Processing and mechanical properties of bio‐derived vinyl ester resin‐based composites

A “green” vinyl ester resin (GVER) is investigated for use in structural applications. The GVER was formulated using a monodisperse vinyl ester created via a novel synthetic route capable of using bio‐waste material from paper and biodiesel industries. The GVER was used either as a neat resin or as blended with a commercial vinyl ester resin. The processing viscosity and gel times are investigated. The GVER reaches a similar viscosity as the commercial resin with only half the styrene monomer content, thereby reducing the volatile organic compounds associated with manufacturing. Composites of the GVER matrix reinforced by carbon fabric were tested for their tensile and flexural properties. The mechanical performance of the GVER compares favorably with commercial resin and provide a route for composites manufacturing from sustainably sourced vinyl ester matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44642.     

High-performance thermosets with tailored properties derived from multi-arm stared vanillin and carbon fiber composites

Vanillin, a rigid compound can be separated from lignin, is a promising sustainable candidate for industrial and high performance polymers, while synthesis of hexa-epoxies is challenging. Meanwhile, carbon fiber reinforced bio-based polymers combining high performance are more difficult to be achieved because of the contradictions of liquidity and high rigidity in the polymer structure and performance. In this paper, a novel hexa-epoxy functionalized bio-based epoxy resin (HPVIGEP) with a multi-arm star structure, which simultaneously reduced the viscosity and improved thermo-mechanical properties. The rheological behavior analysis results of HPVIGEP indicated that the viscosity was 3406.9 mPa·s at 25°C, which dramatically decreased by 75.8% compared to DGEBA (14,096 mPa·s), leading to excellent processability and adaptability. At the same time, the study on mechanical properties revealed that the cured HPVIGEP manifested 30.6%, 33.7% and 49.0% in higher tensile strength, tensile modulus and storage modulus (30°C) than of cured commercial epoxy, respectively. The tensile strength and flexural strength of carbon fiber composites which were applied HPVIGEP were increased by 9.3% and 10.9%, respectively. In a word, this work provides the promise for the application of environmentally friendly bio-based composite materials.     

Preparation and properties of poly(ether‐ester‐amide)/poly(acrylonitrile‐co‐butadiene‐co‐styrene) antistatic blends

A novel antistatic agent poly(ether‐ester‐amide) (PEEA) based on caprolactam, polyethylene glycol, and 6‐aminocaproic acid was successfully synthesized by melting polycondensation. The structure, thermal properties, and antistatic ability of the copolymer were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analyses, and ZC36 megohmmeter. Test results show that PEEA is a block copolymer with a melting point of 217°C and a thermal decomposition temperature of 409°C, together with a surface resistivity of 10⁸ Ω/sq. Antistatic poly(acrylonitrile‐co‐butadiene‐co‐styrene) (ABS) materials were prepared by blending different content of PEEA to ABS resin. The antistatic performances, morphology, and mechanical properties were investigated. It is indicated that the surface resistivity of PEEA/ABS blends decrease with the increasing PEEA content, and the excellent antistatic performance is obtained when the antistatic agent is up to 10–15%. The antistatic performance is hardly influenced by water‐washing and relative humidity, and a permanent antistatic performance is available. The antistatic mechanism is investigated. The compatibility of the blends was studied by scanning electron microscopy images. The ladder distribution of antistatic agent is formed, and a rich phase of antistatic agent can be found in the surface layer. The elongations at break of the blend are improved with the increasing antistatic agent; the tensile strength and the notched impact strength kept almost the same. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Control of shrinkage and final conversion of vinyl ester resins cured in low‐temperature molding processes

