Epoxy resin–poly(ethyl methacrylate) interpenetrating polymer networks: Morphology,mechanical, and thermal properties

Full (interpenetrating networks (IPNs)) and semi-IPNs of the epoxy resin and poly(ethyl methacrylate) (PEMA) were prepared by the sequential mode of synthesis. These were characterized with respect to their mechanical properties, namely, tensile strength, elongation at break, modulus, and toughness. Thermal properties were studied by differential scanning calorimetry and thermogravimetry. The morphological features were studied through scanning electron microscopy (SEM) and polarized light microscopy. The effects of variation of the blend ratios on the above-mentioned properties were examined. There was a gradual decrease of modulus and tensile strength with consequent increases in elongation at break and toughness for both types of IPNs with increases in PEMA content. The weight retentions in the thermal decomposition of both the semi-IPNs and full IPNs were higher than the epoxy homopolymer. This enhancement was presumably related to the presence of the unzipped ethyl methacrylate monomer, which acted as radical scavengers in the epoxy degradation. An inward shift and lowering (with respect to pure epoxy) of the T_g of the IPNs was observed. The polarized light microscopy exhibits bimodal distribution of particle sizes. The fractography as studied by SEM shows change in fracture mechanics from shear yielding to crazing with increasing PEMA content. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1051–1059, 1998     

Synthesis,properties, and permeation of solutes through hydrogels based on poly(ethylene glycol)-co-poly(lactones) diacrylate macromers and chitosan

Triblock copolymers from poly(ethylene glycol) (PEG) and D,L -lactide or ε-caprolactone were synthesized to prepare semi-interpenetrating polymer networks (semi-IPNs) with chitosan by ultraviolet (UV) irradiation method. Then, the solute permeation through these semi-IPNs hydrogels were investigated. The structures of semi-IPNs were confirmed by Fourier transform infrared (FTIR) spectroscopy and wide-angle X-ray diffractometer (WAXD). The equilibrium water content (EWC) of these hydrogels was in the range of 67–75%. The crystallinity, thermal properties, and mechanical properties of semi-IPNs hydrogels were studied. All the hydrogels revealed a remarkable decrease in crystallinity as compared with the PEG macromer itself. The tensile strengths of semi-IPNs hydrogels in a dry state were rather high, but those of hydrogels in a wet state decreased drastically. The permeabilities of solutes of hydrogels followed the swelling behaviors and were regulated by solute size. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2151–2158, 1999     

Water Sorption and Dye Uptake Studies of Highly Swollen AAm/AMPS Hydrogels and Semi-IPNs with PEG

A semi-interpenetrating network (semi-IPNs) hydrogel, composed of acrylamide (AAm) with 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) as co-monomer, with poly(ethylene glycol) (PEG) and two multifunctional cross-linkers such as 1,4-butanediol dimethacrylate (BDMA), and trimethylolpropane triacrylate (TMPTA) was prepared. AAm/AMPS hydrogels and AAm/AMPS/PEG semi-IPNs were synthesized by free radical solution polymerization. Swelling experiments were performed in water at 25°C, gravimetrically. For sorption of Toluidin Blue (Basic Blue 17, TB) into AAm/AMPS hydrogels and AAm/AMPS/PEG semi-IPNs was studied by batch sorption technique at 25°C. Dye removal capacity, removal effiency and partition coefficient of the hydrogels was investigated.     

Mechanical property and swelling behavior of semi-interpenetrating polymer networks based on polyvinyl alcohol and polyurethane

We have studied the mechanical property and swelling behavior of semi-interpenetrating polymer networks (semi-IPNs) of poly(vinyl alcohol) (PVA) and polyurethane (PU) with reactive groups under different experimental conditions. Tensile strength and elongation of these semi-IPNs are strongly dependent on the composition of IPNs and degree of PU crosslinking. It is clear that the composition of PVA and PU forms different IPNs morphology, which would determine the final mechanical property. The experimental results also demonstrate that the degree of crosslinking, which is controlled by heat treating temperature time, and amount of reactive groups, affects the swelling behavior of IPNs. With a change in the degree of crosslinking, the degree of swelling of IPNs is also different. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 473–479, 1998     

