The effects of functional azo initiator on PMMA and polyurethane IPN systems. III. Tear resistance and crack growth of PBD(1,2)-PU/PMMA (50%) blends

The tear strength and crack growth mechanism of PBD(1,2)–PU/PMMA (50%) IPN systems were studied by the trouser tear test and single edge notched (SEN) tensile test. It was found that these blend systems showed similar structures and properties to particulatereinforced elastomers. The tear strength was dominated by the structure of the rubber matrix. The PMMA phase increased the tearing resistance by increasing the hysteresis of the IPN systems. Chemical bonding between the PMMA-rich particle and PU-rich matrix prepared by using a reactive azo initiator inhibited the initiation of the fracture nucleus, decreased the intrinsic flaw size, and increased the tear strength. The crack growth of these IPNs was dependent on both the fracture energy available for crack propagation and the hysteresis of the material. The similar structure of these two blends resulted in the similar crack growth behavior.     

Semiinterpenetrating polymer networks based on polyurethane and polyvinylpyrrolidone. I. Thermodynamic state and dynamic mechanical analysis

Semiinterpenetrating polymer networks (semi‐IPNs) based on polyurethane (PU) and polyvinylpyrrolidone (PVP) have been synthesized, and their thermodynamic characteristics, thermal properties, and dynamical mechanical properties have been studied to have an insight in their structure as a function of their composition. First, the free energies of mixing of the two polymers in semi‐IPNs based on crosslinked PU and PVP have been determined by the vapor sorption method. It was established that these constituent polymers are not miscible in the semi‐IPNs. The differential scanning calorimetry results evidence the T_g of polyurethane and two T_g for PVP. The dynamic mechanical behavior of the semi‐IPNs has been investigated and is in accordance with their thermal behavior. It was shown that the semi‐IPNs present three distinct relaxations. If the temperature position of PU maximum tan δ is invariable, on the contrary, the situation for the two maxima observed for PVP is more complex. Only the maximum of the highest temperature relaxation is shifted to lower temperature with changing of the semi‐IPNs composition. It was concluded that investigated semi‐IPNs are two‐phase systems with incomplete phase separation. The phase composition was calculated using viscoelastic properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 852–862, 2001     

Simultaneous full‐interpenetrating polymer networks of blocked polyurethane and vinyl ester. II. Static and dynamic mechanical properties

Simultaneous full‐interpenetrating polymer networks (full‐IPNs) based on blocked polyurethane (PU) and vinyl ester (VE) have been prepared. The static and dynamic properties of these IPNs have been examined. Results show that the tensile strength and flexural strength of IPNs increased with blocked PU content to a maximum value at 7.5 wt % PU content and then decreased. The tensile modulus, flexural modulus, and hardness of IPNs decreased with increasing blocked PU content. The impact strength of IPNs increased with increasing blocked PU content. The tensile strength, flexural strength, tensile modulus, and flexural modulus of IPNs increased with filler (kaolin) content to a maximum value at 20 to 25 phr filler content and then decreased. The higher the filler content, the greater the hardness, and the lower the impact strength of IPNs. The tensile strength, flexural strength, tensile modulus, flexural modulus, and hardness of IPNs increased with increasing VE initiator content. The dynamic technique was used to determined the damping behavior across a temperature range. Results show that the glass transition temperature (T_g) of IPNs are shifted inwardly compared with pure PU and VE, which indicated that the blocked PU–VE IPNs showed excellent compatible. Meanwhile, the glass transition temperature was shifted to a higher temperature with increased filler content. The dynamic storage modulus (E′) of IPNs increased with increasing VE and filler content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1977–1985, 1999     

