conformity with their mechanicals in displaying the softening characteristics of the system and stabilization over unmodified PVC. The DSC thermograms are also correlated to these observations along with the heterogeneous phase morphology which is displayed by both the systems especially at higher concentration of PBMA incorporation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

17.
To reduce the highly hydrophilic property of chondroitin sulfate (ChS), a semi‐interpenetrating polymer network (semi‐IPN) of chondroitin sulfate/polyacrylic acid (PAA) was prepared as a drug carrier by crosslinking acrylic acid with diethyleneglycol diacrylate. The swelling properties of the semi‐IPNs with different concentrations of crosslinking agent were correlated. The moisture sorption profiles were evaluated using differential thermal analysis. Ketoprofen was used as a drug probe to evaluate the performance of the drug released from the semi‐IPN matrices. The prepared semi‐IPNs demonstrated significant swelling reduction properties with both gastric and intestinal fluids compared with those of both the pure ChS and the ChSAA blend without the crosslinking agent. The amount of accumulated drug released from the semi‐IPNs was less than 30 wt % at pH 1.2 and up to 80 wt % at pH 7.4. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 114–122, 2002  相似文献   

18.
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   

19.
A study on two‐component semi‐ and full‐interpenetrating polymer networks (IPNs) of soyabean‐oil based uralkyd resin (UA) and poly(butyl methacrylate) (PBMA) synthesized by a sequential technique, has been conducted. The IPNs obtained are characterized with respect to their mechanical properties, such as tensile strength, percentage elongation and hardness (Shore A). Phase morphology has been studied by scanning electron microscopy. Glass transition studies have been carried out using differential scanning calorimetry. The thermal characterization of the IPNs was undertaken with the aid of thermogravimetric analysis. The apparent densities of these samples have been determined and are compared. The effect of the compositional variation on the above‐mentioned properties was examined. The tensile strength exhibits a sudden rise (approximately three‐fold) for the semi‐ and full‐IPNs with composition UA: PBMA 40% : 60% compared with the UA:PBMA composition of 20% : 40%. © 2001 Society of Chemical Industry  相似文献   

20.
Wood coatings of PU–NC semi‐interpenetrating polymer networks (semi‐IPNs), made from blown castor oil (BCO), aromatic polyisocyanate (PTDI), and nitrocellulose (NC), were prepared by sequential polymerization method. To investigate the effects of NC on the properties of PU–NC semi‐IPNs wood coatings, three different viscosities of NC (½‐sec, ¼‐sec, and ${1\over 16}$ ‐sec), and a PU catalyst [dibutyltin dilaurate (DBTDL)] were synthesized in this study. The results revealed that the PU–NC semi‐IPNs with ½‐sec NC‐containing coating had the shortest drying time, and their films had the best tensile strength, elongation at break, lightfastness, and solvent resistance. Dynamic mechanical analysis showed that PU–NC semi‐IPNs with ½‐sec NC or ${1\over 16}$ ‐sec NC had good interpenetration between PU and NC, whereas PU–NC semi‐IPNs with ¼‐sec NC had a slight separation phase between PU and NC. In both PU–NC semi‐IPNs with ¼‐sec NC and those with ${1\over 16}$ ‐sec NC, the addition of 0.2% DBTDL could effectively reduce the drying time of the coating and improve the film properties, including tensile strength, elongation at break, and lightfastness. In addition, the miscibility of PU and NC was examined in PU–NC semi‐IPNs with ¼‐sec NC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2157–2162, 2003  相似文献   

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