Semi- and fully interpenetrating polymer networks based on polyurethane–polyacrylate systems. VII. Polyurethane–poly(methyl acrylate) interpenetrating polymer networks

A series of polyurethane–poly(methyl acrylate) sequential interpenetrating polymer networks containing 40 wt % polyurethane were prepared. The triol/diol ratio used in the preparation of the first formed polyurethane network was changed so that the average molecular weight between crosslinks ranged from 9500 to 500 g/mol. In addition to decreasing this average molecular weight, changing the triol/diol ratio alters the hard segment content of the polyurethane. The extent of mixing of the components in these IPNs was investigated using electron microscopy, dynamic mechanical analysis, tensile testing, and sonic velocity measurements. The polyurethane networks were also characterized by swelling studies. It was concluded that, as the triol/diol ratio increased, the extent of mixing increased and there was evidence of phase separation of the hard segments of the polyurethane component at high triol/diol ratios.     

Polyurethane–poly(methyl methacrylate) interpenetrating polymer networks. I. Synthesis,characterization, and preliminary blood compatibility studies

Simultaneous polyurethane–poly(methyl methacrylate) (PU–PMMA) interpenetrating polymer networks (IPNs) were synthesized with the PMMA polymerization initiated at room temperature. Transparent IPNs with better miscibility and synergism of mechanical properties were obtained. Dynamic mechanical analysis data indicated that up to 30% PMMA can be incorporated into PU networks without substantial phase separation. The PU–PMMA 90/10 IPNs elicit less than 2% hemolysis, suggesting that these materials could be used as blood contacting materials. © 1996 John Wiley & Sons, Inc.     

Viscoelastic behavior of interpenetrating polymer networks: Poly(ethyl acrylate)–poly(methyl methacrylate)

The creep behavior of a series of poly(ethyl acrylate)–poly(methyl methacrylate) interpenetrating polymer networks was investigated. For comparison purposes, some stress relaxation data were included. Master curves containing a single broad transition covering approximately 20 decades of time were found for midrange compositions. Although the time–temperature superposition principle and the WLF equation should not strictly apply, reasonable agreement was found over a large portion of shift factor versus temperature plots. Application of a modified Tobolsky-Aklonis-Dupre glass–rubber theory suggested that the breadth of the transition could be attributed to a near continuum of phase compositions in the material, each phase composition making its specific contribution to the relaxation spectrum. Whether or not these phase regions are so small as to arise from random concentration fluctuations in an otherwise compatible polymer pair remains unknown.     

Multiphase materials with lignin: 9. Effect of lignin content on interpenetrating polymer network properties

A series of lignin-based polyurethane/poly(methyl methacrylate) (LPU/PMMA) interpenetrating polymer networks (IPNs) were prepared by solvent casting in film form. While the LPU/PMMA ratio remained constant (1:1), the properties of the LPU were controlled by varying the composition of the hydroxypropyl lignin polyol via chain extension with propylene oxide. An increase in the lignin content of the polyol resulted in a decrease in the molecular weight between crosslinks (M_c) and change in the morphology of the LPU/PMMA composite. This effect resulted in the transition from a two-phase material to a single-phase material when the (true) lignin content of the composite rose above 25 wt%. As the lignin content increased, the strength properties of the composites increased. The dynamic mechanical, thermal and ultimate mechanical properties of the entire series of IPNs could be explained by dual phase continuity.     

聚氨酯/聚甲基丙烯酸甲酯互穿网络的阻尼性能及相态

引言聚合物互穿网络体系由于在其形成过程中产生特殊的物理拓扑结构,使得该体系是一种永久缠结在一起的聚合物"合金"[1]。同时,由于构成该体系的聚合物组分往往不相容或部分相容,在其形成     

Synthesis and behavior of poly(vinyl chloride)-based latex interpenetrating polymer networks

Poly(vinyl chloride)/poly(butadiene–co–acrylonitrile) interpenetrating polymer networks (IPN's) were synthesized in latex form. Dynamic mechanical spectroscopy as a function of temperature revealed that the glass transitions of the individual networks were broadened and in some cases spanned the entire temperature range between the two individual polymer transitions. This was interpreted to indicate extensive but incomplete mixing between the two networks. Depending on overall composition, the cast or molded films were either plastic or tough elastomers at room temperature. Some aspects of phase continuity and structure, including a graded core-shell model, are discussed.     

