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

Semi‐interpenetrating polymer networks (semi‐IPNs) composed of a dicyanate resin and a poly(ether sulfone) (PES) were prepared, and their curing behavior and mechanical properties were investigated. The curing behavior of the dicyanate/PES semi‐IPN systems catalyzed by an organic metal salt was analyzed. Differential scanning calorimetry was used to study the curing behavior of the semi‐IPN systems. The curing rate of the semi‐IPN systems decreased as the PES content increased. An autocatalytic reaction mechanism was used to analyze the curing reaction of the semi‐IPN systems. The glass‐transition temperature of the semi‐IPNs decreased with increasing PES content. The thermal decomposition behavior of the semi‐IPNs was investigated. The morphology of the semi‐IPNs was investigated with scanning electron microscopy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1079–1084, 2003     

Morphology transition of bismaleimide‐modified novolac resin

The bismaleimide (BMI)‐modified novolac resin was synthesized by allylation of the novolac resin and its “Ene” reaction with BMI. The reactions were monitored by Fourier transform infrared analysis (FTIR). The morphology of the BMI‐modified novolac resin changed with degree of allylation (i.e., the amount of BMI used). On the basis of the studies done by dynamical mechanical analysis (DMA), differential scanning calorimetry (DSC), and field emission scanning electron microscopy (FE‐SEM), it was found that when the degree of allylation increased from 48 to 59%, the resin changed from a single‐phase structure to a two‐phase structure. From the research by thermogravimetric analysis (TGA) and DMA, it was found that the higher allyl‐content (when > 48%) caused a decrease of the thermal properties and mechanical properties of the resultant resin. The BMI‐modified allyl novolac resin with 48% degree of allylation has the best thermal properties and the highest dynamic modulus in the current research. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 76–83, 2006     

Modification of novolac resin by interpenetrating network formation with poly(butyl acrylate)

Interpenetrating networks (IPNs) of novolac (phenol formaldehyde) resin and poly(butyl acrylate) (PBA) were prepared by a sequential mode of polymerization. Both full IPNs and semi‐IPNs of different compositions were synthesized and characterized with respect to their mechanical properties, that is, their modulus, ultimate tensile strength (UTS), elongation‐at‐break percentage, and toughness. Their thermal properties were examined with differential scanning calorimetry and thermogravimetric analysis (TGA). A morphological study was performed with an optical microscope. The effects of the variation of the blend ratios on the aforementioned properties were studied. There was a gradual decrease in the modulus and UTS with a simultaneous increase in the elongation‐at‐break percentage and toughness for both types of IPNs as the proportions of PBA were increased. With increasing proportions of PBA, the glass‐transition temperatures of the different IPNs underwent shifts toward a lower temperature region. This showed a plasticizing influence of PBA on the rigid and brittle phenolic matrix. TGA thermograms depicted the classical two‐step degradation for the phenolic resin. Although there was an apparent increase in the thermal stability at the initial stage (up to 350°C), particularly at lower temperatures, a substantial decrease in the thermal stability was observed at higher temperatures under study. In all the micrographs of full IPNs and semi‐IPNs, two‐phase structures were observed, regardless of the PBA content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2407–2417, 2005     

Synthesis and characterization of sequential interpenetrating polymer networks of novolac resin and poly(ethyl acrylate)

Interpenetrating polymer networks (IPN) of Novolac/poly(ethyl acrylate) have been prepared via in situ sequential technique of IPN formation. Both full and semi IPNs were characterized with respect to their mechanical properties that is, ultimate tensile strength (UTS), percentage elongation at break, modulus, and toughness. Physical properties of these were evaluated in terms of hardness, specific gravity, and crosslink density. Thermal behavior was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The morphological features were observed by an optical microscope. There was a gradual decrease in modulus and UTS, with consequent increases in elongation at break and toughness for both types of IPNs with increasing proportions of PEA. An inward shift and lowering (with respect to pure phenolic resin) of the glass transition temperatures of the IPNs with increasing proportions of PEA were observed, thus, indicating a plasticizing influence of PEA on the rigid, brittle, and hard matrix of crosslinked phenolic resin. The TGA thermograms exhibit two‐step degradation patterns. An apparent increase in thermal stability at the initial stages, particularly, at lower temperature regions, was followed by a substantial decrease in thermal stability at the higher temperature region under study. As expected, a gradual decrease in specific gravity and hardness values was observed with increase in PEA incorporation in the IPNs. A steady decrease in crosslink densities with increase in PEA incorporation was quite evident. The surface morphology as revealed by optical microscope clearly indicates two‐phase structures in all the full and semi IPNs, irrespective of acrylic content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Interpenetrating polymer network of blocked polyurethane and phenolic resin. I. Synthesis,morphology, and mechanical properties

