Polyisobutene-poly(methylmethacrylate) interpenetrating polymer networks: synthesis and characterization

Interpenetrating polymer networks (IPNs) combining polyisobutene (PIB) and poly(methyl methacrylate) (PMMA) networks were prepared using a in situ strategy. PIB networks were formed by isocyanate—alcohol addition between the hydroxyl end groups of telechelic dihydroxy-polyisobutene and an isocyanate cross-linker, catalyzed by dibutyltindilaurate (DBTDL). PMMA networks were obtained from free-radical co-polymerization of methyl methacrylate (MMA) with ethylene glycol bismethacrylate (EGDM) in the presence of dicyclohexyl peroxydicarbonate (DCPD) as the initiator. The synthesis of each network during the IPN formation was followed by FTIR spectroscopy. The highest degree of interpenetration is obtained by forming the PIB network first. The corresponding transparent IPNs exhibit two mechanical relaxation temperatures as determined by Dynamic mechanical thermal analysis (DMTA), corresponding to those of PMMA and PIB enriched phases. Mechanical properties of PIB networks are tremendously improved by the presence of PMMA network in such IPN architecture.     

Immobilization of polyisobutene in semi-interpenetrating polymer network architecture

The entrapment of linear polyisobutene (PIB) in semi-IPN architecture is shown to be as efficient as it is in cross-linkable telechelic PIB based full IPN architectures as far as the suppression of cold flow is concerned. Indeed, homogeneous linear PIB/cross-linked polycyclohexylmethacrylate (PCHMA) semi-IPNs containing from 20 to 70 wt% PIB and synthesized without solvent show no cold flow and higher mechanical properties than those of linear PIB or 50 wt% PIB containing blend. In addition, the particular barrier properties toward gas and water are preserved. Those properties arise from the phase co-continuity morphology of the semi-IPN materials which moreover compares with that of corresponding IPNs. A systematic study of the synthesis conditions (nature of the initiator, temperature, cross-linking density) showed that the reacting mixture viscosity is an important parameter that controls the phase separation degree in the final material.     

Polyisobutene/polystyrene interpenetrating polymer networks: Effects of network formation order and composition on the IPN architecture

In order to improve polyisobutene (PIB) mechanical properties, a PIB network is combined with a polystyrene (PS) one into an interpenetrating polymer network (IPN) architecture. PIB network is formed by alcohol addition between the hydroxyl end groups of a telechelic dihydroxy-polyisobutene and a pluri-isocyanate. PS network is synthesized by free-radical copolymerization of styrene with divinylbenzene. Thus, the optimal synthesis conditions are determined by FTIR spectroscopy and the kinetics of the alcohol-isocyanate addition is studied in detail. A short kinetic study of the PS network formation inside the PIB network is also carried out. The highest degree of interpenetration is obtained by forming the PIB network first. The corresponding transparent IPNs exhibit two mechanical relaxations corresponding to those of PS and PIB enriched phases. However, mechanical properties of PIB networks are tremendously improved by the presence of a PS network in such IPN architectures.     

Damping Properties of Polyorganosiloxane/Poly(methyl methacrylate) Interpenetrating Networks

Interpenetrating polymer networks (IPNs) based on polyorganosiloxane/poly(methyl methacrylate) were prepared via sequential polymerization and the damping and mechanical properties of these materials were studied. The effects of crosslinking in both the first‐ and second‐formed networks were investigated. The experimental results show that the extent of damping of the IPNs was decreased and shifted to higher temperature as the content of poly(methyl methacrylate) was increased; the mechanical properties such as tensile strength and hardness (Shore A) were increased with increasing poly(methyl methacrylate) (PMMA) content. The loss factor peak becomes narrower with increasing crosslinker level in the first‐formed network (polysiloxane network), while increasing crosslinker content in the second‐formed network (PMMA network) results in a broadening of the IPN transition peak and moves the IPN transition to higher temperatures as well.     

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     

Polysiloxane-Cellulose acetate butyrate cellulose interpenetrating polymers networks close to true IPNs on a large composition range. Part II

Interpenetrating polymer networks combining cellulose acetate butyrate (CAB) and α,ω-divinyl-polydimethylsiloxane (PDMS) in different weight proportions have been synthesized. The synthesis involves a one pot-one shot process in which all components are first mixed together. For each composition, the relative CAB and PDMS network formation rates are adjusted through the concentration of DBTDL used as CAB network formation catalyst. Thus, the chemically independent networks are formed quasi-simultaneously in order to avoid phase separation. The CAB cross-linking density effect on the PDMS/CAB IPN mechanical properties has also been particularly studied. All synthesized IPNs are transparent and only one mechanical relaxation temperature lying between those of the single CAB and PDMS networks is observed by DMTA analysis. These results show that the networks are correctly interpenetrated and no phase separation is observed at the DMTA level. Some mechanical properties of the PDMS network are significantly improved in this IPN combination and their stress-strain behavior has highlighted a synergistic effect arising from the IPN architecture. Thus, these IPNs exhibit many characteristics, which would allow defining them as close to ‘true’ IPNs.     

