Polyepichlorohydrin polyurethane/poly(methyl methacrylate) interpenetrating polymer networks

Polyurethane (PU) based on polyepichlorohydrin/poly(methyl methacrylate) (PECH/PMMA) interpenetrating polymer networks (IPNs) was synthesized by a simultaneous method. The effects of composition, hydroxyl group number of PECH, NCO/OH ratio and crosslinking agent content in IPNs were investigated in detail. Some other glycols, such as poly(ethylene glycol), poly(propylene glycol) and hydroxyl-terminated polybutadiene, were also used to obtain PU/PMMA IPNs. The interpenetrating and fracture behaviors of the IPNs are explained briefly.     

New interpenetrating polymer networks based on uralkyd/poly(glycidyl methacrylate)

Semi- and full-interpenetrating polymer networks (IPNs) based on uralkyd resin (UA)/poly(glycidyl methacrylate) were synthesized in the laboratory by the sequential technique. Infrared spectra of the homopolymers and the IPNs were studied. A study of the mechanical properties viz. tensile strength and elongation percentage was carried out. The apparent densities of the homopolymers and their IPNs were determined and compared. Glass transition studies of the IPNs were conducted with the aid of differential scanning calorimetry (DSC). Phase morphology of the IPNs was observed using scanning electron microscopy (SEM). DSC results revealed a single glass transition temperature (T_g) for both the semi- as well as the full-IPNs suggesting good interpenetration in them. The SEM micrographs as well as the IR-spectra gave an indication that apart form the interpenetration phenomena, grafting reaction between the -NCO groups of UA and the epoxy group of glycidyl methacrylate might have occurred to some extent.     

Interpenetrating polymer networks of poly(dimethyl siloxane–urethane) and poly(methyl methacrylate)

Simultaneous IPNs of poly(dimethyl siloxane-urethane) (PDMSU)/poly(methyl methacrylate) (PMMA) and related isomers have been prepared by using new oligomers of bis(β-hydroxyethoxymethyl)poly(dimethyl siloxane)s (PDMS diols) and new crosslinkers biuret triisocyanate (BTI) and tris(β-hydroxylethoxymethyl dimethylsiloxy) phenylsilane (Si-triol). Their phase morphology have been characterized by DSC and SEM. The SEM phase domain size is decreased by increasing crosslink density of the PDMSU network. A single phase IPN of PDMSU/PMMA can be made at an M_c = 1000 and 80 wt % of PDMSU. All of the pseudo- or semi-IPNs and blends of PDMSU and PMMA were phase separated with phase domain sizes ranging from 0.2 to several micrometers. The full IPNs of PDMSU/PMMA have better thermal resistance compared to the blends of linear PDMSU and linear PMMA. © 1993 John Wiley & Sons, Inc.     

Poly(ethylene oxide)/poly(methyl methacrylate) (semi-)interpenetrating polymer networks: Synthesis and phase diagrams

Interpenetrating polymer networks (IPNs) of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) were prepared by simultaneous network formation. The PEO network was produced by acid-catlayzed self-condensation of α,ω-bis(triethoxysilane)-terminated PEO in the presence of small amounts of water. The PMMA network was formed by free radical polymerization of MAA in the presence of divinylbenzene as crosslinker. The reaction conditions were adjusted to obtain similar crosslinking kinetics for both reactions. An attempt was made to construct a phase diagram of the IPNs by measuring the composition of the IPNs at the moment of the appearance of the phase separation, as indicated by the onset of turbidity. This composition could be determined because the siloxane crosslinks of the PEO network could be hydrolyzed in aqueous NaOH with the formation of linear, soluble PEO chains. The phase diagram was compared with phase diagrams of blends of linear polymers and of semi-IPNs (crosslinked PMMA and linear PEO), obtained under similar conditions, i.e. polymerization of MMA in the presence of varying amounts of PEO. It was observed that the form of the phase diagrams of the linear polymers is similar to that of the IPNs, but is quite different from that of the semi-IPNs. Thus, homogeneous transparent materials containing up to 60% of PEO could be prepared in the blends and the IPNs, but in the semi-IPNs, phase separation occurred with PEO contents as low as 10%.     

