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.     

Semi- and fully interpenetrating polymer networks based on polyurethane-polyacrylate systems. X. Polyurethane-poly(ethyl acrylate) interpenetrating polymer networks

A series of polyurethane-poly(ethyl acrylate) interpenetrating networks (IPNs) containing 40 wt% polyurethane were prepared, in which the cross-link density of the polyurethane component was varied by altering the ratio of diol/triol. Decreasing the molecular weight between crosslinks from 9500 to 1200 g/mol brought about an increase in the tensile strength accompanied by a decrease in elongation at break. The tensile properties of the IPNs are, however, poorer than those of the equivalent polyurethane homopolymers. Electron microscopy showed that the polyurethane was present as distinct phases, connected by a cellular fine structure, in the poly(ethyl acrylate) matrix. Dynamic mechanical analysis as well as sonic velocity studies gave results which were consistent with this morphological picture.     

Semi- and fully interpenetrating polymer networks based on polyurethane–polyacrylate systems. III. Polyurethane–poly(methyl acrylate) semi-2-interpenetrating polymer networks

Two series of semi-2-IPNs based on a polyurethane and a poly(methyl acrylate) crosslinked with divinyl benzene were prepared and investigated using dynamic mechanical analysis, sonic velocity measurements, and electron microscopy. In the one series, the level of crosslinking was varied to give ultratight networks. In the other, the composition was altered, but the amount of the crosslinking agent used was kept constant. For the first series, it was concluded that the degree of crosslinking had a significant influence on the morphology and properties by controlling the amount of enforced mixing. The dynamic mechanical data for the second series fitted the Davies modulus–composition equation, indicating that both phases are continuous.     

Semi- and fully interpenetrating polymer networks based on polyurethane-polyacrylate systems. IX. Properties of an isomerically related interpenetrating network

Two polyurethane–poly(vinyl acetate) interpenetrating polymer networks of differing composition were synthesized and certain physical properties investigated. The results are compared with semi-1-interpenetrating polymer networks of the same system as well as with, where appropriate, polyurethane-poly(methyl acrylate) interpenetrating polymer networks. Dynamic mechanical analysis clearly indicated phase separation for both compositions. The poly(vinyl acetate) glass transition showed a shift to lower temperatures accompanied by a shift to higher temperatures of the polyurethane transition. Such shifts indicate a certain extent of mixing. Electron microscopy confirmed phase separation and for a material with 20% by weight of polyurethane indicated that both components are continuous. This latter material also had a higher tensile strength and elongation at break than the corresponding poly(vinyl acetate) homopolymer. At 60% by weight of polyurethane the stress-strain characteristics are those of a reinforced rubber. Certain modulus–composition theories, and, also, sonic velocity measurements were consistent with these morphological conclusions.     

Semi- and fully interpentrating polymer networks based on polyurethane–polyacrylate systems. IV. Grafted semi-1-interpenetrating polymer networks

A series of semi-1-IPNs containing 40% polyurethane and 60% polymethyl acrylate was synthesized using Adiprene L-100, trimethylol propane, and polybutadiene diol. This diol was chosen to yield polyurethanes with a large number of potential graft sites for the methyl acrylate which was polymerized after the polyurethane network had been formed. A series of linear polyurethane–polymethyl acrylate blends, covering a range of compositions, was also prepared. The polyurethane for these polyblends was synthesized from Adiprene L-100 and butane-1,4-diol. Both sets of materials were investigated by dynamic mechanical analysis. On the basis of a comparison of solubility parameters, the polyurethanes and polymethyl acrylate would be expected to be incompatible. In the dynamic loss modulus-temperature plots of the polyblends there was a significant shift of the polyurethane T_g to higher temperature, but the polymethyl acrylate transition did not shift. The polyurethane transitions of the semi-1-IPNs were also shifted, but considerably more than in the case of the polyblends. For both systems, it was postulated that grafting had occured to a significant extent. With the semi-1-IPNs, it was found that as M?_c decreased the extent of grafting apparently increased. This was rationalized on the grounds that as the network chain lengths decrease, a higher proportion of the methyl acrylate monomer, prior to polymerization, was close to polyurethane segments and that this is a situation likely to lead to more grafting.     