Polyurethane—polystyrene interpenetrating polymer networks

Two component interpenetrating polymer networks (IPN) of the SIN type (simultaneous interpenetrating networks), composed of a polystyrene network (crosslinked with divinyl benzene) and a polyester-polyurethane network (crosslinked with trimethylolpropane), were made. Electron microscopy and glass-transition measurements showed that phase separation had resulted with some interpenetration, presumably occurring at the boundaries. At a composition of about 75 percent polyurethane, a phase inversion occurred, the continuous phase being polystyrene at polyurethane compositions of less than 75 percent. The stress-strain properties and hardness measurements agreed with these results. Enhanced tensile strength was observed in the IPN's in a concentration range where modulus reinforcement was not evident. A small enhancement in tear strength and thermal stability was also noted.     

Kinetics of phase separation in polyurethane/polystyrene semi-1 interpenetrating polymer networks. 1. Light transmission studies

The phase separation of different in-situ semi-1 interpenetrating polymer networks (IPNs) based on polyurethane and polystyrene has been followed by light transmission. The effect of the presence ab initio of small amounts of homopolystyrene in the initial reaction mixture on the phase separation process has also been examined. If gelation of the polyurethane occurs before the onset of phase separation, the latter is impeded or strongly limited, and transparent semi-1 IPNs are obtained. In the opposite case, phase separation is macroscopic and the material is turbid.     

Cure studies of interpenetrating networks by microdielectrometry

Microdielectrometry has been used to follow the cure kinetics of interpenetrating polymer networks (IPNs). The rate of formation of a polyurethane–poly(n-butyl acrylate) IPN has been characterized at three temperatures. The dielectric data indicate that the relative homonetwork formation rates dominate the resultant material properties.     

Semi- and fully interpenetrating polymer networks based on polyurethane-polyacrylate systems. VIII. The influence of the degree of crosslinking of the second formed network on the morphology and properties of polyurethane polymethylacrylate interpenetrating polymer networks

A series of polyurethane–polymethylacrylate sequential interpenetrating polymer networks containing 40% by weight of polyurethane were prepared in which the levels of crosslinking in the second formed network—polymethylacrylate—was systematically altered over a wide range. The polymethylacrylate networks and the interpenetrating polymer networks were investigated using dynamic mechanical analysis, sonic velocity measurements, and tensile testing. In addition, the interpenetrating polymer networkds were studied using transmission electron microscopy. The interpenetrating polymer networks showed high values of the Oberst damping factor. It was concluded that tightening the second formed network does not produce the dramatic effects associated with decreasing the average molecular weight between crosslinks of the first formed network.     

Semi- and fully interpenetrating polymer networks based on polyurethane–polyacrylate systems. V. An isomerically related semi-1-interpenetrating polymer network system

A series of polyurethane–poly(vinyl acetate) semi-1-IPNs were synthesized, and certain physical properties investigated. Electron microscopy showed all the materials to be substantially phase-separated, but evidence from dynamic mechanical analysis indicated that some mixing occurred, because the polyurethane glass transition was shifted in both the tan σ? and the E″–temperature curves. The variation of modulus with composition was found to be reasonably close to the predictions of the Davies equation. When the exponent in that relation was changed to ?, a good fit was obtained. Synergism with respect to tensile strength was observed for two of the semi-1-IPNs. Stress–relaxation measurements, over a fairly narrow temperature range, were made on the semi-1-IPN containing 40% by weight of the polyurethane network. A master curve was constructed. It was noted that the WLF equation was not obeyed by this semi-1-IPN at temperatures above about 50°C.     

