Thermomechanical properties and morphology of interpenetrating polymer networks of polyurethane–poly(methyl methacrylate)

Interpenetrating networks (IPNs) of polybutadiene‐based polyurethane (PU) and poly(methyl methacrylate) (PMMA) were synthesized. The effect of the incorporation of 2% glycidyl methacrylate (GMA) and 2‐hydroxyethyl methacrylate (2‐HEMA) on the thermal, mechanical, and morphological properties of IPNs was investigated. Both 2‐HEMA and GMA led to improvements in these properties. However, 2‐HEMA‐containing IPNs showed somewhat better tensile strength, elongation, and damping characteristics. The morphology of IPNs containing 2‐HEMA showed better mixing of the components. The improvement in the properties was observed for up to 40% PMMA in the IPNs. Differential scanning calorimetry thermograms showed the presence of three glass transitions. The third glass‐transition temperature was explained by possible grafting of methyl methacrylate onto PU. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1576–1585, 2002     

Interpenetrating polymer networks of castor oil polyester and poly(methyl methacrylate)

The physical and mechanical properties of interpenetrating polymer networks (IPNs) and semi-I IPNs of the castor oil polyester network and poly(methyl methacrylate) were investigated. In the semi-I IPNs, the second component was a copolymer of poly(methyl methacrylate) and polystyrene (PS) or poly(methyl methacrylate) and poly(n-butyl acrylate) (PnBA). The dynamic mechanical properties indicated the semi-I IPNs to be more compatible than the IPNs. The degree of molecular mixing was higher than that for IPNs. The impact strength showed a gradual increase with the increase in the percentage of PS or PnBA in the copolymer. The effect of the copolymerization of the second component on transparency was investigated. The transparency of the semi-I IPNs increased with the increasing composition of PnBA, but reduced with the increasing composition of PS. These results are discussed in light of existing theories.     

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.     

Studies on miscibility of dehydrated castor oil epoxy blend with poly(methyl methacrylate)

Oil epoxies can be used as plasticizers in the processing of hard polymers. For this purpose dehydrated castor oil epoxy (DCOE), a product from sustainable resource, has been chosen for blending with poly(methyl methacrylate) (PMMA) to investigate the compatibility of this blend pair. Blends of DCOE/PMMA were prepared in the weight ratios 80/20, 60/40, 40/60, and 20/80 through solution method by mixing in dimethylsulphoxide. Free‐standing films of the blend were cast and the miscibility of the two components was investigated by viscosity and ultrasonic measurements, which provided valuable information on the degree of compatibility of the pairs of blends in solution. The compatibility was also examined by differential scanning calorimetry and scanning electron microscopy. All the studies revealed that DCOE was immiscible with PMMA. However, the appearance and texture of the films were not found to show any visible change over several months, which indicates stability of this blend system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3094–3100, 2006     

Carbon nanotube‐based thermoplastic polyurethane‐poly(methyl methacrylate) nanocomposites for pressure sensing applications

We have synthesized unique flexible pressure‐sensitive nanocomposites by means of a solution mixing method, by adding multiwalled carbon nanotubes (MWCNTs) into a thermoplastic urethane (TPU) matrix along with poly(methyl methacrylate) (PMMA) microbeads of various sizes. The influence of the various PMMA bead sizes on the pressure sensing properties of the nanocomposites was studied over a range of pressures. The PMMA microbeads were used to achieve an early percolation threshold at low loadings of MWCNTs. We used scanning electron microscopy to study the nanocomposites' morphology, and conducted differential scanning calorimetry analyses to investigate their thermal properties. The nanocomposites' electrical and thermal conductivities were also measured under various applied pressures. The nanocomposites displayed repeatable electrical responses under various applied pressures, demonstrating their suitability for use as pressure sensing materials. The proposed material is an ideal candidate for use in the preparation of pressure‐sensitive devices. POLYM. ENG. SCI. 56:1031–1036, 2016. © 2016 Society of Plastics Engineers     

Polyurethane interpenetrating polymer networks. V. Engineering properties of polyurethane–poly(methyl methacrylate) IPN's

