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1.
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   

2.
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   

3.
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   

4.
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   

5.
Simultaneous full‐interpenetrating polymer networks (full‐IPNs) based on blocked polyurethane (PU) and vinyl ester (VE) have been prepared. The static and dynamic properties of these IPNs have been examined. Results show that the tensile strength and flexural strength of IPNs increased with blocked PU content to a maximum value at 7.5 wt % PU content and then decreased. The tensile modulus, flexural modulus, and hardness of IPNs decreased with increasing blocked PU content. The impact strength of IPNs increased with increasing blocked PU content. The tensile strength, flexural strength, tensile modulus, and flexural modulus of IPNs increased with filler (kaolin) content to a maximum value at 20 to 25 phr filler content and then decreased. The higher the filler content, the greater the hardness, and the lower the impact strength of IPNs. The tensile strength, flexural strength, tensile modulus, flexural modulus, and hardness of IPNs increased with increasing VE initiator content. The dynamic technique was used to determined the damping behavior across a temperature range. Results show that the glass transition temperature (Tg) of IPNs are shifted inwardly compared with pure PU and VE, which indicated that the blocked PU–VE IPNs showed excellent compatible. Meanwhile, the glass transition temperature was shifted to a higher temperature with increased filler content. The dynamic storage modulus (E′) of IPNs increased with increasing VE and filler content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1977–1985, 1999  相似文献   

6.
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   

7.
The mechanical properties of blocked polyurethane(PU)/epoxy interpenetrating polymer networks (IPNs) were studied by means of their static and damping properties. The studies of static mechanical properties of IPNs are based on tensile properties, flexural properties, hardness, and impact method. Results show that the tensile strength, flexural strength, tensile modulus, flexural modulus, and hardness of IPNs decreased with increase in blocked PU content. The impact strength of IPNs increased with increase in blocked PU content. It shows that the tensile strength, flexural strength, tensile modulus, and flexural modulus of IPNs increased with filler (CaCO3) content to a maximum value at 5, 10, 20, and 25 phr, respectively, and then decreased. The higher the filler content, the greater the hardness of IPNs and the lower the notched Izod impact strength of IPNs. The glass transition temperatures (Tg) of IPNs were shifted inwardly compared with those of blocked PU and epoxy, which indicated that the blocked PU/epoxy IPNs showed excellent compatibility. Meanwhile, the Tg was shifted to a higher temperature with increasing filler (CaCO3) content. The dynamic storage modulus (E′) of IPNs increased with increase in epoxy and filler content. The higher the blocked PU content, the greater the swelling ratio of IPNs and the lower the density of IPNs. The higher the filler (CaCO3) content, the greater the density of IPNs, and the lower the swelling ratio of IPNs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1826–1832, 2006  相似文献   

8.
Jinbo Li 《Polymer Bulletin》2006,56(4-5):377-384
Summary Epoxy resin/polyurethane interpenetrating polymer network nanocomposites with various contents of organophilic montmorillonite (oM-EP/PU nanocomposites) were prepared by a sequential polymeric technique and an in situ intercalation method. X-ray diffraction(XRD), and transmission electronic microscopy(TEM) analysis showed that organophilic montmorillonite (oMMT) disperses uniformly in epoxy resin/polyurethane interpenetrating networks(IPNs), and the intercalated or exfoliated microstructures of oMMT are formed. Differential scanning calorimetry(DSC) test proved that oMMT promotes the compatibility of EP phase and PU phase, and glass transition temperature(Tg) of oM-EP/PU nanocomposites improves with increasing oMMT content. Mechanical properties tests and thermal gravity analysis (TGA) indicated that oMMT and the IPNs of EP and PU exhibit synergistic effect on improving mechanical and thermal properties of pure EP. The mechanism of toughing and reinforcing of oM-EP/PU nanocomposites was further discussed by scanning electronic microscope(SEM).  相似文献   

9.
The use of functional azo initiators and the thermal history of the materials have been shown to exert significant effects on the properties of interpenetrating polymer networks (IPNs). The IPNs prepared with a reactive azo initiator from MDI and 1,2-PBD (1,2-polybutadiene diol) with PMMA have been found to exhibit greater ductility, lower rigidity, and lower moduli than IPNs prepared with AIBN. This probably resulted from the attached PMMA blocks modifying the properties of the PU matrix phases. Increasing thermal treatment of IPNs prepared from either the reactive or the normal azo initiators exhibited increased Tg values in both DSC and DMTA scans. These results have been explained by increased association from chemical reactions between the hard segments of the polyurethane and poly(methyl methacrylate) ester groups.  相似文献   