Poly(vinyl acetate)/polyacrylate semi‐interpenetrating polymer networks. II. Thermal,mechanical, and morphological characterization

The thermal, dynamic mechanical, and mechanical properties and morphology of two series of semi‐interpenetrating polymer networks (s‐IPNs) based on linear poly(vinyl acetate) (PVAc) and a crosslinked n‐butyl acrylate/1,6‐hexanediol diacrylate copolymer were investigated. The s‐IPN composition was varied with different monoacrylate/diacrylate monomer ratios and PVAc concentrations. The crosslinking density deeply affected the thermal behavior. The results showed that a more densely crosslinked acrylate network promoted phase mixing and a more homogeneous structure. The variation in the linear polymer concentration influenced both the morphology and mechanical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology and mechanical behavior of poly(vinyl chloride)/poly(butadiene–co–acrylonitrile) latex interpenetrating polymer networks

A series of poly(vinyl chloride)/poly(butadiene–co–acrylonitrile) interpenetrating polymer networks (IPNs), all having 50/(25–25) weight compositions, was synthesized in latex form. The latex particles were studied after each step of the two-staged polymerization and after molding or casting. Transmission electron microscopy together with dynamic mechanical spectroscopy suggest a graded composition within the latexes, in which the poly(vinyl chloride) seed latex network I forms a core that is partially penetrated by the poly(butadiene–co–acrylonitrile) network II, yielding increased amounts of poly(butadiene–co–acrylonitrile) in the shell of the latex particles.     

Effects of polyurethane soft segment and crosslink density on the morphology and mechanical properties of polyurethane/poly(allyl diglycol carbonate) simultaneous interpenetrating polymer networks

Tough, optically clear simultaneous interpenetrating polymer networks (SINs) of polyurethane (PU) and poly(allyl diglycol carbonate) (ADC) at different compositions were synthesized. The effects of the molecular weight of PU soft segment on the morphology, mechanical properties, and thermal transition behavior of the SINs at two levels of crosslinking agent were studied. The miscibility of PU/ADC SINs, studied by TEM and DMA, was greatly influenced by the SIN composition and the molecular weight of poly(caprolactone) diol (PCL) as the PU soft segment. A single‐phase morphology at a PU concentration of 10% changed to a very fine microheterogeneous morphology as the molecular weight of PCL changed from 530 to 1250. The two‐phase morphology of the PU10/ADC90 SIN based on higher PCL molecular weight (PCL 1250) was also confirmed by DMA, which displayed a sharp peak for the ADC‐rich phase and a small shoulder for the PU‐rich phase transition in the tan δ plot. The SINs at 20–30% PU composition exhibited co‐continuous phase morphology in the transmission electron micrographs, in which the phase regions grew larger as the PCL molecular weight increased from 530 to 1250. All the SIN samples possessed excellent optical transparency except two samples with 30% PU composition based on PCL 1250, which showed a hazy appearance. The tensile strength, modulus, and toughness of the SINs decreased by increasing the molecular weight of PCL from 530 to 1250, whereas the elongations at break remained nearly unchanged. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1583–1595, 2003     

Novel dielectrics from IPNs derived from castor oil based polyurethanes

Three series of interpenetrating polymer networks (IPNs) based on a polyurethane (castor oil + toluene diisocyanate) with polystyrene, poly(methyl methacrylate), and poly(n-butyl methacrylate) were synthesized and characterized. Dielectric relaxation studies of these IPNs were carried out from ?150 to 100°C in the 100 Hz to 100 kHz range. The effects of structural variables such as composition, type of vinyl monomer, as well as the effect of interaction of the phases on the dielectric properties were studied. A certain degree of phase mixing was observed to exist in all series as detected by the variation of the glass-transition temperatures of the IPNs. Maxwell–Wagner–Sillars polarization at the interface of the two phases was observed. © 1994 John Wiley & Sons, Inc.     

Thermodynamic state of reinforced interpenetrating polymer networks

The free energies of mixing of two networks in the interpenetrating polymer network based on crosslinked polyurethane and poly(ester acrylate) have been determined by the vapour sorption method. It was established that the constituent networks in the IPN are not miscible. The introduction of fillers of different chemical nature increases the compatibility. The thermodynamic affinity of the fillers to the individual networks and IPN was estimated. It was established that when the free energy of interaction of one or both components of the IPN with the filler is negative, reinforcement leads to the formation of a compatible and equilibrium system. For fillers having no affinity to the polymers, compatibilization is observed, which is connected with slowing down of phase separation in the system in the presence of filler.     