Vinyl ester resin is a major thermoset polymer used in low‐temperature composite manufacturing processes such as the Seemann composite resin infusion‐molding process (SCRIMP). Volume shrinkage and residual styrene are important concerns for composites produced in such processes. A low‐shrinkage additive (LSA) is a typical agent added to control the volume shrinkage of vinyl ester resins during molding. In this study, the effects of LSA content and the temperature profile (the temperature gradient and peak temperature) on the volume shrinkage control of a vinyl ester resin were investigated. The reaction kinetics of the resin system were also studied. We achieved good volume shrinkage control if we raised the curing temperature slowly to allow sufficient time for phase separation and if the curing temperature reached a high value after phase separation to allow microvoid formation. On the basis of experimental results, we designed an improved SCRIMP to increase resin conversion, reduce resin shrinkage, and produce composites with better properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1486–1496, 2003     

The effectiveness of magnesium carbonate‐based flame retardants for poly(ethylene‐co‐vinyl acetate) and poly(ethylene‐co‐ethyl acrylate)

In this report we outline recent work on the evaluation of magnesium carbonate‐based flame retardants for polymers commonly used in halogen‐free flame retardant wire and cable applications: poly(ethylene‐co‐vinyl acetate) (EVA) and poly(ethylene‐co‐ethyl acrylate) (EEA). Natural magnesium carbonate (magnesite), synthetic magnesium carbonate (hydromagnesite), and hydromagnesite/huntite blends were combined with EVA or EEA and tested for flame retardancy effectiveness with the cone calorimeter. The flammability results showed that the effectiveness of these carbonates was polymer dependent, suggesting that polymer degradation chemistry played a role in the flammability reduction mechanism. Hydromagnesites were, in general, more effective in reducing flammability, being comparable in performance to magnesium hydroxide. Finally, we report some polymer–clay (organically treated montmorillonite and magadiite) + magnesium carbonate flame retardant results which showed that the nanocomposite yielded mixed results. Specifically, the polymer–clay nanocomposite samples did not always yield the greatest reductions in peak heat release rate. Copyright © 2007 John Wiley & Sons, Ltd.     

Preparation and properties of PC/SAN alloy modified with styrene‐ethylene‐butylene‐styrene block copolymer

A polycarbonate (PC)/ poly (styrene‐co‐acrylonitrile) (SAN) alloy modified with styrene‐ethylene‐butylene‐styrene (SEBS) block copolymer was prepared and the influence of SEBS content, PC content, and types of modifier on Izod notched impact strength, tensile strength, flexural strength, and Vicat softening temperature was studied. The results showed that the addition of SEBS could obviously increase the Izod notched impact strength and the elongation at break and decrease the tensile and flexural strength and Vicat softening temperature. PC/SAN alloy modified with SEBS had better mechanical properties than the PC/SAN alloy modified with ABS. DSC analysis and SEM photographs revealed that the SEBS was not only distributed in the SAN phase but also distributed in PC phase in a PC/SAN/SEBS alloy while the ABS was mainly distributed in SAN phase in a PC/SAN/ABS alloy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Soybean‐Oil‐Based Thermosetting Resins with Methacrylated Vanillyl Alcohol as Bio‐Based,Low‐Viscosity Comonomer

A novel, bio‐based, aromatic monomer (methacrylated vanillyl alcohol, MVA) is synthesized using vanillyl alcohol and methacrylic anhydride in the absence of solvents. The resulting MVA is used as a sustainable comonomer to replace styrene in a maleinated acrylated epoxidized soybean‐oil (MAESO) resin to produce novel thermosets via free radical polymerization. The influence of MVA loading on the viscosity, gelation time, curing extent, thermomechanical properties, and tensile properties of the MAESO–MVA thermoset is investigated. The synthesized MVA exhibits very low volatility, which is beneficial for the development of construction material with low or zero emission. The viscosity of the MAESO–MVA system can be tailored to meet the commercial requirements. Increasing the MVA content accelerates the crosslinking reaction rate and improves thermal and mechanical properties of the MAESO–MVA system. The glass transition temperature increases with increasing MVA content. Soxhlet extraction experiments show that more than 90% of the components are incorporated into the crosslinking network. Overall, the developed MVA monomer shows promising properties to be used as an effective, green comonomer to replace styrene.     