10.
Two semiinterpenetrating polymer networks (semi‐IPNs) based on trihydroxyl methylpropane–polyurethane (T‐PU) or castor oil–polyurethane (C‐PU) were prepared by curing the mixed solution of the polyurethane prepolymer and nitrochitosan (NCH). During the curing process, crosslinking and grafting reaction between the molecules of the PU prepolymer and NCH occurred, because of the high reactivity of remaining hydroxyl groups in the NCH with ? NCO groups of PU. The structure of the original semi‐IPN sheets and the sheets treated with acetone were studied by infrared, 13C‐NMR, scanning electron microscopy, and dynamic mechanical analysis, showing interpenetration of NCH molecules into the PU networks. When nitrochitosan content (CNCH) was lower than 10 wt %, the semi‐IPN sheets T‐PU and C‐PU had higher density and tensile strength (σb) than the systems with CNCH more than 20%. The trihydroxymethyl propane‐based PU reacted more readily with nitrochitosan to form the semi‐IPNs than castor oil‐based PU. The semi‐IPN coatings T‐PU and C‐PU were used to coat cellophane, resulting in intimate interfacial bonding. The mechanical strength and water resistivity of the cellophane coated with T‐PU coating were improved remarkably. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3109–3117, 2001  相似文献   

11.
Semi‐interpenetrating polymer networks (semi‐IPNs) of castor oil‐based polyurethane prepolymer and nitroguar gum (NGG) with different crosslinking density of the PU network, coded as UNG films, were prepared through varying the trimethanol propane (TMP)/1,4‐butanediol (BDO) molar ratios in the chain extender mixture. The effects of crosslinking density on the structure and properties of the UNG films was investigated by attenuated total reflection Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical thermal analysis, scanning electron microscopy, crosslinking density measurements, solvent‐extracting tests, and tensile tests. The experimental results revealed that incorporation of TMP crosslinker into the hard segments of polyurethane resulted in a decrease in the aggregation of hard segments. With an increase of the TMP/BDO molar ratios, the semi‐IPN films exhibited the higher crosslinking density, glass temperature (Tg), stiffness, and tensile strength (σb). Furthermore, the experimental results also indicated that NGG restricted the formation of crosslinking networks when the TMP content is relatively high, which led to the negative deviation of the theoretically predicted crosslinking density and Dibenedetto's equation. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers  相似文献   

12.
Simultaneous two-component interpenetrating polymer networks (IPNs) of polyurethane (PU)–poly(methyl acrylate) (PMA) were prepared, as well as the corresponding pseudo-IPNs. A comparison was made between the full IPNs, pseudo-IPNs, and the respective homopolymers. Their ultimate mechanical properties were obtained and the dynamic glass transition temperatures (Tg's) were found using a thermomechanical analyzer. At all compositions, a single Tg(except 50–50 wt %) was found.  相似文献   

13.
organoclay‐modified polyurethane/epoxy interpenetrating network nanocomposites (oM‐PU/EP nanocomposites) were prepared by adding organophilic montmorillonite (oMMT) to interpenetrating polymer networks (IPNs) of polyurethane and epoxy resin (PU/EP) which had been prepared by a sequential polymerization technique. Wide‐angle X‐ray diffraction (WAXD) and transmission electronic microscopy (TEM) analysis showed that the interpenetrating process of PU and EP improved the exfoliation and dispersion degree of oMMT. The effects of the NCO/OH ratio (isocyanate index), the weight ratio of PU/EP and oMMT content on the phase structure and the mechanical properties of the oM‐PU/EP nanocomposites were studied by tensile testing and scanning electronic microscopy (SEM). Water absorption tests showed that the PU/EP interpenetrating networks and oMMT had synergistic effects on improvement in the water resistance of the oM‐PU/EP nanocomposites. Differential scanning calorimetry (DSC) analysis showed that PU was compatible with EP and that the glass transition temperature (Tg) of the oM‐PU/EP nanocomposites increased with the oMMT content up to 3 wt%, and then decreased with further increasing oMMT content. The thermal stability of these nanocomposites with various oMMT contents was studied by thermogravimetric analysis (TGA), and the mechanism of thermal stability improvement was discussed according to the experimental results. Copyright © 2005 Society of Chemical Industry  相似文献   