New elastomers based on uralkyd/polyethyl methacrylate semi- and full interpenetrating polymer networks

Two-component semi- and full interpenetrating polymer networks (IPNs) of soybean-oil-based uralkyd resin (UA) and polyethyl methacrylate (PEMA) were synthesized by the sequential technique. The elastomers obtained were characterized by mechanical properties such as tensile strength, elongation, and hardness (Shore A). The apparent densities of these samples were determined and compared. Glass-transition studies were carried out using differential scanning calorimetry. The thermal characterization of the elastomers was undertaken with the aid of thermogravimetric analysis. Phase morphology was studied by scanning electron microscopy. The effect of the compositional variation on the aforementioned properties was examined. The maximum elongation for both the semi- and full IPNs was observed at 60% UA and 40% PEMA. Glass-transition studies revealed that there was a phase separation in the semi-IPNs as two T_gs were obtained, whereas the full IPNs showed one T_g, indicating a single phase transition. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4302–4308, 1999     

Viscoelastic and damping characteristics of poly(n‐butyl acrylate)‐poly(n‐butyl methacrylate) semi‐IPN latex films

This article reports the synthesis, characterization, and damping characteristics of semi‐interpenetrating (semi‐IPN) latex systems composed of poly n‐butyl acrylate (PBA) core and poly n‐butyl methacrylate (PBMA) shell. The IPN's were prepared by seeded emulsion polymerization using crosslinked PBA seeds with varying crosslinker (m‐diisopropenyl benzene) concentration. The polymer weight ratio in the first and second stage polymerization is maintained at 1:1 in all the cases. The particle size determined by dynamic light scattering shows a decrease in the shell thickness with increasing crosslinker concentration of the seed. The mechanical properties, like Shore A hardness of the films, increased from 18 to 65 when the crosslinker concentration is increased from 0 to 4.8 mol%. The dynamic mechanical studies show that the modulus value of the IPN's is below that of non‐crosslinked films, and the value depends upon the crosslink density of the seed. Mechanical models, such as the Kerner's model and the Takayanagi's model, were used to explain the variation in the dynamic mechanical properties with the degree of seed crosslinking. The study indicates lower bound (rubbery) behavior for the films with lightly crosslinked cores. The study also shows that, at lower crosslinker concentration enhanced phase separation and better damping properties are achieved but at higher cross linker concentration (>2 mol%) greater interpenetration of the shell monomer to the cores takes place and tough films, with reduced damping properties are formed. Copyright © 2007 John Wiley & Sons, Ltd.     

New silicone hydrogels based on interpenetrating polymer networks comprising polysiloxane and poly(vinyl alcohol) networks

A method for the synthesis of a new silicone hydrogel as a biphase material for soft contact lenses is considered. The method is based on the synthesis of sequential interpenetrating polymer networks (IPN) and includes the following stages: (1) cross‐linked silicone synthesis by the reaction of vinyl‐ and hydride‐containing oligosiloxanes; (2) silicone network saturation with vinyl acetate and cross‐linking monomer followed by UV‐initiated polymerization to form an IPN comprising the silicone and cross‐linked poly(vinyl acetate) (PVAc) network; (3) PVAc network alcoholysis with methanol to obtain silicone hydrogels comprising the silicone and cross‐linked poly(vinyl alcohol) (PVAl). A study of hydrophilic, optical, mechanical, and structural features of the silicone hydrogels showed that optical transparency is achieved for materials with the highest density of silicone network cross‐linking where the size of IPN structural units does not exceed 100 nm. The water content in hydrophilic networks of silicone hydrogel is found to be below the values typical of cross‐linked PVAl, leading to non‐additivity of IPN mechanical properties. Indeed, the elasticity moduli (E) of the hydrophilic and silicone networks are 0.4–0.7 and 0.7–1.8 MPa, respectively, whereas for some IPN this value reaches 3.0 MPa. The optimal parameters of synthesis providing the reduction of E to 0.8–1.6 MPa without deterioration of the required performance characteristics (optical transparency 90–92%, water content 20–39 wt%) are determined. Copyright © 2009 John Wiley & Sons, Ltd.     

Characterization and degradation of poly(methylphenylsiloxane)–poly(methyl methacrylate) interpenetrating polymer networks

Poly(methylphenylsiloxane)–poly(methyl methacrylate) interpenetrating polymer networks (PMPS–PMMA IPNs) were prepared by in situ sequential condensation of poly(methylphenylsiloxane) with tetramethyl orthosilicate and polymerization of methyl methacrylate. PMPS–PMMA IPNs were characterized by infrared (IR), differential scanning calorimetry (DSC), and ²⁹Si and ¹³C nuclear magnetic resonance (NMR). The mobility of PMPS segments in IPNs, investigated by proton spin–spin relaxation T₂ measurements, is seriously restricted. The PMPS networks have influence on the average activation energy E_a,av of MMA segments in thermal degradation at initial conversion. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1717–1724, 1999     

Viscoelastic properties of nanostructured natural rubber/polystyrene interpenetrating polymer networks

