Phase separation in the polyurethane/poly(2‐hydroxyethyl methacrylate) semi‐interpenetrating polymer networks synthesized by different ways

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     

Semiinterpenetrating polymer networks based on polyurethane and polyvinylpyrrolidone. I. Thermodynamic state and dynamic mechanical analysis

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 T_g of polyurethane and two T_g 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     

Semi‐interpenetrating polymer networks based on polyurethane and polyvinylpyrrolidone. II. Dielectric relaxation and thermal behaviour

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 (T_g) 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 T_g 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     

Damping analysis of polyurethane/polyacrylate interpenetrating polymer network composites filled with graphite particles

The graphite‐filled polyurethane/poly(methyl methacrylate‐butyl methacrylate) (PU/P(MMA‐BMA)) semi‐interpenetrating polymer networks (IPNs) were synthesized by sequential method. The influences of graphite particle content and size on the 60/40 PU/P(MMA‐BMA) IPNs were studied. The damping properties of IPN composites were evaluated by dynamic mechanical thermal analysis (DMA) and cantilever beam resonance methods. The mechanical performances were investigated using tensile and hardness devices. DMA results revealed that the incorporation of graphite particles improved damping properties of IPNs significantly. The 5% graphite‐filled IPN composite exhibited the widest temperature range and the highest loss factor (tan δ) when the test frequency was 1 Hz. As to the damping properties covering a wide frequency range from 1 to 3,000 Hz, the addition of graphite particles broadened the damping frequency range (Δf, where tan δ is above 0.3) and increased the tan δ value of IPNs. Among them, the composite with 7.5% graphite showed the best damping capacity. And the hardness and the tensile strength of IPN composites were also improved significantly. POLYM. COMPOS., 2013 © 2013 Society of Plastics Engineers     

Semi‐interpenetrating polymer networks based on polyurethane and poly(vinyl pyrrolidone) obtained by photopolymerization: Structure‐property relationships and bacterial adhesion

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.     

Cure kinetics and physical properties of dicyanate/polyetherimide semi‐IPNs

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.     

Curing and mechanical properties of dicyanate/poly(ether sulfone) semi‐interpenetrating polymer networks

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     

Effect of the synthesis route on the structure and properties of polyurethane/nitrokonjac glucomannan semi‐interpenetrating polymer networks

With a synthesis route differing from previous methods, novel semi‐interpenetrating polymer networks (semi‐IPNs), coded UNK‐II, were synthesized by the initial mixing of nitrokonjac glucomannan (NKGM) with castor oil in butanone and the subsequent addition of toluene diisocyanate (TDI) to begin the polymerization reaction in the presence of 1,4‐butanediol (BD) as a chain extender at 60°C. The results from dynamic mechanical analysis, differential scanning calorimetry, and ultraviolet spectroscopy indicated that a certain degree of microphase separation occurred between soft and hard segments of polyurethane (PU) in the UNK‐II sheets. The α‐transition temperature, glass‐transition temperature, heating capacity, and tensile strength increased with an increase in the NKGM content, and this suggested an interaction between PU and NKGM in the UNK‐II sheets. In a previous method, semi‐IPN materials (PUNK) were synthesized by the polymerization reaction between castor oil and TDI, and then this PU prepolymer was mixed with NKGM and cured in the presence of BD as a chain extender. The PUNK sheets had relatively good miscibility and mechanical properties. However, for UNK‐II sheets prepared by the method reported in this work, NKGM mainly played a role in reinforcement. When the NKGM content was less than 10%, the UNK‐II sheets exhibited good miscibility, tensile strength (26–28 MPa), and breaking elongation (130–140%), similar to those of PUNK materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1948–1954, 2003     

Sequential interpenetrating polymer network based on styrene butadiene rubber and polyalkyl methacrylates

A series of sequential interpenetrating polymer network (IPNs) based on styrene butadiene rubber (SBR) and polyalkyl (methyl, ethyl, and butyl) methacrylates have been prepared by using tetraethylene glycol dimethacrylate as crosslinker. The IPNs were characterized by infrared spectrophotometer, dynamic mechanical analyzer, thermogravimetric analyzer, and swelling study. IPNs have exhibited higher tensile properties compared with pure SBR. IPNs based on PMMA have shown higher tensile strength compared with others. Dynamic mechanical analysis has shown that the IPNs have superior dynamic properties than SBR. Because of IPN formation, tan δ peak shifted inward between SBR and acrylates. Although the magnitude of tan δ decreased, the peaks were broadened because of micro heterogeneous phase separation. At higher concentration of methacrylate, splitting in tan δ peak was noticed because of phase separation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1120–1126, 2007     