Characterization of degraded hydrogels based on poly(vinyl alcohol) grafted with poly(lactide‐co‐glycolide)

Poly(vinyl alcohol) (PVA) grafted with poly(lactide‐co‐glycolide) and cross‐linked as a material of increased hydrophobicity relative to PVA was produced. The properties were examined with respect to the mass loss, water uptake, hydrophilicity, and mechanical characteristics upon hydrolytical degradation. The hydrogels investigated display water uptake increasing with degradation time because of increasing hydrophilicity. The mass loss amounts up to 15% after eight weeks of degradation. The mechanical properties of the hydrogels are within the range of those of natural tissue, the E modulus is 18 MPa, or even 100–200 MPa, depending on the structure of material. The mechanical characteristic and their dependence degradation show the most recognizable correlation with the chemical structure. Studies of the topography of degraded samples (scanning electron microscopy) and IR measurements demonstrate the degradation to occur at slow rate due to the high degree of grafting. The mass loss is rather low and a bulk degradation mechanism takes place. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

UV curing behavior of methacrylated hyperbranched poly(amine‐ester)s

Methacrylated hyperbranched poly(amine ester)s as oligomers in radiation curing resins have a lower viscosity and a higher cure speed. Their viscosity was reduced sharply when an amount of a monomer was added or the temperature was increased. Their polymerization rate and final conversion of the double bond differ with the variation of the chemical structure of the end group, molar mass, and monomer content. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 51–57, 2001     

Melting behavior and surface morphology of poly(vinyl acetate‐co‐vinyl alcohol) copolymer

In a study of the surface morphology of commercial poly(vinyl acetate‐co‐vinyl alcohol) (ACA copolymer) with different percents of hydrolysis, different structures like fibrils, spherulites, micelles, vesicles, and spheroids were seen. The copolymer was crystallized by annealing at two different temperatures. The morphology of the polymer after crystallization and also without crystallization was studied. A decrease in the melting temperature just by heating to the melting temperature was observed, and for a detailed study, repetitive heating of the copolymer was carried out and changes in the mass and heat of fusion after every heating was recorded. The morphology of the copolymer after repetitive heating was studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1211–1218, 2002     

Preparation and properties of some thermosets derived from allyl‐functional naphthoxazines

A series of novel naphthoxazine monomers containing allyl functionalities were synthesized from the reaction of 1‐naphthol, 2‐naphthol, and 1,5‐dihdroxynaphthalene with allylamine and formalin. Another series of naphthoxazines were similarly prepared by using aniline instead of allylamine for comparison. The chemical structures of these novel monomers were confirmed by IR, ¹H NMR, and elemental analysis. DSC of the aniline‐ based naphthoxazines showed an exotherm due to the ring‐opening polymerization of oxazine. For allylamine‐based naphthoxazines, two exotherms were observed. The first exotherm is attributed to the thermal crosslinking of the allyl group and the second is due to the ring‐ opening polymerization of oxazine. The thermal cure of the allylamine‐based naphthoxazine monomers gave thermoset resins with novel structure comprising of polynaphthoxazine with extended network via the polymerization of allyl functionalities. Dynamic mechanical analyses and thermogravimetric analyses showed that the thermosets derived from allyl‐ functional naphthoxazines have high T_g's and stable storage moduli to higher temperature as well as better thermal stability than that of aniline‐based naphthoxazines. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3769–3777, 2006     

Poly(ethylene‐co‐vinyl acetate) blends with phenoxy

EVA was blended with phenoxy over the whole range of composition using a twin‐screw Brabender. Two‐phase separation caused by EVA crystallization was observed in the EVA‐rich blends and the dispersed domain of EVA was not clearly shown in the phenoxy‐rich blends. Differential scanning calorimetry (DSC) showed that the glass transition temperature (T_g) of EVA was increased by 5–10°C in the EVA‐rich blends but the T_g of phenoxy was superposed over the melting behavior of EVA. X‐ray diffraction measurement indicated that EVA crystallization was restricted in the phenoxy‐rich blends and the EVA crystal structure was influenced by incorporation of phenoxy into the EVA‐rich blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 227–236, 1999     