The engineering properties of polyurethane–poly(methyl methacrylate) simultaneous interpenetrating networks (SIN's) were evaluated. The hardness behavior reflected the observed phase inversion in the electron-microscopic studies. The maximum ultimate tensile strength was observed at 85% polyurethane–15% poly(methyl methacrylate) IPN and was due to the filler-reinforcing effect of the rigid poly(methyl methacrylate) phase. The ultimate tensile strenght of the 75/25 polyurethane–poly(methyl methacrylate) IPN was higher than that of the corresponding pseudo-IPN's (only one network crosslinked) and the linear blend. The leathery and glassy compositions did not show any reinforcement in the ultimate tensile strength. This indicated that the reinforcement in the ultimate tensile strength was not directly related to interpenetration (by increased physical entanglement crosslinks), but indirectly related by reducing the rigid phase domain sizes and increasing the adhesion between the two phases, thus enhancing the filler-reinforcing effect similar to that observed in a carbon black-filled rubber. The tear strengths of the polyurethane-rich IPN's pseudo-IPN's, and linear blends were found to be higher than that of the pure polyurethane as a combined result of increased modulus and tensile strength. The weight retentions in the thermal decomposition of the IPN's, pseudo-IPN's, and linear blends were higher than the proportional average of the component networks. The results seemed to indicate that this enhancement was related to the presence of the unzipped methyl methacrylate monomer. It was suggested that the monomers acted as radical scavengers in the polyurethane degradation, thus delaying the further reaction of the polyurethane radicals into volatile amines, isocyanates, alcohols, olefins, and carbon dioxide.     

Biocompatibility and microscopic evaluation of polyurethane–poly(methyl methacrylate)–titnanium dioxide based composites for dental applications

We prepared and then blended polyurethanes (PUs) with poly(methyl methacrylate)s (PMMAs) and TiO₂ by varying the percentage compositions to form pellets. The chemistry of all of the blended samples was confirmed by Fourier transform infrared spectroscopy. The incorporation of TiO₂ into the PU–PMMA matrix was confirmed with scanning electron microscopy analysis. Differential scanning calorimetry analysis and compression testing was performed, and the results are discussed. The cytotoxicity level of the prepared blends displayed dependence on the composition ratio of the PU–PMMA blends. The results reveal that the optimum PU contents in the PU–PMMA–TiO₂ blend were responsible for its better biocompatibility. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39806.     

Interpenetrating polymer networks from castor oil based polyurethane and poly(methyl methacrylate), III

Liquid prepolyurethanes (PPU) were obtained from castor oil and toluene-2,4-diisocyanate under different experimental conditions varying NCO/OH ratio. All these prepolyurethanes were subsequently interpenetrating with poly(methyl methacrylate) made by radical polymerization initiated with benzoyl peroxide. The novel PPU/PMMA interpenetrating polymer networks were obtained as though films by transfer moulding. They were characterized by thermal studies (DSC and TGA) and mechanical properties viz., tensile strength, modulus of elasticity, and percent elongation at break. The morphological behaviour was analyzed by scanning electron microscopy.     

Novel poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers through atom transfer radical polymerization

Poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers have been synthesized successfully through atom transfer radical polymerization of methyl methacrylate using telechelic bromo‐terminated polyurethane/CuBr/N,N,N,N″,N″‐pentamethyldiethylenetriamine initiating system. As the time increases, the number‐average molecular weight increases linearly from 6400 to 37,000. This shows that the poly methyl methacrylate blocks were attached to polyurethane block. As the polymerization time increases, both conversion and molecular weight increased and the molecular weight increases linearly with increasing conversion. These results indicate that the formation of the tri‐block copolymers was through atom transfer radical polymerization mechanism. Proton nuclear magnetic resonance spectral results of the triblock copolymers show that the molar ratio between polyurethane and poly (methyl methacrylate) blocks is in the range of 1 : 16.3 to 1 : 449.4. Differential scanning calorimetry results show T_g of the soft segment at ?35°C and T_g of the hard segment at 75°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Feather‐like morphology of poly(methyl methacrylate)/poly(ethylene oxide) blends: The effect of cooling rate and poly(methyl methacrylate) content

The effect of cooling rate on the crystallization morphology and growth rate of poly(ethylene oxide) (PEO) and PEO/poly(methyl methacrylate) (PMMA) blends has been observed by Hot Stage Polarized Microscopy (HS‐POM). The isothermal crystallization kinetics study was carried out by differential scanning calorimetry (DSC). The spherulite morphology has been observed for the neat PEO with molecular weight of 6000 g/mol. By adding of PMMA with molecular weight of 39,300 g/mol, the growth fronts become irregular. With the increasing of PMMA content, the irregularity of growth front becomes more obvious, and the feather‐like morphology can be observed. When PMMA content is 60%, the spherulite is seriously destroyed. This phenomenon is more obvious for the slow cooling process. Based on the measurement of spherulite, the growth rate curves were obtained. According to the curves, it can be seen that the growth rate decreases with the increasing of PMMA content, and the growth rate during the slow cooling process is higher than that of the fast cooling process. The isothermal crystallization experiment indicates that the crystallization rate decreases dramatically with the increasing of PMMA content. And the Avrami parameter n was obtained, which is non‐integral and less than 3. Finally, it can be concluded that the higher value of n can be obtained for the condition with low crystallization rate. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41705.     