Recent studies on interpenetrating polymer networks

Recent investigations on interpenetrating polymer networks (IPNs) have included two component IPNs from polyurethanes and poly(methacrylates) and two component IPNs from polyurethanes and epoxies. All the IPNs were prepared by the simultaneous polymerization technique (SIN-IPNs). Two types of IPNs, polyurethane-poly(methyl methacrylate) (PU/PMMA) and polyurethane-poly(methyl methacrylate-methacrylic acid) (PU/PMMA-MAA) were prepared. Improved phase miscibility and decreasing extent of phase separation was observed in both types of IPNs with increasing the NCO/OH ratio, decreasing molecular weight of the polyol in the PU and introduction of charge groups. A comparison was made between full-IPNs, pseudo-IPNs, graft copolymers and related homopolymers from polyurethanes and epoxies. Increased compatibility in full-IPNs and graft copolymers was observed by means of DSC, SEM and was also further substantiated by a shift toward single T_gs as determined by dynamic mechanical spectroscopy. The introduction of opposite charge groups in two-component IPNs from polyurethanes and epoxies led to improved compatibility (no phase separation) and enhanced mechanical properties.     

Dynamic mechanical properties of semi‐interpenetrating polymer network‐based on nitrile rubber and poly(methyl methacrylate‐co‐butyl acrylate)

In this article, semi‐interpenetrating polymer network (Semi‐IPNs) based on nitrile rubber (NBR) and poly(methyl methacrylate‐co‐butyl acrylate) (P(MMA‐BA)) were synthesized. The structure and damping properties of the prepared Semi‐IPNs blends were characterized and by fourier transform infrared spectrum (FTIR), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), thermogravimetric analysis (TGA/DTG), and tensile mechanical properties. The results showed that interpenetrating network based on P(MMA‐BA) and NBR was successfully obtained, which showed the improved thermal stability compared to NBR/P(MMA‐BA)‐based two‐roll mill blends. Furthermore, Semi‐IPNs showed significantly better the dynamic mechanical properties than that of the two‐roll mill system. With the increasing feed ratio of BA and MMA during the preparation of Semi‐IPNs, the loss peak position for P(MMA‐BA) in NBR/PMMA IPNs shifted to a lower temperature from 20°C to ?17°C, and when NBR in Semi‐IPNs was accounted for 40 wt %, the dynamic mechanical thermal analysis showed that much more advanced damping material with wider temperature range (?30°C < T < 80°C) as tan δ > 0.45 can be achieved. Therefore, it was expected as a promising way to obtain the excellent damping materials with good oil‐resisted properties according the Semi‐IPNs system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40217.     

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     

Thermal decomposition of some azo initiators. Influence of chemical structure

In view of applying 2,2'-azobis(2-cyanopropanol) (ACP) to the synthesis of macro azo initiators it is necessary to study its thermal behaviour and to compare it with two other azo compounds, i.e. 2,2'-azobis(2-methylpropionitrile) (AIBN) and 4,4'-azobis(4-cyanopentanoic acid) (ACPA). Other azo initiators obtained from the reaction of ACP with a monoisocyanate, i. e. p-tolyl isocyanate, or with a diisocyanate, i. e. pure 4,4'-methylenediphenyl diisocyanate (MDI) or MDI pre-reacted with α,ω-dihydroxypoly(ε-caprolactone) (M_n = 1 000 g mol^–1), were also studied. Thermal decomposition in bulk and in solution was studied using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and ultra violet spectroscopy. DSC and TGA measurements show that the temperature range of decomposition of different azo initiators and their derivatives is not the same. The kinetic and thermal parameters of ACP in bulk were found to be different from that found for AIBN, ACPA and azo or macro azo initiators based on ACP, while similar decomposition activation energy values were obtained for ACP, AIBN and ACPA in solution.     

Preparation of compatible blends of poly(methyl methacrylate) used in dentistry with a reactive terpolymer containing maleic anhydride and their thermomechanical characterization

This study focuses on the preparation of compatible blends with the poly(methyl methacrylate) (PMMA) using a reactive terpolymer maleic anhydride–styrene–vinyl acetate (MA–St–VA). In the first series of experiments, binary blends of the PMMA and the MA–St–VA terpolymer have been prepared in tetrahydrofurane. The PMMA and the MA–St–VA terpolymer formed the compatible blends. The effects on thermomechanical properties of MA–St–VA terpolymer ratio in the blends were studied. The glass transition temperatures (T_g), thermal expansion coefficient (α), and other thermomechanical parameters for the blends have been established by TMA method and the compatibility of two polymers has been evaluated by these TMA parameters. The addition of MA–St–VA terpolymer to PMMA made a plasticizing effect on PMMA. This effect regularly changed with the increasing of the terpolymer in the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 363–367, 2006     