Interpenetrating polymer networks (IPNs) based on blocked polyurethane (BPU)/phenolic (PF) were prepared using simultaneous polymerization method. The IPN was prepared from BPU prepolymer with m‐xylylenediamine as the chain extender and PF prepolymer using p‐toluene sulfonic acid as a catalyst. From Fourier transform infrared spectra analysis, it was found that the major reactions in the BPU/PF IPN system are the polymerization of BPU/MXDA and the self‐polymerization of PF. It was confirmed from scanning electron micrography that the BPU/PF IPN compatibility of the networks was improved, and the system was heterogeneous and more than one phase existed in the IPN. The tensile properties, flexural properties, impact, and hardness of the prepared IPN were studied. To obtain the best mechanical properties of IPN materials, the filler added in IPN materials has to be investigated. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

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

The curing behavior and physical properties of dicyanate/polyetherimide (PEI) semi‐interpenetrating polymer network (IPN) systems were investigated. Differential scanning calorimetry (DSC) was used to study the curing behavior of the dicyanate/PEI semi‐IPN systems. The curing rate of the semi‐IPN system decreased as the PEI content increased. An autocatalytic reaction mechanism can describe well the curing kinetics of the semi‐IPN systems. The reaction kinetic parameters were determined by fitting DSC conversion data to the kinetic equation. The glass transition temperature of the semi‐IPNs decreased with increasing PEI content. Two glass transitions due to phase‐separated morphology were observed for the semi‐IPN containing over 15 phr (parts per hundred parts of dicyanate resin) PEI. The thermal stability and dynamic mechanical properties of the semi‐IPNs were measured by thermal analysis.     

Morphology,mechanical properties,and failure topography of semi‐interpenetrating polymer networks based on natural rubber and polystyrene

Semi‐interpenetrating networks (semi‐IPNs) were prepared from natural rubber (NR) and polystyrene (PS) by the sequential method. In these semi‐IPNs the NR phase was crosslinked while the PS phase was uncrosslinked. Different initiating systems such as dicumyl peroxide (DCP), benzoyl peroxide (BPO), and the azobisisobutyronitrile (AIBN) system were used for polymerizing the PS phase. The blend ratio was varied by controlling the swelling of NR in the styrene monomer. The mechanical properties of the semi‐IPNs, namely, density, tensile strength, tear strength, elongation at break, tension set, tensile set, impact strength, and hardness, were determined. The morphology of different IPNs was studied using scanning electron microscopy. A compact morphology with a homogeneous phase distribution was observed in the semi‐IPNs. The properties of the semi‐IPN do not change much with the initiating system. However, in most cases, the DCP initiating system showed slightly superior performance. The tensile and tear‐strength values of the IPNs were found to increase with increasing plastomer content. The crosslink density of the semi‐IPNs also increased with increase in the polystyrene content. The experimental values were compared with theoretical models such as series, parallel, Halpin Tsai, Coran, Takayanaki, Kerner, and Kunori. The tensile and tear‐fracture surfaces were examined using a scanning electron microscope. The fracture patterns were correlated with the strength and nature of the failure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2327–2344, 2000     

Studies on castor oil–based polyurethane/polyacrylonitrile interpenetrating polymer network for toughening of unsaturated polyester resin

Tricomponent interpenetrating polymer network (IPN) systems involving castor oil, toluenediisocyanate (TDI), acrylonitrile (AN), ethylene glycol diacrylate (EGDA), and general‐purpose unsaturated polyester resin (GPR) were prepared with various compositions. The structures of the IPNs at various stages were confirmed using FTIR. The thermal stability of the IPNs was studied using TGA, which indicated that the polyurethane/polyacrylonitrile/GPR (PU/PAN/GPR) IPN underwent single‐stage decomposition, showing perfect compatibility at the IPN composition of 10 : 90 (PU/PAN : GPR). The mechanical properties such as tensile, flexural, impact, and hardness for the IPNs with various compositions were determined. It was found that the tensile strength of the GPR matrix was decreased and flexural and impact strengths were increased upon incorporating PU/PAN networks. The swelling properties in water and toluene were also studied. The morphology of the IPNs was studied using SEM. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 817–829, 2004     