Poly(ethylene oxide)/polybutadiene based IPNs synthesis and characterization

Interpenetrating polymer networks (IPNs) were prepared from hydroxytelechelic polybutadiene (HTPB) and poly(ethylene oxide) (PEO) via an in situ process. The PEO network was obtained by free radical copolymerization of poly(ethylene glycol) methacrylate and dimethacrylate. Addition reactions between HTPB and a pluri-isocyanate cross-linker (Desmodur^® N3300) led to the HTPB network. Polymerization kinetics were followed by Fourier transform spectroscopy in the near and middle infrared. Mechanical properties and the IPN morphology were investigated by dynamic mechanical analysis and transmission electron microscopy. The relation between the formation rates of the two networks and the IPN final morphology is discussed.     

Behavior of polyoxyethylene‐containing interpenetrating polymer networks and their LiCLO4 complexes as phase transfer catalysts and ionic conductors

Simultaneous grafted interpenetrating polymer networks (IPNs) based on [castor oil–poly(ethylene glycol) (PEG)] polyurethane and poly(alkyl methacrylate) were synthesized by simultaneously coupling castor oil and PEG with 2,4‐toluene diisocyanate and by radical polymerization of alkyl methacrylate with castor oil. The gel content of the IPNs is ～96% in most cases. The IPNs were characterized by infrared spectroscopy. The effects of compositional variation of the IPNs on phase transfer catalytic efficiency and mechanical properties, and conductivity of the IPNs complexed with LiClO₄ were also studied. The results show that the IPNs have good phase transfer catalytic ability in the Williamson reaction and exhibit a maximum conversion of potassium phenolate at 55% polyoxyethylene (PEO). The phase transfer catalytic ability of the IPN increases with molecular weight of PEG used in the IPN synthesis and with the length of alkyl groups of the grafts, but decreases with increasing crosslinking degree. The complex of the IPNs with LiClO₄ exhibits good ionic conductivity at room temperature in the range 10^?5–3 × 10^?4 S/cm. This ionic conductivity decreases with increasing either the crosslinking degree or the molecular weight of PEG used, but increases with increasing PEO content. The more compatible are the grafts with PEO, the lower is the conductivity. Either butyl methacrylate or ethyl methacrylate is a good choice for the monomer in the synthesis of the IPNs for use as phase transfer catalysts and ion conducting materials. The IPNs showed high tensile strength in the range 10–20 MPa. The good mechanical properties of the IPNs favor their applications as a strong solid polymer electrolyte film and an easily recoverable phase transfer catalyst. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 830–836, 2003     

Effect of crosslinking density on the physical properties of interpenetrating polymer networks of polyurethane and 2-hydroxyethyl methacrylate-teminated polyurethane

Interpenetrating polymer networks (IPNs) of 2-hydroxyethyl methacrylate-terminated polyurethane (HPU) and polyurethane (PU) with different crosslinking densities of the PU network were prepared by simultaneous solution polymerization. Dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) show that compatibility of component polymers in IPN formation depends on the crosslinking density of the PU network. Physical properties such as density and water absorption rely on the subtle balance between the degree of phase separation and the crosslinking density of the PU network. In spite of the occurrence of phase separation, the tensile moduli and tensile strength of the IPNs increase with the crosslinking density of the PU network. Morphological observation by scanning electron microscopy revealed different fracture surfaces between the compatible and incompatible IPNs. Surface characteristics of the IPNs, indicated as hydrogen bonding index and hard-to-soft segment ratio, are altered considerably by varying surface morphologies. Improved blood compatibility of IPN membranes is due to the variation of the hydrophilic and hydrophobic domain distribution.     

Poly(ether urethane)/poly(ethyl methacrylate) IPNs with high damping characteristics: The influence of the crosslink density in both networks

Interpenetrating polymer networks (IPNs) with a controlled degree of microphase separation were synthesized from a poly(ether urethane) (PUR) and poly(ethyl methacrylate) (PEMA). The influence of the crosslink density of both networks was investigated in the 70:30 PUR/PEMA IPN. The extent of damping was evaluated by dynamic mechanical thermal analysis. Mechanical properties were studied using tensile testing and hardness measure-ments. Control of crosslinking was successful in tailoring the damping profile. Higher crosslinking in the first-formed network (polyurethane) seemed to increase slightly the area under the linear loss modulus curve, LA, whereas no influence was obvious when changing the crosslink density in the second network. TGA studies revealed improved thermal properties for the IPNs with a higher crosslink density in the PUR network. TEM micrographs confirmed a finer morphology for the materials with a higher crosslink density in the PUR, whereas increasing the crosslink density in the PEMA network resulted in a decrease of phase mixing. © 1996 John Wiley & Sons, Inc.     