Swelling Characterization and Adsorptive Features of Acrylamide/Itaconic Acid Hydrogels and Semi-IPNs for Uranyl Ions

A novel semi-interpenetrating network (semi-IPNs) hydrogel, composed of acrylamide (AAm) with itaconic acid (ITA) as co-monomer, with poly (ethylene glycol)(PEG) and trimethylolpropane triacrylate (TMPTA) was prepared. Hydrogels and semi-IPNs were synthesized by free radical solution polymerization. Swelling experiments were performed in water and aqueous solutions of uranyl acetate. Diffusion behavior was investigated and their diffusion into hydrogels was found to be non-Fickian in character. Sorption of uranyl ion onto the polymeric system was studied by a batch sorption technique at 25°C. The sorption capacity, removal effiency and partition coefficient of the hydrogels were investigated.     

Polymers from renewable resources. VII: Thermal properties of the semi-interpenetrating polymer networks composed of castor oil polyurethanes and cardanol-furfural resin

A number of semi-interpenetrating polymer networks (semi-IPNs) were synthesized by reacting polyurethanes (prepared from castor oil and various diisocyanates) and a phenolic resin (prepared from cardanol and furfural) The physico-chemical properties of the semi-IPNs have been investigated. The thermogravimetric analysis of polymers was followed using a computer analysis method for assigning the kinetic mechanism. Various kinetic equations have been used to evaluate the kinetic parameters. The suggested mechanism of degradation of the semi-IPNs is based on the kinetic parameters.     

A study of epoxy resin–acrylated polyurethane semi-interpenetrating polymer networks

Epoxy resin–acrylated polyurethane semi-interpenetrating polymer networks (semi-IPNs) were synthesized containing various ratios of the diglycidyl ether of bisphenol-A (DGEBA)-based epoxy resin and an acrylated aliphatic urethane oligomer. The synthesis was carried out in the presence of a mixture of triarylsulfonium hexafluoroantimonate salts as a dual photoinitiator that initiates both the cationic polymerization of the epoxy resin and the free-radical polymerization of the acrylated urethane oligomer simultaneously, upon irradiation with ultraviolet light. The simultaneous photopolymerization, followed by isothermal differential scanning calorimetry measurements, gave rise to simultaneous semi-interpenetrating polymer networks (semi-SINs). During polymerization, partial inhibition of the cationic polymerization was noticed. This was investigated by determination of the gel content and the infrared spectroscopy of the soluble fraction, after extraction of the synthesized polymer films in a Soxhlet apparatus, and by determination of the network density of investigated systems with thermal mechanical analysis. The compatibility of the components in the semi-IPNs was investigated by dynamic mechanical thermal analysis. It was found that glass transition temperatures are shifted inwardly, which indicated that the epoxy resin–acrylated polyurethane semi-IPNs were compatible. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:111–119, 1998     

Three-dimensional macro/mesoporosity developments in polydimethylsiloxane

Macro/mesoporous polydimethylsiloxanes (PDMS) were prepared with the purpose of vascular grafts. Oligoester-containing semi-interpenetrating polymer networks (semi-IPNs) can be used as precursors for generation of networks with tunable pore sizes. Novel poly(methyl methacrylate)/PDMS semi-IPNs were prepared by varying structural parameters. Extraction of uncrosslinked oligoester subchains from semi-IPNs was investigated. To tailor the morphology of porous structure, influence of some factors including porogen type, different polymerization conditions, monomer type, and concentration, crosslinking agent concentration were studied. PDMS networks were examined by field emission scanning electron microscopy. A uniform porous structure with interconnected pores was detected in horizontal and vertical cross sections of PDMS.     