The effects of the blend ratio and initiating system on the viscoelastic properties of nanostructured natural rubber/polystyrene‐based interpenetrating polymer networks (IPNs) were investigated in the temperature range of ?80 to 150 °C. The studies were carried out at different frequencies (100, 50, 10, 1, and 0.1 Hz), and their effects on the damping and storage and loss moduli were analyzed. In all cases, tan δ and the storage and loss moduli showed two distinct transitions corresponding to natural rubber and polystyrene phases, which indicated that the system was not miscible on the molecular level. However, a slight inward shift was observed in the IPNs, with respect to the glass‐transition temperatures (T_g's) of the virgin polymers, showing a certain degree of miscibility or intermixing between the two phases. When the frequency increased from 0.1 to 100 Hz, the T_g values showed a positive shift in all cases. In a comparison of the three initiating systems (dicumyl peroxide, benzoyl peroxide, and azobisisobutyronitrile), the dicumyl peroxide system showed the highest modulus. The morphology of the IPNs was analyzed with transmission electron microscopy. The micrographs indicated that the system was nanostructured. An attempt was made to relate the viscoelastic behavior to the morphology of the IPNs. Various models, such as the series, parallel, Halpin–Tsai, Kerner, Coran, Takayanagi, and Davies models, were used to model the viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by group contribution analysis; this showed that the damping was influenced by the phase morphology, dual‐phase continuity, and crosslinking of the phases. Finally, the homogeneity of the system was further evaluated with Cole–Cole analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1680–1696, 2003     

Heterogeneity of glass transition dynamics in polyurethane‐poly(2‐hydroxyethyl methacrylate) semi‐interpenetrating polymer networks

The peculiarities of segmental dynamics over the temperature range of ?140 to 180 °C were studied in polyurethane‐poly(2‐hydroxyethyl methacrylate) semi‐interpenetrating polymer networks (PU‐PHEMA semi‐IPNs) with two‐phase, nanoheterogeneous structure. The networks were synthesized by the sequential method when the PU network was obtained from poly(oxypropylene glycol) (PPG) and adduct of trimethylolpropane (TMP) and toluylene diisocyanate (TDI), and then swollen with 2‐hydroxyethyl methacrylate monomer with its subsequent photopolymerization. PHEMA content in the semi‐IPNs varied from 10 to 57 wt %. Laser‐interferometric creep rate spectroscopy (CRS), supplemented with differential scanning calorimetry (DSC), was used for discrete dynamic analysis of these IPNs. The effects of anomalous, large broadening of the PHEMA glass transition to higher temperatures in comparison with that of neat PHEMA, despite much lower T_g of the PU constituent, and the pronounced heterogeneity of glass transition dynamics were found in these networks. Up to 3 or 4 overlapping creep rate peaks, characterizing different segmental dynamics modes, have been registered within both PU and PHEMA glass transitions in these semi‐IPNs. On the whole, the united semi‐IPN glass transition ranged virtually from ?60 to 160 °C. As proved by IR spectra, some hybridization of the semi‐IPN constituents took place, and therefore the effects observed could be properly interpreted in the framework of the notion of “constrained dynamics.” The peculiar segmental dynamics in the semi‐IPNs studied may help in developing advanced biomedical, damping, and membrane materials based thereon. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 963–975, 2007     

Gas barrier and adhesion of interpenetrating polymer networks based on poly(diurethane bismethacrylate) and different epoxy-amine networks

Interpenetrating polymer networks (IPNs) composed of poly(methacrylate) and epoxy-amine networks made in situ between two oriented polypropylene sheets were examined in terms of their oxygen barrier and adhesion to the substrate properties. A particular attention was devoted to a system presenting an obvious phase separation. Kinetics of network formation and phase behavior were investigated by infrared and UV-visible spectroscopy, respectively. Since the poly(methacrylate) network could be instantaneously generated by photoirradiation, IPNs differing in network sequence formation were prepared. The influence of the moment at which irradiation was induced, on gas barrier properties of different films was examined. It was shown that similar oxygen transmission rates are obtained whatever the moment of irradiation.     