Mechanical properties of blocked polyurethane/epoxy interpenetrating polymer networks

The mechanical properties of blocked polyurethane(PU)/epoxy interpenetrating polymer networks (IPNs) were studied by means of their static and damping properties. The studies of static mechanical properties of IPNs are based on tensile properties, flexural properties, hardness, and impact method. Results show that the tensile strength, flexural strength, tensile modulus, flexural modulus, and hardness of IPNs decreased with increase in blocked PU content. The impact strength of IPNs increased with increase in blocked PU content. It shows that the tensile strength, flexural strength, tensile modulus, and flexural modulus of IPNs increased with filler (CaCO₃) content to a maximum value at 5, 10, 20, and 25 phr, respectively, and then decreased. The higher the filler content, the greater the hardness of IPNs and the lower the notched Izod impact strength of IPNs. The glass transition temperatures (T_g) of IPNs were shifted inwardly compared with those of blocked PU and epoxy, which indicated that the blocked PU/epoxy IPNs showed excellent compatibility. Meanwhile, the T_g was shifted to a higher temperature with increasing filler (CaCO₃) content. The dynamic storage modulus (E′) of IPNs increased with increase in epoxy and filler content. The higher the blocked PU content, the greater the swelling ratio of IPNs and the lower the density of IPNs. The higher the filler (CaCO₃) content, the greater the density of IPNs, and the lower the swelling ratio of IPNs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1826–1832, 2006     

Comparison between the effects of alcohols and diols on polymethyl‐methacrylate and polyacrylamide with positron annihilation lifetime and electric conductivity measurements

Comparison between the effect of alcohols and diols on poly(methylmethacrylate) (PMMA) and polyacrylamide (PAA) was investigated by positron annihilation lifetime (PAL) spectroscopy and electric conductivity measurements. The samples were prepared by adding alcohols, such as ethanol (E), isopropyl alcohol (P), and butyl alcohol (B), and diols, such as ethanediol (E_1,2), isoproponendiol (P_1,2), and butanediol (B_1,2, B_1,3, B_1,4). The o‐Ps lifetime values (τ₃) of PMMA–alcohol or PMMA–diol composites are shorter than the τ₃ value of the virgin PMMA, whereas the τ₃ values of PAA–alcohol or PPA–diol composites fluctuate above and blow the corresponding value of virgin PAA. On the other hand, a significant increased was observed in the o‐Ps intensities (I₃) of both PMMA and PAA composites with added alcohols and diols compared with pure PMMA and PAA. The electric conductivity (σ) also increased for both PMMA and PAA composites with added alcohols and diols compared with the virgin PMMA or PAA polymer. A correlation was found between positron annihilation lifetime parameters and electric conductivity of PAA composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3078–3083, 2003     

Azo initiator selection to control the curing order in dimethacrylate/epoxy interpenetrating polymer networks