Studies on semi‐interpenetrating polymer network based on nitrile rubber and poly(methyl methacrylate)

Sequential interpenetrating polymer networks (IPNs) based on nitrile rubber and poly(methyl methacrylate) (PMMA) were synthesized. IPN compositions were varied by varying the swelling time. Two methods were adopted for making IPNs. The first method is “single‐step IPN” (SIPN) and the second method is “multistep IPN” (MIPN). The compositions were fixed around 90, 80, 70, 60 and 50% of NBR. In SIPN mode, swelling in monomer and subsequent curing was done once. In MIPN mode, swelling in monomer and curing was repeatedly done. Tensile strength of IPNs was found to increase with PMMA content, MIPN showing higher strength compared to SIPN. Dynamic modulus showed a similar trend. The tan δ value was found to decrease with PMMA content. At 62/38 nitrile rubber (NBR)/PMMA, MIPN composition isolated tan δ peaks appeared near glass transition temperatures of NBR and PMMA, respectively. Scanning electron micrograph showed phase‐separated morphology at the same MIPN composition. Solvent resistance increased with IPN formation maintaining higher resistance for MIPN compared to SIPN. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 354–360, 2004     

Effect of OMMT on the phase morphology controlling of PU/EP IPN

Organic montmorillonite (OMMT) modified polyurethane (PU) /epoxy resin (EP) (OMMT-PU/EP) graft interpenetrating polymer network nanocomposites with different content of OMMT were prepared. The effect of the OMMT content on the phase behavior of the PU/EP IPN system has been studied by Dynamic mechanical analysis (DMA). With the content of OMMT increased, the tan δ turned from single peak to two peaks and the damping temperature range became wider when the isocyanate index is low. Transmission electron microscope (TEM) and atomic force microscope (AFM) results showed that high content of OMMT favored phase separation to form a larger-size domain in nanocomposites, resulting in the broadening of damping temperature range. This work demonstrates that we can control phase behaviour of OMMT-PU/EP IPNs by changing the OMMT content. This result provides potential opportunity for this type of materials to be used as sound and vibration damping polymers over wide temperature ranges.     

The application of bulk polymerized acrylic and methacrylic interpenetrating polymer networks to noise and vibration damping

Novel acrylic/methacrylic interpenetrating polymer networks (IPNs) were examined by dynamic mechanical spectroscopy for their damping capabilities. While simple homopolymers exhibit high damping properties only over a 20–30°C range, multicomponent polymer systems with controlled degree of miscibility, such as IPNs, may exhibit high damping properties over temperature ranges as broad as approximately 100°C. Two series of IPNs based on poly(n-butyl acrylate) and poly(n-butyl methacrylate) were synthesized and the dynamic mechanical properties were investigated using a Rheovibron. Graphite was incorporated into the poly(n-butyl acrylate) homopolymer and a few IPNs to measure the change in the damping properties. For important IPN compositions, tan δ values between 0.4 and 0.85 were observed over a 75°C plus temperature range. Graphite increased the damping properties of poly(n-butyl acrylate) and the IPNs, as indicated by the tan δ values.     

Structure and properties of semiinterpenetrating polymer networks based on polyurethane and nitrochitosan

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 (C_NCH) was lower than 10 wt %, the semi‐IPN sheets T‐PU and C‐PU had higher density and tensile strength (σ_b) than the systems with C_NCH 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     

Synthesis and characterization of modified bismaleimide/polysulfone semi‐interpenetrating polymer networks

The present work reports a new method of preparing semi‐interpenetrating polymer network (semi‐IPN) membranes through in situ polymerization of bismaleimide (BMI) within polysulfone (PSF). It was found that BMI could be polymerized at ambient conditions in the presence of a proton donor and PSF without the use of an initiator or a catalyst. Chemical structure characterization of these semi‐IPNs by Fourier transform infrared attenuated total reflection (FTIR‐ATR) revealed the possibility of imide cleavage and formation of amic acid when BMI polymerization was continued for a longer time while X‐ray photoelectron spectroscopy (XPS) revealed the protonation of imide nitrogen at shorter polymerization time. It was also found that size of thermoset BMI phase within the PSF thermoplastic has a significant impact on glass‐transition temperature of resulting semi‐IPN. By controlling the thermoset/thermoplastic phase separation of semi‐IPNs through dope composition and formation techniques, gas separation membranes with comparable selectivity and permeance that were up to 12 times higher than corresponding PSF membranes were formed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 369–379, 2006     