Silicon‐based materials prepared by IPN formation and their properties

Both “condensation” and “hydrosilylation” reactions have been successfully applied to the synthesis of silicon‐based interpenetrating polymer networks (IPNs) consisting of a stable Si—O and/or a Si—C linkage. A ladder silsesquioxane oligomer (LDS 1, commercial name: Glass Resin™ GR100) and a polycarbosilane (PCS) by hydrosilylation polymerization of bifunctional Si—H and Si—vinyl monomers were used as the two components for the IPN (Table I ). Si‐based IPN material was prepared by melt‐and‐compression‐molding method of the B‐staged resin. Evaluating the flow‐curing nature of the B‐staged resin thus obtained with a KOKA‐type flow tester led to suitable conditions for melt‐and‐compression molding. LDS/PCS materials with various shapes (3–4 mm thick) were prepared by melt‐and‐compression molding. The mechanical properties of the LDS/PCS materials were evaluated. The flexural modulus and Izod impact strength of LDS/PCS (8:2 w/w) were larger than those of each component, a tendency that proved to be a positive effect derived from IPN formation in the LDS/PCS combined system. In addition, the thermal, electrical, and optical properties of these silicon‐based materials were studied and are reported on. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 724–731, 2000     

Synthesis and characterization of nanocomposites of silicon dioxide and polyurethane and epoxy resin interpenetrating network

Nanocomposites with varying concentrations of nanosized silicon dioxide particles were prepared by adding nanosilica to interpenetrating polymer networks (IPN)s of polyurethane and epoxy resin (PU/EP). The PU/EP IPNs and nanocomposites were studied by dynamic mechanical analysis, scanning electronic microscopy, wide‐angle X‐ray diffraction and small‐angle X‐ray scattering. The result showed that adding nanosize silicon dioxide can improve the properties of compatibility, damping and phase structure of IPN matrices. Copyright © 2003 Society of Chemical Industry     

Studies on novel semi‐2‐IPNs from polyetherimide and citraconimide

A series of novel semi‐2‐interpenetrating polymeric networks (semi‐2‐IPNs) were prepared through blending in solution using two different polyimides, biscitraconamic acid as a precursor of biscitraconimide (MBMI) with various proportions of polyetherimide (PEI) to achieve optimum properties. Biscitraconamic acid was prepared by reacting citraconic anhydride (CA), 3,3',4,4'‐benzophenone tetracarboxylic dianhydride (BTDA) and bis(3‐aminopropyl)phenyl phosphine (BAPPP) and it was characterized by differential scanning calorimetry (DSC), FTIR, and ¹H‐NMR spectroscopy. Both biscitraconamic acid and PEI were blended in N,N‐dimethylacetamide (DMAc) solution, casted and thermally cured up to 300°C to give semi‐2‐IPNs. The MBMI/PEI semi‐IPN systems were characterized by UV‐Vis spectroscopy, FTIR spectroscopy and thermal techniques. The phase morphology, isothermal aging, and water uptake of semi‐IPN systems have also been studied. The morphological studies on phase distribution were investigated by scanning electron microscopy (SEM). Thermal performance of MBMI/PEI semi‐IPN systems were evaluated by DSC and thermo gravimetric analysis (TGA). All the compositions of semi‐IPN polyimide system were stable up to 400°C and their thermal stability increased with increase in the content of PEI. Isothermal aging studies done at 300°C for various time periods showed good thermo‐oxidative stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical and dynamic mechanical studies of resol/vinyl acetate‐2‐ethylhexylacrylate/ hexamethoxymethylmelamine interpenetrating network systems

Resol was solution blended with vinyl acetate–2‐ethylhexylacrylate (VAc–EHA) resin in aqueous medium, in varying weight fractions, with hexamethoxymethylmelamine (HMMM) as crosslinker, and data was compared with a control. The present work was aimed at getting an optimum combination of tensile strength, dynamic mechanical strength, impact strength, and toughness by synthesis of an interpenetrating network (IPN) of the resins. The control gave a semi‐IPN system, in which the resol crosslinked, while the acrylic did not, whereas the blend, where HMMM was the crosslinker, gave a full IPN system. Full IPNs of the resol/VAc–EHA system had higher moduli and ultimate tensile strength than the semi‐IPNs. Dynamic mechanical study showed that full IPN systems have higher T_g values than semi‐IPN systems. The impact strength increases with increasing proportions of VAc–EHA copolymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1765–1771, 2003     

Preparation and properties of polyurethane‐modified epoxy cured in different simulated gravity environments