Differential Scanning calorimetry (DSC) and Fourier‐transform infrared (FT‐IR) spectroscopic studies have been undertaken of the cure of interpenetrating polymer networks (IPNs) formed with imidazole‐cured diglycidyl ether bisphenol‐A (DGEBA) and with either diethoxylated bisphenol‐A dimethacrylate (DEBPADM) or bisphenol‐A diglycidyl dimethacrylate (bisGMA), polymerized by a range of azo initiators (AIBN64, VAZ088, VR110 and AZO168). Due to the differing decomposition rates of the azo initiators, the neat dimethacrylate resin either cured faster than (with AIBN64 and VAZO88), or similar to (VR110), or slower than (AZO168), the neat epoxy resin. In the neat DGEBA/1‐methyl imidazole (1‐MeI), DEBPADM/AIBN64, DEBPADM/VAZO88 and DEBPADM/VR110 resins, close to full cure was achieved. For the neat, high‐temperature DEBPADM/AZO168 resin, full cure was not attained, possibly due to the compromise between using a high enough temperature for azo decomposition while avoiding depolymerization or decomposition of the methacrylate polymer. IPN cure studies showed that, by appropriate initiator selection, it was possible to interchange the order of cure of the components within the IPN so that either the dimethacrylate or epoxy cured first. In the isothermal cure of the 50:50 DEBPADM/AIBN64:DGEBA/1‐Mel IPN system, the cure rate of both species was less than in the parent resins, due to a dilution effect. For this system, the dimethacrylate cured first and to high conversion, due to plasticization by the unreacted epoxy, but the subsequent cure of the more slowly polymerizing epoxy component was restricted by the high crosslink density developed in the IPN. After post‐curing, however, high conversion of both reactive groups was observed and the fully cured IPN exhibited a single high‐temperature T_g, close to the T_g values of the parent resins. In the higher‐temperature, isothermal cure of the 50:50 DEBPADM/VR110:DGEBA/1‐Mel IPN system, the reactive groups cured at a similar rate and so the final conversions of both groups were restricted, while in the 50:50 DEBPADM/AZO168:DGEBA/1‐Mel system it was the epoxy which cured first. Both of these higher‐temperature azo‐initiated IPN systems exhibited single T_gs, indicating a single‐phase structure; however, the T_gs are significantly lower than expected, due to plasticization by residual methacrylate monomer and/or degradation products resulting from the high cure temperature. Copyright © 2004 Society of Chemical Industry     

Accelerant‐promoted free radical polymerization of methacrylates by stabilized nitroxide unimolecular initiators: synthesis and characterization

BACKGROUND: This investigation evaluates the effectiveness of initiator adducts for living and controlled polymerization of methacrylates, crosslinking of dimethacrylates and thermal stabilities of the resulting polymers. Adducts of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy with benzoyl peroxide and with azobisisobutyronitrile were prepared and evaluated as stabilized unimolecular initiators for the free radical polymerization of methacrylate monomers using sulfuric acid as catalyst. The monomers used were methyl methacrylate, triethylene glycol dimethacrylate (TEGDMA) and ethoxylated bisphenol A dimethacrylate (EBPADMA). RESULTS: Successful polymerization was achieved at 70 and 130 °C with reaction times ranging from 45 min to 120 h. The dispersity (D) of poly(methyl methacrylate) (PMMA) was 1.09–1.28. The livingness and extent of control over polymerization were confirmed with plots of M_n evolution as a function of monomer conversion and of the first‐order kinetics. The glass transition temperature (T_g) for PMMA was 123–128 °C. The degradation temperature (T_d) for PMMA was 350–410 °C. T_d for poly(TEGMA) was 250–310 °C and for poly(EBPADMA) was 320–390 °C. CONCLUSION: The initiators are suitable for free radical living and controlled polymerization of methacrylates and dimethacrylates under mild thermal and acid‐catalyzed conditions, yielding medium to high molecular weight polymers with low dispersity, high crosslinking and good thermal stability. Copyright © 2008 Society of Chemical Industry     

Surface treatment of cellulose fibers with methylmethacrylate for enhanced properties of in situ polymerized PMMA/cellulose composites

Cellulose micro/nanofibers (CNF), prepared from jute fibers were surface treated with methyl methacrylate (MMA) for better dispersion into poly methyl methacrylate (PMMA) matrix. PMMA/cellulose composites were prepared by in situ suspension polymerization technique. The surface treatment of CNF was confirmed by Fourier transform infrared spectroscopy (FTIR) and Nuclear magnetic resonance (NMR) analysis. MMA‐treated cellulose micro/nanofibers (MCNF) demonstrated improved affinity and dispersion in MMA monomer as well as in the PMMA/cellulose composites. Thermal properties of the cellulose composites were analyzed by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The glass transition temperature (T_g) of PMMA increased by nearly 19°C in the in situ cellulose composites compared to that of unreinforced PMMA as indicated by DSC. TGA showed increased thermal stability of the cellulose composites. Enhanced tensile properties as well as significantly lower moisture uptake were observed in the in situ prepared PMMA/cellulose composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39808.     