Polyamide–polyurethane interpenetrating polymer networks prepared by synthesis in the melt

Two types of interpenetrating polymer networks based on polyamide (nylon 12) and a polyurethane formed in the polyamide melt were prepared. The first type (A), which could be regarded as a semi-2-IPN, consisted of a polyurethane component crosslinked with trimethylolpropane whereas for the second type (B), which would meet the definition of a thermoplastic IPN, the polyurethane component was chain-extended with butane-1,4-diol only. The phase morphologies of these IPNs were investigated using electron microscopy, dynamic mechanical analysis, tensile testing, and sonic velocity measurements. Electron micrographs were compared by using the conventional TEM technique and a Robinson-type backscattered electron detector in combination with a SEM. It was concluded that the materials are phase separated, but with a fine continuous-dispersed phase structure. For a 44 wt % polyurethane IPN a cocontinuous phase structure with a subcellular texture was indicated. One physically blended sample was compared with the analogous IPN-type sample.     

Semi- and fully interpenetrating polymer networks based on polyurethane–polyacrylate systems. II. Polyurethane–poly(methyl acrylate) semi-1-interpenetrating polymer networks

A series of semi-1-IPNs based on polyurethane networks and poly(methyl acrylate) were prepared, and their properties and morphologies investigated. All the materials showed substantial phase separation, but the phase sizes were orders of magnitude smaller than those observed for blends of the same linear polymers. The effects of the isocyanate/hydroxyl ratio used in the preparation of the polyurethane, of the molecular weight of the linear polymethyl acrylate component, of the overall composition, and of the molecular weight between crosslinks in the polyurethane networks were investigated. Stress-relaxation experiments were conducted over a range of temperatures and master curves were produced for both components of the semi-1-IPNs and for a semi-1-IPN containing 40 wt% polyurethane. It was found that both the components obeyed a WLF type of equation, but that the semi-1-IPN only showed this type of behavior over a limited temperature range. Several reinforcement theories were applied to experimental dynamic storage modulus data. The closest fit was given by the Davies equation and by the logarithmic rule of mixing. By changing the exponent in the Davies equation to 1/10, a close fit was found. Application of a modified Takayanagi model indicated that these semi-1-IPNs showed some dual phase continuity when the poly(methyl acrylate) composition was relatively high.     

Acronal-polymethyl acrylate interpenetrating polymer networks

Four interpenetrating polymer networks were prepared by swelling crosslinked Acronal (a copolymer of styrene and butyl acrylate) with methyl acrylate plus crosslinking agent and then polymerizing the methyl acrylate in situ. Certain properties of the constituent network materials, plus the interpenetrating polymer networks which contained 70, 50, 35 and 25% by weight of polymethyl acrylate, were investigated. Electron microscopy showed the interpenetrating polymer networks to be two-phase materials with the polymethyl acrylate domain size increasing with increasing polymethyl acrylate content. Longitudinal sonic velocity measurements indicate that at around 50% by weight of polymethyl acrylate both phases become continuous while dynamic mechanical spectroscopy leads to the view that the constituent networks were not extensively mixed.     

Dynamic‐mechanical behavior of hydrophobic–hydrophilic interpenetrating copolymer networks

Sequential interpenetrating polymer networks (IPNs) were prepared by free‐radical polymerization. One of the components of the IPN was a poly(butyl acrylate) (PBA) network, and the other one was a poly(methyl methacrylate‐co‐hydroxyethyl methacrylate) copolymer network. Dynamic‐mechanical experiments show that the IPNs are phase separated: two main α relaxations occur in all samples, the low temperature one corresponding to the PBA network and that appearing at higher temperature due to the copolymer network. The latter shows a shape analogous to a pure poly(hydroxyethyl methacrylate) (PHEMA) network independently of the copolymer composition. The influence of water absorption on the dynamic‐mechanical spectrum shows that only a small amount of water reaches the butyl acrylate segments. The dependence of the mechanical behavior of the poly(methyl methacrylate‐co‐hydroxyethyl methacrylate) copolymer networks with the copolymer composition has been also analyzed. POLYM. ENG. SCI., 46:930–937, 2006. © 2006 Society of Plastics Engineers     

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.     