Viscoelastic properties,morphology, and thermal stability of rigid and plasticized poly(vinyl chloride)/poly(methyl methacrylate) blends

Viscoelastic properties, morphology, and thermal stability of rigid and plasticized poly(vinyl chloride)/poly (methyl methacrylate) (PVC/PMMA) blends were studied. For that purpose, blends of variable composition from 0 to 100 wt% were prepared in the presence (15, 30, and 50 wt%) and in the absence of di(2‐ethylhexyl) phthalate as plasticizer. Their miscibility was investigated by using dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). The DMTA and SEM results showed that the two polymers are miscible. Thermogravimetric studies on these blends were carried out in a flowing atmosphere of air from ambient temperature to 550°C. The results showed that the thermal degradation of rigid and plasticized PVC/PMMA in this broad range of temperature is a three‐step process and that PMMA exerted a stabilizing effect on the thermal degradation of PVC during the first step by reducing the rate of dehydrochlorination. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

On the linear viscoelastic limit of polymers—exemplified on poly(methyl methacrylate)

The linear viscoelastic limit of poly(methyl methacrylate) (PMMA) is established on the basis of the Reiner-Weissenberg criterion of strength. The obtained limit is not simply a “strainlimit” or a “stress-limit” but a function of both strain and stress, an energetical limit. In stress-strain representation the limit is independent of time and temperature, which means that the linear or non-linear behavior of the material depends only on the actual values of strain and stress. Some experimental data obtained on PMMA confirm the theory.     

Interpenetrating polymer networks based on polyol modified castor oil polyurethane and poly(2‐ethoxyethyl methacrylate): Synthesis,chemical, mechanical,thermal properties,and morphology

Interpenetrating polymer networks (IPNs) of glycerol modified castor oil polyurethane (GC‐PU) and poly(2‐ethoxyethyl methacrylate) poly(2‐EOEMA) were synthesized using benzoyl peroxide as initiator and ethylene glycol dimethacrylate (EGDM) as crosslinker. GC‐PU/poly (2‐EOEMA) interpenetrating polymer networks were obtained by transfer molding. The novel GC‐PU/poly (2‐EOEMA) IPNs are found to be tough films. These IPNs are characterized in terms of their resistance to chemical reagents thermal behavior (DSC, TGA) and mechanical behavior, including tensile strength, Young's modulus, shore A hardness, and elongation. The morphological behavior was studied by scanning electron microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1029–1034, 2004     

Synthesis and thermal properties of poly(methyl methacrylate)‐poly(L‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer

Poly(methyl methacrylate)‐poly(L ‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer was prepared using atom transfer radical polymerization (ATRP). The structure and properties of the copolymer were analyzed using infrared spectroscopy, gel permeation chromatography, nuclear magnetic resonance (¹H‐NMR, ¹³C‐NMR), thermogravimetry, and differential scanning calorimetry. The kinetic plot for the ATRP of methyl methacrylate using poly(L ‐lactic acid) (PLLA) as the initiator shows that the reaction time increases linearly with ln[M]₀/[M]. The results indicate that it is possible to achieve grafted chains with well‐defined molecular weights, and block copolymers with narrowed molecular weight distributions. The thermal stability of PLLA is improved by copolymerization. A new wash‐extraction method for removing copper from the ATRP has also exhibits satisfactory results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(methyl methacrylate)

Summary Poly(n-propyl methacrylate) is known to be immiscible with poly(methyl methacrylate) (PMMA). However, we have found that poly(methoxymethyl methacrylate) is miscible with PMMA, indicating the importance of ether oxygen atoms in achieving miscibility. On the other hand, poly(methylthiomethyl methacrylate) is immiscible with PMMA.     

Effects of compatibilizer on the morphological,mechanical, and rheological properties of poly(methyl methacrylate)/poly(N‐methyl methacrylimide) blends

The effects of compatibilizer on the morphological, thermal, mechanical, and rheological properties of poly(methyl methacrylate) (PMMA)/poly(N‐methyl methacrylimide) (PMMI) (70/30) blends were investigated. The compatibilizer used in this study was styrene–acrylonitrile–glycidyl methacrylate (SAN‐GMA) copolymer. Morphological characterization of the PMMA/PMMI (70/30) blend with SAN‐GMA showed a decrease in PMMI droplet size with an increase in SAN‐GMA. The glass‐transition temperature of the PMMA‐rich phase became higher when SAN‐GMA was added up to 5 parts per hundred resin by weight (phr). The flexural and tensile strengths of the PMMA/PMMI (70/30) blend increased with the addition of SAN‐GMA up to 5 phr. The complex viscosity of the PMMA/PMMI (70/30) blends increased when SAN‐GMA was added up to 5 phr, which implies an increase in compatibility between the PMMA and PMMI components. From the weighted relaxation spectrum, which was obtained from the storage modulus and loss modulus, the interfacial tension of the PMMA/PMMI (70/30) blend was calculated using the Palierne emulsion model and the Choi‐Schowalter model. The results of the morphological, thermal, mechanical, and rheological studies and the values of the interfacial tension of the PMMA/PMMI (70/30) blends suggest that the optimum compatibilizer concentration of SAN‐GMA is 5 phr. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43856.     