14.
In this research, processability and some important thermomechanical properties of polybenzoxazine (BA‐a) modified with a highly flexible urethane elastomer (PU) are discussed. This copolymer has been reported to show synergy in its glass transition temperature and some mechanical properties thus provides a fascinating group of high temperature polymers with enhanced flexibility. The results reveal that a processing window of the BA‐a/PU mixtures is widened with the increasing urethane prepolymer fraction, that is, the liquefying temperature is lowered and the gel point shifted to higher temperature with the amount of the PU. Synergism in glass transition temperature (Tg) of this copolymer was clearly confirmed, i.e., Tg's of the BA‐a/PU alloys were significantly greater than those of the parent resins, i.e., BA‐a (Tg = 166°C) and PU (Tg = ? 70°C). In addition, flexural modulus was found to systemically decrease from 5.4 GPa of the neat polybenzoxazine to 2.1 GPa at 40% by weight of the PU. Flexural strength of the alloys also shows a synergistic behavior at the BA‐a/PU ratio of 90/10. Coefficient of thermal expansion of the polymer alloys were also found to show a minimum value at BA‐a/PU = 90/10. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

15.
The miscibility, crystallization behavior, and component interactions of two binary blends, poly(L ‐lactide) (L ‐PLA)/poly(vinylpyrrolidone) (PVP) and poly(D ,L ‐lactide) (DL ‐PLA)/PVP, were studied with differential scanning calorimetry and Fourier transform infrared (FTIR) spectroscopy. The composition‐dependent changes of the glass‐transition temperature (Tg) and degree of crystallinity (Xc) of the L ‐PLA phase indicated that L ‐PLA and PVP were immiscible over the composition range investigated. However, the sharp decrease of Xc with increasing PVP content in the second heating run demonstrated that the cold crystallization process of L ‐PLA was remarkably restricted by PVP. In DL ‐PLA/PVP blends, the existence of two series of isolated Tg's indicated that DL ‐PLA and PVP were phase‐separated, but evidence showed that there was some degree of interaction at the interface of the two phase, especially for the blends with low DL ‐PLA contents. FTIR measurements showed that there was no appreciable change in the spectra of L ‐PLA/PVP with respect to the coaddition of each component spectrum, implying the immiscibility of the two polymers. In contrast to L ‐PLA, the intermolecular interaction between DL ‐PLA and PVP was detected by FTIR; this was evidenced by the observation of a high‐frequency shift of the C?O stretching vibration band of PVP with increasing DL ‐PLA content, which suggested some degree of miscibility. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 973–979, 2003  相似文献   

16.
Polyurea-urethanes with multifunctional properties were synthesized by reacting 4,4′-diphenylmethane disocyanate (MDI) with a two diol mixture of polytetramethylene glycol (PTMG (1000, 2000) and biocidal quaternary ammonium monomer ((N-benzyl-N-dodecyl-N-bis2-hydroxyethyl) ammonium chloride (BDAC)), and extended with N-(2-hydroxyethyl) ethylene diamine (HEDA) to form PU polymers. The PU polymer was then grafted with a disperse dye via a coupling agent of epichlorohydrin to form a dye grafted polyurethane with biocidal and covalent bond dyeing properties. In consideration of the mechanical properties, it is found that both the modulus and the strength of the dye grafted PU polymer films are lower than those of pure PU polymers due to the bulkiness of their dye molecules. For thermal properties, the dye grafted PU polymers exhibit higher Tgh than those without dye molecules. However,neither the Tgs nor the Tms vary in the presence of BDAC or dye molecules, but they are changed with various chain lengths of the soft segment. For dyeing properties, the effective dyeing efficiency of dye grafted PU is over 85%. Moreover, the dye grafted PU polymers exhibit lower dye migration (Mp%) than those of simple mixtures of PU and dyestuff, and they show a higher grade of color fastness when exposed to light. In the shake method of antibacterial testing, the modified PU polymers exhibit a long lasting biocidal activity.  相似文献   