Synthesis and processing of PMR-15/LaRC-TPI semi-IPN systems

To improve the fracture toughness of PMR-15 polyimide and to alleviate its high susceptibility to microcracking induced by thermal cycling, a thermoplastic polyimide, LARC-TPI, was incorporated to form a sequential semi-interpenetrating polymer network (semi-2 IPN). The imidization kinetics of LARC-TPI in the semi-IPNs were studied using a thermal gravimetric analyzer. Both the solvent and the glass transition temperature of the semi-IPN were found to have significant effects on the imidization kinetics. The kinetics could be modeled by a two-step reaction: the first step being a second-order reaction followed by a second step, which is a first-order diffusion-controlled reaction. Differential scanning calorimetry was chosen to investigate the curing of PMR-15 and PMR-15/LARC-TPI semi-IPNs. The curing process was well correlated by a first-order reaction kinetics, which suggested that the reverse Diels-Alder reaction of the Norbornene end group was the rate controlling step. The glass transition temperatures of these semi-IPNs were again found to play important an important role in dictating the curing kinetics. A higher proportion of LARC-TPI or a higher glass transition temperature of the semi-IPN prepolymer tended to result in a slower curing reaction. The optimum molding cycle of PMR-15 and PMR-15/LARC-TPI semi-IPNs were then determined from the obtained kinetics. © 1995 John Wiley & Sons, Inc.     

Thermal effects in poly(hexamethylene adipamide) and polyoxymethylene at high hydrostatic pressures

The dynamic mechanical properties, transition behavior, and morphology of polycarbonate (PC)-polyurethane (PU) semi-interpenetrating polymer networks (semi-IPNs) and linear blends were studied by means of Rheovibron, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). Two glass transition temperatures corresponding to polycarbonate and polyurethane were observed and microphase separation was further evident with TEM. In PC/PU semi-IPNs, two glass transition temperatures were shifted inwardly indicating that the interpenetrating network of polyurethane increases the mutual miscibility of PC and PU. The average phase domain was 500Å in semi-IPNs and the phase domains were in the range 1000–6000 Å in linear blends of the corresponding polymers. The compatibilities of PC and PU were greatly influenced by the molecular weight of polyols in PU prepolymer and the ratio of NCO/OH; lower molecular weight polyols and higher NCO/OH ratio resulted in better compatibility, and finer phase domains in PC and PU linear blends and semi-IPNs.     

Effect of Imidazolium–p-Chloro-phenacylide on Properties of Semi-interpenetrating Polymer Network from Poly(zinc acrylate) and Poly(styrene-co-methylmethacrylate)

The effect of nitrogen ylide, namely imidazolium–p-chlorophenacylide (ICPY), on the properties of semi-interpenetrating polymer network (semi-IPNs) of poly(zinc acrylate) as component I and styrene-co-methylmethacrylate as component II, using divinyl benzene as crosslinking agent, has been studied and compared with those obtained with α-α′-azobisisobutyronitrile (AIBN). The semi-IPNs have been characterized by infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy. The crosslink density as well as thermal stability of the IPNs synthesized in the presence of ylide (ICYP) is less than that with AIBN. © of SCI.     

Semi-IPNs formed from poly(ethylene glycol monomethyl ether acrylate) and an epoxy thermoset

Poly(ethylene glycol monomethyl ether acrylate) (PEGMEA) was synthesized from the reaction of poly(ethylene glycol monomethyl ether) (PEGME) with acryloyl chloride. Semi-IPNs based on various weight ratios of diglycidyl ether of bisphenol A (DGEBA)/PEGMEA were prepared, using isophronediamine (IPDA) and 2,2′-azo-bis(isobutyronitrile) (AIBN) as curing agents. The glass transition temperature and exothermic peak shifts were studied with differential scanning calorimetry (DSC). Viscosity changes during semi-IPN formation were measured with a Brookfield viscometer. Dynamic mechanical properties were investigated by rheometric dynamic spectroscopy (RDS). Stress–strain curves were obtained with an Instron tensile tester, while impact resistance was measured with a computer aided falling dart impact tester. Experimental results revealed retarded curing rates for all semi-IPNs, as evidenced from the shifts of curing exothermic peaks to higher temperatures, together with retarded viscosity increases during semi-IPN formation. These phenomena were interpreted in terms of chain entanglement between epoxy and PEGMEA. Nevertheless, the semi-IPNs indicated good compatibility as inferred from a single T_g in DSC and a single damping peak in RDS for each semi-IPN. Improved tensile stress and strain along with toughness improvements were noticed for this semi-IPN system. Shear band yielding was proposed to interpret this result. © 1999 Society of Chemical Industry     