Great attention has been paid to the composites with interpenetrating polymer networks (IPNs) because of their special performance. However, the influence of sedimentation and convection from different gravity environments on the formation of IPNs and the properties of IPNs blends has received little attention. To understand their influence, environments with different gravity accelerations of 0g, 1g, and 2g were simulated with a superconducting magnet, and tests, including differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), coefficient of thermal expansion (CTE), scanning electron microscopy, and three‐point bending, of the IPNs blends cured in different gravity environments were conducted and analyzed. Fourier transform infrared spectroscopy, DSC, and DMA proved the formation of IPNs during the reaction between the polyurethane prepolymer (PUP) and epoxy resin (E51). The curves of DSC also certified the differences in the curing degree between the different parts along the direction of gravity of a sample. With the increase of mass fraction of PUP, the change trends of the storage modulus presented a linear decrease when samples cured in microgravity environment, but presented a parabolic trend when samples were cured in terrestrial environment. The damping properties of samples cured in simulated microgravity environments are better than those cured in terrestrial environment. With the increase in the simulated acceleration of gravity, the diameter of dispersed phase in a sea‐island structure increased, but their number decreased and the bending stress and CTE of the IPN blends all decreased. These results show the formation of IPNs was affected by different gravity values, and the thermal and mechanical properties of the IPN composites were influenced by the changed IPN components. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42063.     

Mechanical properties,thermal stability,and flame retardance of novolac‐type phenolic resin blended with poly(dimethylsiloxaneadipamide)

Mechanical properties (flexural strength, flexural modulus, and notched Izod impact strength), thermal stability, and flame retardance of poly(dimethylsiloxane adipamide) (PDMSA)‐toughened novolac type phenolic resin were investigated. Mechanical properties of modified novolac‐type phenolic resin increase with PDMSA contents, because the soft segment of PDMSA absorbs the loads in the network of brittle novolac‐type phenolic resins. TGA results show that the thermal degradation temperatures are higher than 400°C, and the temperature of 10% weight loss increases with increasing the PDMSA content. The char yield increases with novolac‐type phenolic resin content. The morphologies of the fracture surface of the modified novolac‐type phenolic resin were investigated by scanning electron microscopy (SEM). Morphological results agree with those from mechanical properties of the modified novolac‐type phenolic resin. The modified novolac‐type phenolic resin also shows excellent flame retardance that is UL‐94, V‐1, and the limited oxygen index is higher than 35. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 631–637, 2001     

Epoxy–poly(butyl methacrylate) interpenetrating polymer networks: Morphology and various physical,mechanical, and thermal properties

Semi- and full interpenetrating polymer networks (IPNs) of epoxy resin and poly(butyl methacrylate) (PBMA) were prepared by the sequential mode of synthesis. These were characterized with respect to their mechanical properties, such as ultimate tensile strength, percent elongation at break, and modulus. The densities of these samples were evaluated and compared. Differential scanning calorimetry (DSC) and thermogravimetric analysis were undertaken for thermal characterization of the IPNs. Phase morphology was studied by polarized light microscopy of the undeformed specimens and by scanning electron microscopy of the fractured surfaces of samples undergoing tensile failure. The effects of variations of the blend ratios on the above-mentioned properties were examined. A gradual decrease in modulus and tensile strength was observed for both the semi- and full IPNs with consequent increases in elongation at break and toughness as the proportion of PBMA increased. The densities also followed the same pattern. Semi-IPNs, however, were characterized by higher densities, tensile strengths, and moduli than the corresponding full IPNs. The DSC tracings displayed broadening of transitions, indicating some phase blending. The percent weight retentions in the thermal decomposition of the IPNs and pseudo-IPNs were higher than that observed during the thermal degradation of the epoxy resin homopolymer network. Phase-separated PBMA domains of various sizes were presumed to be responsible for the increased toughness of PBMA-modified epoxy. © 1996 John Wiley & Sons, Inc.     