Study of sintering of poly(methyl methacrylate)

Sintering of poly(methyl metacrylate) spheres to the blocks of the same material was studied at temperatures ranging from 127° to 207°C. The analysis of the data based on the empirical Ostwald relation indicates that the predominant mechanism responsible for this process is non-Newtonian viscous flow. The type of the flow changes with temperature of sintering, being pseudo-plastic at lower temperatures and tending to dilatancy at higher ones.     

Rheological properties of polystyrene and poly(methyl methacrylate) blends

Rheological properties of the polystyrene (PS) and poly(methyl methacrylate) (PMMA) blends were studied by Advanced Rheometric Expansion System (ARES). Storage modulus and loss modulus of the PS and PMMA blends were measured, and the interfacial tension of the PS and PMMA blends were obtained with various emulsion models by using the storage modulus and loss modulus of the blends. The value of interfacial tension estimated from the Palierne emulsion model was found to be 2.0 mN/m. Also, the interfacial tension between PS and PMMA was calculated by a theoretical model. The values of interfacial tension of the PS and PMMA blends obtained by the experiment and theoretical model were found to be in good agreement.     

Preparation and properties of silicone‐containing poly(methyl methacrylate) gels

Poly(methyl methacrylate) (PMMA) gels with varying amounts of silicone and solvent and constant amounts of crosslinker were prepared by solution free radical crosslinking copolymerization of methyl methacrylate (MMA), ethylene glycol dimethacrylate (EGDM), tetraethoxysilane (TEOS) and vinyltriethoxysilane (VTES) comonomer systems. They were then studied in benzene at a total monomer concentration of 3.5 mol L^?1 and 70 °C. The conversion of monomer, volume swelling ratio, weight fraction and gel point were measured as a function of the reaction time, silicone concentration and benzene content up to the onset of macrogelation. Structural characteristics of the gels were examined by using equilibrium swelling in benzene, gel fraction and Fourier‐transform infrared (FTIR) analysis. The morphology of the copolymers was also investigated by SEM. Based on the obtained results, it was concluded that the FTIR data did not have the capacity to show the presence of the VTES or TEOS moiety in these kinds of copolymers. On the other hand, the variation of weight fraction of gel, W_g, and its equilibrium volume swelling ratio in benzene, q_v, exhibited the same behaviour as that of MMA/EGDM copolymers. Also, the dilution of the monomer mixture resulted in an increase in the gel point and swelling degree and a decrease in the percent of conversion and gel fraction. Finally, TEOS is not an ideal silicone compound for reaction in the MMA/EGDM copolymerization system, whereas VTES is a suitable silicone comonomer for this system and it has been proved useful. Copyright © 2005 Society of Chemical Industry     

Effect of nanoclay on the morphology and properties of poly(methyl methacrylate)/high‐density polyethylene blends

The effect of nanoclay on the morphology and properties of poly(methyl methacrylate) (PMMA)/high‐density polyethylene (HDPE) blends was studied. A scanning electron microscopy study of the PMMA/HDPE (70/30 w/w) blends with nanoclay indicated a reduction in the average domain sizes of the dispersed HDPE phase and, hence, a better extent of mixing compared to that of the blends without any nanoclay. An X‐ray diffraction study and transmission electron microscopy revealed the localization of intercalated nanoclay in the PMMA matrix of the PMMA/HDPE (70/30 w/w) blend. However, the same effect of clay was not observed in the PMMA/HDPE (30/70 w/w) blend when HDPE became the matrix. In the PMMA/HDPE (30/70 w/w) blend, the addition of nanoclay increased the domain size of the dispersed PMMA domains by preferential location of the clays inside the PMMA domains. The addition of polyethylene‐grafted maleic anhydride in both compositions of the PMMA/HDPE blend effectively reduced the domain size of the disperse phases in the blend. However, the presence of clay increased the tensile strength and storage modulus of the PMMA/HDPE blends in both blend compositions. Thus, in the PMMA/HDPE blend, the clay platelets acted as a effective compatibilizer as long as they were dispersed mainly in the matrix phase. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010