Synthesis and characterization of high performance,transparent interpenetrating polymer networks with polyurethane and poly(methyl methacrylate)

Transparent, interpenetrating polymer network (IPN) materials were synthesized using polyurethane (PU) and poly(methyl methacrylate) (PMMA). PMMA contributed to the transparency and rigidity necessary for use in impact‐resistant applications, whereas PU contributed to toughness. Several factors affecting the physical properties, such as the ratio of PU to PMMA, curing profile, inclusion of different isocyanates for the PU phase, and use of an inhibitor in the PMMA phase, were investigated. Full‐IPNs were synthesized so that the two polymer networks would remain entangled with one another, and domain sizes of each system were reduced, mitigating phase separation. Both simultaneous IPNs, polymerization of monomers occurring at the same time, and sequential IPNs, polymerization of monomers occurring at different temperatures, were synthesized for studying the reaction kinetics and final morphologies. The phase morphology and the final thermal and mechanical properties of the IPNs prepared were evaluated. Findings suggest that samples containing ～80 wt% PMMA, 1,6‐diisocyanatohexane 99+% (DCH), and an inhibitor with the MMA monomer created favorable results in the thermo‐mechanical and optical properties. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

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     

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     

Ionomer interpenetrating polymer networks from polyurethane anionomers and polyurethane isocyanurate

Two-component interpenetrating polymer network (IPN) systems composed from polyurethane isocyanurate and polyurethane anionomer were prepared by simultaneous polymerization and crosslinking in solution. Specific attractive forces that occurred among various networks helped to make them compatible and led to the formation of true homogeneous topologically interpenetrating polymer networks. These ionomer IPNs were characterized by means of stress-strain properties, hardness, thermogravimetric analysis, density and conductivity. The morphology of the IPNs was studied by thermomechanical analysis and dynamic mechanical analysis.     

Miscibility and thermal and dynamic mechanical behaviour of semi‐interpenetrating polymer networks based on polyurethane and poly(hydroxyethyl methacrylate)

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     

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     

Synthesis and characterization of interpenetrating networks from polycarbonate and cellulose acetate butyrate

Polycarbonates (PC) are currently used for organic optical glass; nevertheless they show a poor impact resistance which may be increased by combination with cellulose acetate butyrate (CAB) into a PC/CAB interpenetrating polymer network (IPN), without altering the material transparency as we show here. A series of rigid IPNs based on an aliphatic polycarbonate and CAB was prepared through in situ polymerization techniques. The kinetics of the formation of two networks in the IPNs were studied by FTIR spectroscopy. Effects of the CAB cross-linking and weight proportions of the two components in the IPNs were investigated by dynamic mechanical thermal analysis.     

Molecular demixing in poly[cross-(ethyl acrylete)]-inter-poly[cross-(methyl methacrylate)] interpenetrating polymer networks brought about by selective decrosslinking and annealing

The extent of molecular demixing of poly[cross-(ethyl acrylate)]-inter-poly[cross-(methyl methacrylate)] interpenetrating polymer networks (PEA/PMMA IPNs), of mid-range composition was investigated by decrosslinking and/or annealing using dynamic mechanical spectroscopy. A single broad transition characteristic of extensive but incomplete molecular mixing was observed for the PEA/PMMA IPN. The presence of crosslinking in both phases of an IPN enhances the mutual miscibility of the polymers. Through the use of a labile crosslinker, acrylic acid anhydride (AAA), polymer networks may be decross-linked, allowing the chains to separate and form two distinct phases. Annealing further sharpens the transitions, and phase separation becomes most pronounced when decrosslinking is followed by annealing.     

Mechanical properties of polyurethane-unsaturated polyester interpenetrating polymer networks

Interpenetrating polymer networks (IPNs) based on a polyurethane (PU) and two unsaturated polyester (UPE) resins (a commercially available UPE and a partially endcapped UPE) were prepared. The mechanical properties, such as tensile strength, elongation at break, impact strength, and dynamic mechnical properties of IPNs, were studied by changing reaction temperature, PU reaction rate, and UPE reaction rate. Owing to the unique microgel formaton of UPE, the first formed network tends t be the dispersed phase in the PU-UPE IPN system. The reaction sequence was found to be an important factor in determining the phase mixing and phase morphology of the IPNs. When the PU reaction was faster, extensive phase mixing due to strong grafting or chain interpenetration was obtained. When the UPE reacted first, grafting was retarded by the microgel formation of the UPE network. It was found that simultaneous reaction of the two reacting system resulted in a co-continuous structure that provided enhanced tensile properties and impact strength.     

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