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.     

Polyurethane acrylate/epoxy–amine acrylate hybrid polymer networks

New classes of hybrid polymer networks (HPNs), having variable polyurethane acrylate (PUA) and epoxy–amine acrylate (EAA) compositions, were prepared using initially miscible systems in methyl methacrylate (MMA). The initial systems were based on PUA prepolymer and EAA monomer solutions in MMA. HPNs were a result of epoxy–amine and radical polymerization competition. Phase separation occurred during the course of HPN formation. Mechanical dynamic analysis of the prepared HPNs showed good affinity between the PUA and PMMA phases and lower affinity between the EAA and PMMA phases. Mechanical property evolution and transmission electronic microscopy showed that, for all the composition ranges used in this study (PUA/EAA/PMMA 15/45/40–45/15/40 wt %), the PUA‐rich phase was the continuous phase. EAA‐rich phases, 20–50 nm, in the PUA‐rich matrix were obtained for HPNs containing up to 30 wt % EAA. For higher EAA concentration (45 wt %), 2 μm EAA‐rich phases were obtained in the PUA‐rich matrix. A substructure was also observed in each phase. PUA/EAA copolymers were prepared and used successfully for the compatibilization of the different phases of the HPNs. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2711–2717, 2000     

Polyurethane–polyacrylate interpenetrating polymer networks. II

Two component topologically interpenetrating polymer networks of the SIN type (simultaneous interpenetrating networks) composed of a melamine-cured polyacrylate and three different polyether-based polyurethanes were prepared. The linear polymers and prepolymers were combined in solution, together with the necessary crosslinking agents and catalysts, films were cast and subsequently chain extended and crosslinked in situ. In all cases, maxima in tensile strength significantly higher than the tensile strengths of the component networks occurred at 50% polyurethane : 50% polyacrylate. This was explained by an increase in crosslink density resulting from interpenetration. One of the interpenetrating polymer networks showed only one glass transition temperature (T_g) (measured calorimetrically) intermediate in temperature to the T_g's of the components and as sharp as the component T_g's. This is indicative of phase mixing and indicates at least partial chain entanglement (interpenetration). Some enhancement of other physical properties was also noted.     

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 fluorine‐containing polyurethane–acrylate core–shell emulsion

Fluorinated polyurethane–acrylate (FPUA) hybrid emulsion was prepared by copolymerization of polyurethane, methyl methacrylate, and 1H,1H,2H,2H‐heptadecafluorooctyl acrylate (FA) via emulsion polymerization in the presence of a perfluoronated reactive surfactant. The polyurethane was synthesized from isophorone diisocyanate, poly(propylene glycol)‐1000, dimethylolpropionic acid, 1,4‐butanediol, and 2‐hydroxyethyl methylacrylate. The influence of the monomer on the surface properties, wetting behaviors, particle size, and viscosity of the emulsion was investigated. The mechanical properties of FPUA latex films were improved, and water absorption and contact angle were improved with the addition of methyl methacrylate and FA. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43357.     

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     

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     

Semi‐ and full‐interpenetrating polymer networks based on polyurethane produced from canola oil and poly(methyl methacrylate)

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     

Semi- and fully interpenetrating polymer networks based on polyurethane–polyacrylate systems. I. The polyurethane networks

The polyurethane networks based on commerical prepolymer, Adiprene L-100, and trimethylol propane (system 1) and on toluene diisocyanate, polypropylene gylcol, and trimethylol propane (system 2) were prepared and characterized in a number of ways. The materials constitute the first formed networks in a series of interpenetrating polymer networks and semi-interpenetrating polymer networks to be reported in subsequent papers in this series. System 1 networks were characterized by swelling tests which showed the M _c values to be sensitive to the amount of polyurethane present in the polymerization solvent. Stress–strain, stress–relaxation, and dynamic mechanical analyses wer also conducted. For system 2, M _c was measured, by both the swelling and the Mooney–Rivlin techniques, for materials in which the diol-to-triol ratios had been altered. the latter showed C₁ increasing as M _c decreased while C₂ was small and changed onlyy slightly indicating approximately ideal behavior. These M _c values were about 13 % larger than predicted by swelling.     

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.