Synthesis and characteristics of the interpenetrating polymer network hydrogel composed of chitosan and polyallylamine

A temperature‐ and pH‐dependent hydrogel was studied with interpenetrating polymer network (IPN) hydrogels constructed with water‐insoluble chitosan and polyallylamine. Various IPNs were prepared from different weight ratios of chitosan–polyallylamine. Crosslinked‐IPN hydrogels exhibited relatively high equilibrium water content (EWC) in the range 80–83%. The EWC of IPN hydrogels depended on pH and the amount of complex, which is the content of chitosan and polyallylamine. The differential scanning calorimeter (DSC) thermogram of fully swollen IPN hydrogels appeared between 3 to 4 °C. The IPNs exhibited two glass‐transition temperatures (T_gs), indicating the presence of phase separation in the IPNs as exhibited by dielectric analysis (DEA). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 498–503, 2002     

Electrical behavior of chitosan and poly(hydroxyethyl methacrylate) hydrogel in the contact system

Semi‐interpenetrating polymer networks (semi‐IPNs), as polymer hydrogels composed of chitosan and poly(hydroxyethyl methacrylate) (PHEMA), exhibiting electrical‐sensitive behavior, were prepared. The swelling behavior of the chitosan/PHEMA hydrogels was studied by immersing the gels in various concentrations of aqueous NaCl solution. The electrical responses of the semi‐IPN hydrogel, in applied electric fields, were also investigated. When the semi‐IPN hydrogels were swollen, where one electrode was placed in contact with the gel and the other fixed 30 mm apart from one, they exhibited bending behavior on the application of an electric field on a contact system. The electroresponsive behavior of the present semi‐IPN was also affected by the electrolyte concentration of the external solution. The semi‐IPN also showed various degrees of increased bending behavior depending on the electric stimulus. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 915–919, 2004     

Effect of nitrocellulose on the properties of PU–NC semi‐IPN wood coatings

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     

Miscibility and properties of semi‐interpenetrating polymer networks based on polyurethane and nitroguar gum

Films from castor oil‐based polyurethane (PU) prepolymer and nitroguar gum (NGG) with different contents (10–70 wt %) were prepared through solution casting method. The networks of PU crosslinked with 1,4‐butanediol were interpenetrated by linear NGG to form semi‐interpenetrating polymer networks (semi‐IPNs) in the blend films. The miscibility, morphology, and properties of the semi‐IPNs coded as PUNG films were investigated with Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, dynamic mechanical thermal analysis, wide‐angle X‐ray diffraction, density measurement, ultraviolet spectroscopy, thermogravimetric analysis, tensile, and solvent‐resistance testing. The results revealed that the semi‐IPNs films have good miscibility over the entire composition ratio of PU to NGG under study. The occurrence of hydrogen‐bonding interaction between PU and NGG played a key role in improvement of the material performance. Compared with the pure PU film, the PUNG films exhibited higher values of tensile strength (11.7–28.4 MPa). Meanwhile, incorporating NGG into the PU networks led to an improvement of thermal stability and better solvent‐resistance of the resulting materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 4068–4079, 2007     

Poly(2‐hydroxyethyl methacrylate) hydrogel: from a brittle material to a nanofilled semi‐interpenetrating polymer network with potential application in wound dressings

In this work we report the photopolymerization of poly(2‐hydroxyethyl methacrylate) (PHEMA) together with a hydrophilic chitosan derivate (carboxymethyl‐chitosan) to yield a semi‐interpenetrating polymer network (semi‐IPN) that was filled with poly(N‐vinylcaprolactam)/poly(ethylene glycol methacrylate) core–shell nanogels in order to enhance the mechanical properties of the resulting hydrogels. The mechanical properties of the nanofilled semi‐IPNs were found to be more suitable for wound dressing applications than the PHEMA hydrogel as described by dynamic mechanical analysis in dry form and submerged in water. This was evidenced by a higher Young's modulus and higher elongation at break in the semi‐IPNs compared to blank PHEMA hydrogels. Furthermore, when the hydrogels were filled with nanogels, there was an elongation at break similar to that of skin with only a slightly lower Young's modulus. © 2019 Society of Chemical Industry     

Thermal characterizations of semi‐interpenetrating polymer networks composed of poly(ethylene oxide) and poly(N‐isopropylacrylamide)

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 (T_m) of semi‐IPNs appeared at around 60°C using DSC. DEA was employed to ascertain the glass transition temperature (T_g) and determine the activation energy (E_a) of semi‐IPNs. From the results of DEA, semi‐IPNs exhibited one T_g indicating the presence of phase separation in the semi‐IPN, and T_gs 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