Epoxy/poly(methyl methacrylate) interpenetrating polymer networks—morphology,mechanical and thermal properties

Full and semi-IPNs were prepared from epoxy and poly methyl methacrylate (PMMA), by the sequential mode of synthesis and were characterized by measurements of ultimate tensile strength (UTS), elongation at break, modulus, and toughness. Aromatic polyamine adducts and ethylene glycol dimethacrylate were used as the crosslinkers for epoxy and comonomer/crosslinker for methyl methacrylate monomer, respectively. Higher UTS and modulus of the semi-IPNs over full IPNs were attributed to the higher probability of interpenetration. The weight retention in the thermal decomposition of the IPNs and semi-IPNs were higher than the epoxy homopolymer. This enhancement was presumably related to the presence of the unzipped methyl methacrylate monomer which acted as radical scavangers in the epoxy degradation. © 1994 John Wiley & Sons, Inc.     

Dynamic mechanical study of filled semi-interpenetrating polymer networks: Influence of γ-Fe2O3 on microphase structure

The preparation of filled two-component semi-interpenetrating polymer networks (semi-IPNs) is described and the results of an investigation of their morphology by means of dynamic mechanical spectroscopy are considered. The influence of an active dispersed filler (γ-Fe₂O₃) on the semi-IPNs phase structure is studied. A comparison is made between filled and unfilled semi-IPNs consisting of compatible or incompatible polymers. In the case of a semi-IPN of compatible polymers, the introduction of γ-Fe₂O₃ was observed to cause phase separation. With a two-phase semi-IPN the introduction of the filler enhanced the phase separation. The presence of two distinct peaks (the dynamic glass transition temperatures) corresponding to those of the two initial homopolymers shows the semi-IPN to have a two-phase structure.     

Study on the properties and application of epoxy resin/polyurethane semi-interpenetrating polymer networks

Damping properties of epoxy resin/polyurethane (EP/PU) semi-interpenetrating polymer networks (IPNs) were studied by the dynamic mechanical analysis (DMA) method. It shows that the semi-IPNs have excellent damping properties at ordinary temperature. The maximum value of tan δ is about 1 when the weight composition of EP/PU is 70/30. Tensile tests also indicate that the system has good tensile strength and elongation at break at this ratio. The effects of structure on the properties of the semi-IPNs are discussed. Applied to the cavitation corrosion resistant coating, the semi-IPNs show good cavitation corrosion resistance. © 1996 John Wiley & Sons, Inc.     

Morphology and mechanical properties of styrene-butadiene-styrene/polystyrene semi-interpenetrating polymer networks and their blends

SBS/PS semi-interpenetrating polymer networks (semi-IPNS) were synthesized by swelling a linear styrene-butadiene-styrene (SBS) triblock copolymer (SBS, Kraton 1102) with styrene monomer plus benzoin as photoinitiator and divinylbenzene as cross-linking agent. Polyblends were prepared by solution casting of SBS and polystyrene (PS) in their ideal solvents. Measurements were made for viscoelastic properties and mechanical properties of phase-separated polymer alloy (including SBS copolymers Kraton 4122), semi-IPNs and polyblends of several SBS and PS, with the same total PS content (48% PS). The dynamic mechanical behaviour shows distinct transitions for each polymer, in agreement with electron microscopy results that SBS/PS polymer alloy forms two phases; however, the phase domains were finer in the semi-IPNs than in SBS triblock copolymer and in polyblends of the corresponding polymers. Stress-strain data show that semi-IPNs exhibit higher tensile strength and modulus than the other two corresponding polymer alloys. A master curve was plotted to illustrate the stress relaxation behaviour of samples at higher temperatures. Our results also reveal that semi-IPNs have much better high-temperature mechanical strength.     