Effect of CePO<Subscript>4</Subscript> nanostructures in transparent PMMA/castor-oil based PU IPNs on thermal stability,optical and mechanical properties

Interpenetrating polymer networks (IPNs) based on PMMA/castor-oil based PU/cerium phosphate nanoparticles (CePO₄) constitute an important type of materials to modulate the stiffness and confers ductile behavior to PMMA. A comparison of CePO₄ dispersion into different ratios of PMMA/PU IPNs between sonication method and the classic magnetic stirring during the sequential polymerization synthesis was done through structural, optical, thermal, morphological and mechanical analysis. The results demonstrated that sonication is the adequate method to disperse CePO₄ in low viscous systems such as PMMA/PU 70/30 and 60/40 wt.%, while magnetic stirring favors the dispersion in high viscous systems (PMMA/PU 50/50 wt.%). Thanks to the physical interaction, the good compatibility/miscibility between PMMA/PU and CePO₄ is reached. The obtained experimental results indicated that the luminescent CePO₄ nanoparticles, in addition to improve the structural properties and the Young’s modulus, can reduce voids in the networks.     

Semi‐interpenetrating polymer networks based on polyurethane and polyvinylpyrrolidone. II. Dielectric relaxation and thermal behaviour

Semi‐interpenetrating polymer networks (semi‐IPNs) based on crosslinked polyurethane (PU) and linear polyvinylpyrrolidone (PVP) were synthezised, and their thermal and dynamic mechanical properties and dielectric relaxation behavior were studied to provide insight into their structure, especially according to their composition. The differential scanning calorimetry results showed the glass transitions of the pure components: one glass‐transition temperature (T_g) for PU and two transitions for PVP. Such glass transitions were also present in the semi‐IPNs, whatever their composition. The viscoelastic properties of the semi‐IPNs reflected their thermal behavior; it was shown that the semi‐IPNs presented three distinct dynamic mechanical relaxations related to these three T_g values. Although the temperature position of the PU maximum tan δ of the α‐relaxation was invariable, on the contrary the situation for the two maxima observed for PVP was more complex. Only the maximum of the highest temperature relaxation was shifted to lower temperatures with decreasing PVP content in the semi‐IPNs. In this study, we investigated the molecular mobility of the IPNs by means of dielectric relaxation spectroscopy; six relaxation processes were observed and indexed according the increase in the temperature range: the secondary β‐relaxations related to PU and PVP chains, an α‐relaxation due to the glass–rubber transition of the PU component, two α‐relaxations associated to the glass–rubber transitions of the PVP material, and an ionic conductivity relaxation due to the space charge polarization of PU. The temperature position of the α‐relaxation of PU was invariable in semi‐IPNs, as observed dynamic mechanical analysis measurements. However, the upper α‐relaxation process of PVP shifted to higher temperatures with increasing PVP content in the semi‐IPNs. We concluded that the investigated semi‐IPNs were two‐phase systems with incomplete phase separation and that the content of PVP in the IPNs governed the structure and corresponding properties of such systems through physical interactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1191–1201, 2003     

Thermal characteristics of IPNs composed of poly(propylene glycol) and poly(acrylic acid)

Interpenetrating polymer networks (IPNs) based on poly(propylene glycol) (PPG) and poly(acrylic acid) (PAAc) were prepared by UV irradiation and characterized using fourier transform infrared (FTIR), differential scanning calorimetry (DSC), dielectric analysis (DEA), and thermogaravimetry (TGA). The glass transition temperatures (T_gs) of these IPNs exhibited a relatively higher temperature with an increased PAAc content. The decomposition temperature of PAAc is lower than that of PPG. PAAc affects the thermal stability of IPN more than PPG. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2570–2574, 2003     

Thermal characteristics of interpenetrating polymer networks composed of poly(vinyl alcohol) and poly(N‐isopropylacrylamide)