17.
Main chain and segmental dynamics of polyisoprene (PI) and poly(methyl methacrylate) (PMMA) chains in semi IPNs were systematically studied over a wide range of temperatures (above and below Tg of both polymers) as a function of composition, crosslink density, and molecular weight. The immiscible polymers retained most of its characteristic molecular motion; however, the semi IPN synthesis resulted in dramatic changes in the motional behavior of both polymers due to the molecular level interpenetration between two polymer chains. ESR spin probe method was found to be sensitive to the concentration changes of PMMA in semi IPNs. Low temperature spectra showed the characteristics of rigid limit spectra, and in the range of 293-373 K, complex spectra were obtained with the slow component mostly arising out of the PMMA rich regions and fast component from the PI phase. We found that the rigid PMMA chains closely interpenetrated into the highly mobile PI network imparts motional restriction in nearby PI chains, and the highly mobile PI chains induce some degree of flexibility in highly rigid PMMA chains. Molecular level interchain mixing was found to be more efficient at a PMMA concentration of 35 wt.%. Moreover, the strong interphase formed in the above mentioned semi IPN contributed to the large slow component in the ESR spectra at higher temperature. The shape of the spectra along with the data obtained from the simulations of spectra was correlated to the morphology of the semi IPNs. The correlation time measurement detected the motional region associated with the glass transition of PI and PMMA, and these regions were found to follow the same pattern of shifts in α-relaxation of PI and PMMA observed in DMA analysis. Activation energies associated with the Tg regions were also calculated. T50G was found to correlate with the Tg of PMMA, and the volume of polymer segments undergoing glass transitional motion was calculated to be 1.7 nm3. C-13 T measurements of PMMA carbons indicate that the molecular level interactions were strong in semi IPN irrespective of the immiscible nature of polymers. The motional characteristics of H atoms attached to carbon atoms in both polymers were analyzed using 2D WISE NMR. Main relaxations of both components shifted inward, and both SEM and TEM analysis showed the development of a nanometer - sized morphology in the case of highly crosslinked semi IPN.  相似文献   

18.
Interpenetrating polymer networks (IPNs) of polydimethylsiloxane (PDMS) and poly(2‐hydroxyethyl methacrylate) (PHEMA) were prepared by sequential method. The dynamic mechanical parameters of obtained IPNs and their variations with the structural composition were evaluated. The results for the IPNs were compared with corresponding physically blended systems. The tensile properties and damping factor (tan δ) were assessed by stress–strain measurement and dynamic mechanical thermal analysis (DMTA), respectively. The glass–rubber transition temperature (Tg) was assessed by DMTA and differential scanning calorimetry (DSC). The results showed higher tensile strength and elongation at break for IPNs than those for physical blends. The shifts of Tg for that two components that make up the IPNs were greater than those for corresponding blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3480–3485, 2002  相似文献   

19.
Interpenetrating polymer networks (IPNs) composed of poly(vinyl alcohol) (PVA) and poly(N‐isopropylacrylamide) (PNIPAAm) were prepared by the sequential‐IPN method. The thermal characterization of the IPNs was investigated using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). Depression of the melting temperature (Tm) of the PVA segment in IPNs was observed with increasing PNIPAAm content using DSC. DEA was employed to ascertain the glass‐transition temperature (Tg) of IPNs. From the result of DEA, IPNs exhibited two Tg values, indicating the presence of phase separation in the IPNs. The thermal decomposition of IPNs was investigated using TGA and appeared at near 200°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 881–885, 2003  相似文献   

20.
Recent investigations on interpenetrating polymer networks (IPNs) have included two component IPNs from polyurethanes and poly(methacrylates) and two component IPNs from polyurethanes and epoxies. All the IPNs were prepared by the simultaneous polymerization technique (SIN-IPNs). Two types of IPNs, polyurethane-poly(methyl methacrylate) (PU/PMMA) and polyurethane-poly(methyl methacrylate-methacrylic acid) (PU/PMMA-MAA) were prepared. Improved phase miscibility and decreasing extent of phase separation was observed in both types of IPNs with increasing the NCO/OH ratio, decreasing molecular weight of the polyol in the PU and introduction of charge groups. A comparison was made between full-IPNs, pseudo-IPNs, graft copolymers and related homopolymers from polyurethanes and epoxies. Increased compatibility in full-IPNs and graft copolymers was observed by means of DSC, SEM and was also further substantiated by a shift toward single Tgs as determined by dynamic mechanical spectroscopy. The introduction of opposite charge groups in two-component IPNs from polyurethanes and epoxies led to improved compatibility (no phase separation) and enhanced mechanical properties.  相似文献   

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