The role of branching architecture in shape memory semi-IPNs: Shape memory effect and tube model analysis

The impact of branching architecture of one continuous uncrosslinked phase on properties of classic shape memory semi-interpenetrating polymer networks (semi-IPNs) was explored. Crosslinked poly (methyl methacrylate) (PMMA)/star-shaped polyethylene glycol (PEG) (PMMA/SPEG) semi-IPNs and PMMA/linear PEG (PMMA/LPEG) semi-IPNs were synthesized with the same PEG content. Mechanical properties, phase structure, thermal properties, dynamic mechanical properties, and shape memory properties of these two semi-IPNs systems were compared. Due to the better compatibility of SPEG in the PMMA network, which was derived from little crystallization compared with PMMA/LPEG semi-IPNs, PMMA/SPEG semi-IPNs exhibited a combination of large tensile strength and high elongation at break. PMMA/SPEG semi-IPNs, which had little crystallization exhibited superior shape recovery versus PMMA/LPEG semi-IPNs, which had more crystallization. Moreover, the higher the crystallinity in PMMA/PEG semi-IPNs was the worse long-term temporary shape retention. Based on tube model theory, the high shape recovery capacity of PMMA/SPEG semi-IPNs is mainly ascribed to the retraction of free PEG arms, which is entropically favorable and thermally activated due to the fluctuations of the path length. This result is supported by stress relaxation analysis and the influence of long shape fixity time on shape fixity ratio for these two systems.     

Shape-memory behavior of poly (methyl methacrylate-co –N-vinyl-2-pyrrolidone) / poly (ethylene glycol) semi-interpenetrating polymer networks based on hydrogen bonding

Based on hydrogen bonding interactions, Poly(methyl methacrylate-co-N-vinyl-2-pynolidone) (P(MMA-co-VP)) networks and linear poly(ethylene glycol) (PEG) can form semi-interpenetrating polymer networks (semi-IPNs), i.e. P(MMA-co-VP)/PEG semi-IPNs, which has shape memory behaviour; its maximum storage modulus ratio can be more than 400, and its shape recovery ratio could reach 99%. The morphology, thermal behaviors and dynamic mechanical properties of P(MMA-co-VP)/PEG semi-IPNs were studied by FTIR, TEM, DSC and DMA. When PEG with higher molecular weight was introduced into P(MMA-co-VP) networks, they possess higher glassy state modulus and higher recovering rate. In such a system, the maximum molecular weight of PEG required for the semi-IPN formation reaches 1000.     

Structuring and characterization of a novel highly microporous PEI/BMI semi-interpenetrating polymer network

Syntheses of semi-interpenetrating polymer networks (semi-IPNs) with polyetherimide/bismaleimide (PEI/BMI) chromophore composites showing molecular sieve characteristics are reported. A tunable and compatible chemical structure with fine morphology was obtained through in situ controlled sol-gel polymerization, crosslinking, chemical modification and membrane fabrication. The novel semi-IPN synthesized and assembled using ethanol as polar protic modifier and pore former, had superior structure and morphology for making gas separation membranes. These semi-IPN membranes gave 15 times higher gas flux than those membranes prepared from pure PEI without significant decrease in gas selectivity. The chemical structures of these novel semi-IPNs were elucidated by FTIR, XPS and SEM. It appears that in situ simultaneous ethoxylation, anionic polymerization of BMI and imide modifications were responsible for creating the new chemical structure and molecular morphology that was different from traditional BMI resins. In addition, these chemical processes give superior structures using green chemistry techniques such as ambient temperature reaction and polymerization without initiators.     

Physical,mechanical, and morphological behavior of sequential polybutadiene–poly(methyl methacrylate) interpenetrating polymer networks

Both full and semi-interpenetrating polymer networks (IPNs) of polybutadiene and poly(methyl methacrylate) were synthesized by sequential polymerization. The effect of compositional variation and the cross-linking agent of both elastomer and plastomer on the physical, mechanical, and morphological properties were investigated. Full-IPNs exhibited improved tensile strength, modulus, tear strength, gel content, and density, whereas the corresponding semi-IPNs exhibited better toughness and elongation at break. Phase morphology of full-IPNs were characterized by compact, tight network structures compared to those of semi-IPNs. © 1994 John Wiley & Sons, Inc.