Dependence of viscoelastic properties on segregation degree of components in interpenetrating polymer networks

The temperature dependences of elastic moduli, loss moduli, and mechanical loss angle tangent were investigated for the interpenetrating polymer networks: polyurethane–polyurethane acrylate by the method of dynamic mechanical spectroscopy (DMS). The segregation degree of components due to phase separation have been calculated from the parameters of relaxation maxima. An essential change was found in the segregation degree of components with the curing sequence of individual networks being changed. It was shown that, with the conditions and sequence of IPN formation changed, the phase separation degree can be fixed at a particular stage, i.e., the structures with a different segregation degree of components are obtainable. For the IPNs under investigation the variation of elastic moduli of the composites proved possible by fixing the separation degree of components.     

Polyurethane interpenetrating polymer networks. V. Engineering properties of polyurethane–poly(methyl methacrylate) IPN's

The engineering properties of polyurethane–poly(methyl methacrylate) simultaneous interpenetrating networks (SIN's) were evaluated. The hardness behavior reflected the observed phase inversion in the electron-microscopic studies. The maximum ultimate tensile strength was observed at 85% polyurethane–15% poly(methyl methacrylate) IPN and was due to the filler-reinforcing effect of the rigid poly(methyl methacrylate) phase. The ultimate tensile strenght of the 75/25 polyurethane–poly(methyl methacrylate) IPN was higher than that of the corresponding pseudo-IPN's (only one network crosslinked) and the linear blend. The leathery and glassy compositions did not show any reinforcement in the ultimate tensile strength. This indicated that the reinforcement in the ultimate tensile strength was not directly related to interpenetration (by increased physical entanglement crosslinks), but indirectly related by reducing the rigid phase domain sizes and increasing the adhesion between the two phases, thus enhancing the filler-reinforcing effect similar to that observed in a carbon black-filled rubber. The tear strengths of the polyurethane-rich IPN's pseudo-IPN's, and linear blends were found to be higher than that of the pure polyurethane as a combined result of increased modulus and tensile strength. The weight retentions in the thermal decomposition of the IPN's, pseudo-IPN's, and linear blends were higher than the proportional average of the component networks. The results seemed to indicate that this enhancement was related to the presence of the unzipped methyl methacrylate monomer. It was suggested that the monomers acted as radical scavengers in the polyurethane degradation, thus delaying the further reaction of the polyurethane radicals into volatile amines, isocyanates, alcohols, olefins, and carbon dioxide.     

Synthesis and characterization of polyurethane/polybenzoxazine‐based interpenetrating polymer networks (IPNs)

Sequential interpenetrating polymer networks (IPNs), based on polyurethane and polybenzoxazine, were synthesized. Fourier Transform infrared spectrometry was employed to monitor the formation kinetics, which indicated that only physical bonding existed in the resulting IPNs. Morphological investigations revealed a lightly phase separation behaviour in all of the IPNs studied. © 2003 Society of Chemical Industry     

Interpenetrating polymer network from blocked isocyanates. I. Structure and properties of polyurethane-urea polyvinyl simultaneous interpenetrating networks

A series of polyurethane-urea/polyvinyl simultaneous interpenetrating polymer networks (SINs) were prepared starting from a mixture of isocyanate prepolymer blocked with N-(1-1′-dimethyl-3-cxobutyl) acrylamide oxime, chain extender, vinyl monomers, and catalysts. Their physical properties and morphology were investigated using differential scanning calorimetry, dynamic mechanical measurements, and small-angle X-ray scattering. The polyurethane-urea networks examined were two-phase in nature. The vinyl network was formed with diacetone acrylamide oxime, trimethylolpropane trimethacrylate, and N-vinyl-pyrrolidone. Calorimetric analyses revealed that the polyether soft segment phase separated within the SINs. At higher temperature, dynamic mechanical measurements demonstrated the presence of only one glass transition temperature (T_g) intermediate in temperature to the T_g of the vinyl network and the T_g of the urethane hard phase. This is indicative of chain entanglement (interpenetration) between the vinyl network and the polyurethane hard segments resulting in a two-phase morphology. Small-angle X-ray scattering analyses provided measurements of diffuse phase boundary thickness, phase mixing, and domain size distribution. Appreciable interfacial thickness was not observed and thus phase mixing occurred within the phases. Domain size distribution indicated that high network constraints hindered the development of domains and limited the phase segregation.