Semi‐interpenetrating polymer networks based on crosslinked poly(N‐isopropyl acrylamide) and methylcellulose prepared by frontal polymerization

In this work, semi‐interpenetrating gels of poly(N‐isopropyl acrylamide) and methylcellulose were successfully synthesized by using the Frontal Polymerization (FP) technique. The gels were obtained in the presence of dimethyl sulfoxide and trihexyltetradecylphosphonium persulfate, as polymerization solvent and radical initiator, respectively, hence avoiding the formation of bubbles during polymerization. Then, some of the gels containing dimethyl sulfoxide were thoroughly washed with water, hence obtaining the corresponding hydrogels. The effects of the ratio between poly(N‐isopropyl acrylamide) and methylcellulose, the amount of crosslinker and solvent medium (i.e., dimethyl sulfoxide and water) were thoroughly studied, assessing the influence of temperature and velocity of FP fronts on the glass transition temperature values (dried samples), on the swelling behavior and on the dynamic‐mechanical properties (gels swollen both in water and dimethyl sulfoxide). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 437–443     

Synthesis and characterization of poly (n-butyl acrylate)-poly (methyl methacrylate) latex interpenetrating polymer networks by radiation-induced seeded emulsion polymerization

A series of latex interpenetrating polymer networks (LIPNs) were prepared via a two-stage emulsion polymerization of methyl methacrylate (MMA) or mixture of MMA and n-butyl acrylate (n-BA) on crosslinked poly(n-butyl acrylate)(PBA) seed latex using ⁶⁰Co γ-ray radiation. The particles of resultant latex were produced with diameters between 150 and 250 nm. FTIR spectra identified the formation of crosslinked copolymers of PMMA or P(MMA-co-BA). Dynamic light scattering (DLS) showed that with increasing n-BA concentration in second-stage monomers, the particle size of LIPN increased. Transmission electron microscope(TEM) photographs showed that the morphology of resultant acrylate interpenetrating polymer network (IPN) latex varied from the distinct core-shell structure to homogenous particle structure with the increase of n-BA concentration, and the morphology was mainly controlled by the miscibility between crosslinked PBA seed and second-stage copolymers and polarity of P(MMA-co-BA)copolymers. In addition, differential scanning calorimeter (DSC) measurements indicated the existence of reinforced miscibility between PBA seed and P(MMA-co-BA)copolymer in prepared LIPNs.     

Simultaneous interpenetrating polymer networks based on epoxy–acrylate combinations

Simultaneous interpenetrating polymer networks (SINs) based on epoxy/poly(n-butyl acrylate) systems were synthesized at 120°C. The polymerization kinetics were studied both in situ by Fourier Transform Infrared Spectroscopy (FT–IR). Three key events occurred during the polymerization, namely the gelation of the network I, gelation of the network II, and phase separation of one polymer from the other. Thus, metastable phase diagrams describing the relations between the three events were constructed. Three-dimensional tetrahedrons characterizing the four-component system (the two monomers and the two polymers) allow the visualization of these three key events and also define some critical points, for example, the loci of the points where simultaneous gelation of the two networks occurs. The inside of the tetrahedron was also investigated using partially reacted model compounds. These tetrahedrons can be used as guidelines for setting up a synthesis strategy leading to desired morphologies. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1973–1984, 1997     

ESR spin-label study of poly(styrene-co-methacrylic acid)/poly(epsilon-caprolactone) semi-interpenetrating polymer networks with controlled hydrogen-bond interactions

The morphology and miscibility of semi-interpenetrating polymer networks (semi-IPN) prepared with poly(styrene-co-methacrylic acid) [P(S-co-MAA)] of different carboxylic acid contents and poly(epsilon-caprolactone) (PCL) have been studied by ESR spin-label method. The ESR spectra of spin-labeled PCL showed one motional component at any specific temperature. It indicated that the spin-labeled molecules were located in one type of environment. The coexistence of two motional components in the ESR spectra of all semi-IPN samples was observed over a certain temperature range. This phenomenon suggested that the semi-IPNs were not compatible systems; they contained two microphases, a PCL-rich microdomain and a P(S-co-MAA)-rich microdomain. The miscibility could be improved by increasing the carboxylic acid content, which could enhance the hydrogen-bonding interactions between the ester groups of PCL and carboxylic acid groups in P(S-co-MAA). It was also found that the intracomponent cross-linking of the semi-IPNs was not in favor of the miscibility. The microphase separation occurred in all semi-IPNs, even in the samples having strong hydrogen-bonding interactions. With increasing cross-linking density, the microphase separation became more remarkable.     

Polyurethane/polystyrene one-shot interpenetrating polymer networks with good damping ability: Transition broadening through crosslinking,internetwork grafting and compatibilization

Good damping materials should exhibit a high loss factor value over a broad temperature range. Polyurethane and polystyrene are highly immiscible polymers with glass transition regions far apart. The interpenetrating polymer network topology can restrict phase separation and result in materials with a broad transition region. Simultaneous polyurethane/polystyrene interpenetrating polymer networks were synthesized by the one-shot route. Different methods of improving the miscibility of the two polymers were investigated. These included the vanation of the crosslink level in both polymer networks, the controlled introduction of internetwork grafting and the incorporation of compatibilizers into the polystyrene network. Dynamic mechanical thermal analysis indicated that the latter two were successful in achieving a compatibilization of the polymer components. With some materials, a high, broad transition region exhibiting a loss factor > 0.3 over more than 135°C was obtained. The morphology observed via transmission electron microscopy ranged from macrophase separated materials in the lightly crosslinked IPNs to a fine, microheterogeneous morphology in the grafted ones. Modulated differential scanning calorimetry measurements confirmed the trend of the glass transition locations observed with dynamic mechanical thermal analysis.     