Interpenetrating polymer networks (IPNs) composed of poly(vinyl alcohol) (PVA) and poly(N‐isopropylacrylamide) (PNIPAAm) were prepared by the sequential‐IPN method. The thermal characterization of the IPNs was investigated using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). Depression of the melting temperature (T_m) of the PVA segment in IPNs was observed with increasing PNIPAAm content using DSC. DEA was employed to ascertain the glass‐transition temperature (T_g) of IPNs. From the result of DEA, IPNs exhibited two T_g values, indicating the presence of phase separation in the IPNs. The thermal decomposition of IPNs was investigated using TGA and appeared at near 200°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 881–885, 2003     

Pultruded fiber-reinforced poly(methyl methacrylate) composites. II. Static and dynamic mechanical properties,environmental effect,and postformability

This paper presents a novel process developed to manufacture poly(methyl methacrylate) (PMMA) pultruded composite. The mechanical, thermal, and dynamic mechanical properties, environmental effect, postformability of various fiber (glass, carbon, and Kevlar 49 aramid fiber) reinforced pultruded PMMA composites have been studied. Results show mechanical properties (i.e., tensile strength, specific tensile strength, tensile modulus, and specific flexural strength) and thermal properties (HDT) increase with fiber content. Kevlar fiber/PMMA composites possess the highest specific tensile strength and HDT, carbon fiber/PMMA composites show the highest tensile strength and tensile modulus, and glass fiber/PMMA composites show the highest specific flexural strength. Pultruded glass-fiber-reinforced PMMA composites exhibit good weather resistance. These composite materials can be postformed by thermoforming under pressure, and mechanical properties of postformed products can be improved. The dynamic shear storage and loss modulus (G′, G″) of pultruded glass-fiber-reinforced PMMA composites increased with decreasing pulling rate, and their shear storage moduli are higher than those of pultruded Nylon 6 and polyester composites.     

Surface‐initiated atom transfer radical polymerization from Mg(OH)2 nanoparticles to prepare the well‐defined polymer‐Mg(OH)2 nanocomposites

Well‐defined polymer‐Mg(OH)₂ nanocomposites were prepared by atom transfer radical polymerization (ATRP). The ATRP initiators were covalently attached to the Mg(OH)₂ by esterification of 2‐chloropropionyl chloride with hydroxyl group. The amount of polymer grafted from Mg(OH)₂ can be controlled using a different catalyst system and adding a small amount of polar solvent. The well‐defined diblock copolymer, consisting of poly(styrene) (PS) and poly(methyl methacrylate) (PMMA) were synthesized. The products were characterized by nuclear magnetic resonance, Fourier transform infrared, differential scanning calorimetry, and thermal gravimetric analysis. The morphologies of PS/PMMA and PS/PMMA/Mg(OH)₂‐g‐PS‐b‐PMMA blends are compared by using a scanning electron microscope. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3680–3687, 2007     

Preparation and properties of catalyzed polyimide/dicyanate semi‐interpenetrating networks for polymer gas membrane with suppressed CO2‐plasticization

The work presents an approach to reduce the plasticization of polymeric membranes caused by condensable gases, and particularly the effect of plasticization caused on polyimides by CO₂ at high pressure. A technical polyimide, Matrimid^®, was chosen as a reference of polyimide membrane and the approach applied consisted of incorporating reactive oligomers to have cross‐linkable mixed systems, which do not plasticize at high CO₂ pressure. Films of semi‐interpenetrating networks (semi‐IPNs) based on Matrimid^® and phenolphthalein dicyanate as cross‐linking monomer in ratios 90/10, 80/20, and 70/30, were prepared using a catalyst to lower the curing temperature from 280 to 180°C. Semi‐IPNs properties such as thermal stability, mechanical properties, glass transition temperatures, or density were measured to characterize the films and were correlated with the dicyanate monomer content. The CO₂ gas permeation behavior of the three semi‐IPNs was studied using a CO₂ feed pressure ranging from 1 to 30 atm. The gas separation properties were mainly explained attending to the density of the films, which depended on the dicyanate content used. In the three catalyzed semi‐IPNs, the CO₂ permeability coefficients remained almost constant all along the investigated range of CO₂ pressure while Matrimid^® treated at 180°C did show a clear tendency to plasticization over a critical feed pressure of about 17 bar. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012