Engineering properties of Novolac resin‐PMMA{poly(methyl methacrylate)} IPN system

Full and semi interpenetrating polymer networks (IPNs) based on phenol‐formaldehyde resin (Novolac) and poly(methyl methacrylate) have been made by in situ sequential technique of IPN formation. These systems of different compositions were characterized with respect to their mechanical properties, such as, ultimate tensile strength (UTS), percentage elongation at break, modulus, and toughness. Thermal properties were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Extent of phase mixing of the two polymers was envisaged from the micrographs obtained by polarizing light microscopy (PLM). The effects of variation of the blend ratios on the above‐mentioned properties were examined. There was a decreasing trend of modulus and UTS with consequent increases in elongation at break and toughness for both types of IPNs with increase in proportions of PMMA. Lowering of glass transition temperatures (with respect to pure crosslinked Novolac resin) of the IPNs with increasing proportions of PMMA was observed, indicating a plasticizing influence of PMMA on the rigid and brittle matrix of phenolic resin. The TGA thermograms exhibit lowering in thermal stability of the IPNs with respect to pure phenolic resin in the regions of higher temperatures. With increase in proportion of PMMA the onset of degradation of the IPNs is shifted towards lower temperature zone. The surface morphology as revealed by PLM indicates distribution of discrete domains of PMMA in the phenolic resin matrix. The two phase interfaces are quite sharp at higher concentrations of PMMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2764–2774, 2004     

Studies on engineering properties of PVC–PMMA semi‐interpenetrating polymer networks

Semi1 and semi2 interpenetrating polymer networks (IPNs) of PVC and in situ formed PMMA have been synthesized using diallyl phthalate and ethylene glycol dimethacrylate as the crosslinkers of PVC and PMMA, respectively. These two types of IPNs have been compared w.r.t their physical, mechanical, and thermal properties and an endeavor has been made to find a correlation of these properties with the morphology generated in these systems. The semi1 IPNs displayed a decrease in their mechanical parameters and the physical properties as well, while in contrast, the semi2 IPNs exhibited a marginal increase in the corresponding values after an initial drop upto about 15% of crosslinked PMMA incorporation when compared to the crosslinked PVC in the case of semi1 IPN and linear PVC in the case of semi2 IPN. The various samples of semi1 and semi2 IPNs showed a two‐stage degradation typical of PVC, while confirming the increased stability with the samples having higher percentages of PMMA. The influence of crosslinking of the major matrix in semi1 IPN was almost counterbalanced by the influence of crosslinking in the dispersed PMMA phase in the case of semi2 IPN. The softening characteristics as detected by the extent of penetration of the probe, as has been detected by thermomechanical analysis, are in conformity with their mechanicals. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1725–1735, 2005     

Synthesis and characterization of nanocellulose reinforced full‐interpenetrating polymer network based on poly(vinyl alcohol) and polyacrylamide (both crosslinked) composite films

An interpenetrating polymer network (IPN) is a novel blend of two polymers at least one of which is synthesized or crosslinked in the immediate presence of the other so that there is the least possibility of any gross phase separation. Full‐IPNs, prepared from poly(vinyl alcohol) and polyacrylamide, have shown superior performances over the conventional individual polymers. The ranges of applications have grown rapidly for such class of materials. Cellulose nanoparticles extracted from sugarcane bagasse in‐house are used to reinforce this PVA/PAAm (80:20) full‐IPN in different proportions during the synthesis of IPN. The characteristics of this new series of IPN composite materials have been evaluated by Fourier transform infrared spectroscopic analysis, mechanical, thermal (thermogravimetric analysis and differential scanning calorimetry), and scanning electron microscopy techniques. A loading of 5 wt% of nanocellulose lead to the highest tensile strength amongst the different IPN composite films. Although the non‐reinforced full‐IPN and the various reinforced composites with nanocelluloses are almost identical in their thermal stability, they prove to be much superior compared to the neat polymers. POLYM. COMPOS., 38:1720–1731, 2017. © 2015 Society of Plastics Engineers     

Synthesis of novel phosphorous‐containing biphenol, 2‐(5, 5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorin‐6‐yl)‐1,4‐benzenediol and its application as flame‐retardant in epoxy resin

A novel phosphorous‐containing biphenol, 2‐(5,5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorin‐6‐yl)‐ 1,4‐benzenediol (DPODB), was prepared by the addition reaction between 5,5‐dimethyl‐4‐phenyl‐2‐oxy‐1,3,2‐dioxaphosphorinane phosphonate (DPODP) and p‐benzoquinone (BQ). The compound (DPODB) was used as a reactive flame retardant in o‐cresol formaldehyde novolac epoxy resin (CNE) for electronic application. The structure of DPODB was confirmed by FTIR and NMR spectra. Thermal properties of cured epoxy resin were studied using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The flame retardancy of cured epoxy resins was tested by UL‐94 vertical test and achieved UL‐94 vertical tests of V‐0 grade (nonflammable). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3842–3847, 2006     

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