Simultaneous interpenetrating networks of a polyurethane and poly([methyl methacrylate]-stat-[N,N-dimethylacrylamide])

In a previous study, tetrahedron metastable phase diagrams were presented for a model simultaneous interpenetrating network (SIN) system of cross-polyurethane-inter-cross-poly(methyl methacrylate) (PU-PMMA). One triangular face of the overall tetrahedron diagram represented the ternary system MMA-PMMA-“U”, wherein “U” denotes the monomer/prepolymer mixture for the PU. In this article, a comonomer, N,N-dimethylacrylamide (DMA), is incorporated into the PMMA network. Thus, the above-mentioned ternary system is altered to “A”-PA-“U,” where “A” denotes the acrylic monomer mixture [MMA + DMA] and PA denotes the resulting copolymer. Glass transitions of fully cured samples were determined by dynamic mechanical spectroscopy (DMS). Phase separation was determined by the onset of turbidity, and gelation of the first gelling polymer was determined by the sudden resistance of the system to flow. The critical point, representing simultaneous phase separation and PA gelation, divides the overall composition for the reaction mixture (and the final SIN) into two parts. For one, gelation of the acrylic network precedes phase separation, and vice versa for the other part. In the absence of DMA in the PA network, the gelation-first region is very narrow, but with increasing amounts of copolymerized DMA, the critical point moves along the triangular face to increase the working area of the gelation-first region. © 1996 John Wiley & Sons, Inc.     

Interpenetrating polymer networks of poly(carbonate-urethane) and polyvinyl pyridine

Simultaneous interpenetrating polymer networks (IPN's), pseudo IPN's, and liner blends of aliphatic poly(carbonate-urethane) (PCU) and polyvinyl pyridine (PVP) have been prepared and characterized by DSC, DMA, and TEM. The full IPN's of PCU and PVP had a single phase morphology only above 50 wt % PCU, as determined by both DSC and DMA and confirmed by transmission electron microscopy (TEM). However, in both pseudo IPN's of PCU and PVP and in their linear blends there exist multiple glass transitions and melting points seen by DSC and DMA indicating phase incompatibility. The full IPN's exhibited superior ultimate mechanical properties and solvent resistance as compared to the pseudo IPN's, liner blends, and the pure crosslinked PCU and PVP networks.     

Interpenetrating polymer networks based on polyurethane and poly(butyl methacrylate): Interrelation between reaction kinetics and microphase structure

The effect of the reaction kinetics on the formation of semi-IPNs based on crosslinked polyurethane and linear poly(butyl methacrylate) of various compositions has been studied. New data are presented concerning the interconnection between the reaction kinetics, gelation and rheokinetics of IPN formation, between kinetics and crosslinking density, microphase structure and degree of microphase separation. It was shown that kinetic factors determine the conditions of microphase separation and formation of microphase structure.     

Poly(methyl acrylate)/poly(hydroxyethyl acrylate) sequential interpenetrating polymer networks. Miscibility and water sorption behavior

Sequential poly(methyl acrylate)/poly(hydroxyethyl acrylate) interpenetrating polymer networks with different poly(hydroxyethyl acrylate) contents were prepared by free radical polymerization of hydroxyethyl acrylate inside the previously polymerized poly(methyl acrylate) network. Differential scanning calorimetry on dry samples shows that the interpenetrating polymer networks exhibit phase separation, and no differences are found between the glass transition temperatures of the two phases present in the interpenetrating polymer network and those of the pure components. Thermally stimulated depolarization current experiments were used to study the influence of water sorption on the mobility of the different molecular groups in the poly(hydroxyethyl acrylate) phase of the interpenetrating polymer network. Isothermal water sorption of the interpenetrating polymer networks and pure poly(methyl acrylate) and poly(hydroxyethyl acrylate) networks is analyzed with different theories to compare the behavior of the poly(hydroxyethyl acrylate) phase in the interpenetrating polymer networks with that of the pure poly(hydroxyethyl acrylate) network. Diffusion coefficients of water in the interpenetrating polymer networks are obtained by means of dynamic sorption experiments. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1587–1599, 1999