Thermal properties of blends of poly(hydroxybutyrate‐co‐hydroxyvalerate) and poly(styrene‐co‐acrylonitrile)

Thermal properties of blends of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) and poly(styrene‐co‐acrylonitrile) (SAN) prepared by solution casting were investigated by differential scanning calorimetry. In the study of PHBV‐SAN blends by differential scanning calorimetry, glass transition temperature and melting point of PHBV in the PHBV‐SAN blends were almost unchanged compared with those of the pure PHBV. This result indicates that the blends of PHBV and SAN are immiscible. However, crystallization temperature of the PHBV in the blends decreased approximately 9–15°. From the results of the Avrami analysis of PHBV in the PHBV‐SAN blends, crystallization rate constant of PHBV in the PHBV‐SAN blends decreased compared with that of the pure PHBV. From the above results, it is suggested that the nucleation of PHBV in the blends is suppressed by the addition of SAN. From the measured crystallization half time and degree of supercooling, interfacial free energy for the formation of heterogeneous nuclei of PHBV in the PHBV‐SAN blends was calculated and found to be 2360 (mN/m)³ for the pure PHBV and 2920–3120 (mN/m)³ for the blends. The values of interfacial free energy indicate that heterogeneity of PHBV in the PHBV‐SAN blends is deactivated by the SAN. This result is consistent with the results of crystallization temperature and crystallization rate constant of PHBV in the PHBV‐SAN blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 673–679, 2000     

Influence of hydrogen donors on peroxide‐initiated melt grafting of vinylsilane to poly(ethylene‐co‐vinyl acetate)

A technique has been examined for reducing the extent of crosslinking resulting from 1,1‐di(t‐butylperoxy)‐3,3,5‐trimethylcyclohexane (L‐231) initiating melt grafting of vinyltriethoxysilane (VTEOS) onto poly(ethylene‐co‐vinyl acetate) (EVA). Using measurements of crosslink density and VTEOS conversion, a standard of selectivity for the EVA/VTEOS/L‐231 system at 145 °C was defined and used to assess the influence of a range of additives (0.25 mol per mole VTEOS). The data indicated that compounds such as 4‐nonene, N,N‐dimethylaniline, and cumene improve reaction selectivity, whereas dodecane and cyclohexyl acetate have no effect. A strong correlation between the minimum C? H bond dissociation energy and the influence of a given compound is evident, suggesting that a labile C? H bond is the key element of an effective additive. A mechanism of additive function on the basis of hydrogen atom donation is proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2397–2402, 2002     

Synthesis and reactive features of a terpolymer: Poly(N‐vinyl‐2‐pyrrolidone‐co‐vinyl acetate‐co‐glycidyl methacrylate)

A polyvinyl pyrrolidone terpolymer system is described that can be chemically cross‐linked at moderate, 70–100°C, temperatures. The system has significant potential for development of durable long‐lasting pyrrolidone coatings in a wide range of applications, particularly in water filtration membrane construction where leaching is an unresolved, serious problem. The synthesis of the terpolymer, poly(N‐vinyl‐2‐pyrrolidone‐co‐vinyl acetate‐co‐glycidyl methacrylate), by free radical polymerization is described. The reactive features of this terpolymer are presented in the context of acidic anhydride curing. In a polar aprotic solvent, the terpolymer is reacted with poly(methyl vinyl ether‐co‐maleic acid) and cured thermally. Key aspects of the terpolymer synthesis and the acid anhydride cross‐linking reaction using DSC, rheology, FTIR, and a small molecule model system to study the cross‐linking chemistry are presented. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Relationship between the network morphology and properties of commercial vinyl ester resins

Two commercial vinyl ester resins, Derakane 411‐350 (resin D) and Derakane 411‐350 Momentum (resin M), were characterized. Despite the large quantity of publications in the literature about vinyl ester resins, few experimental results have been reported for resin M. The effect of the styrene content on the mechanical properties and morphological structure was studied. An increase in the styrene content produced a network with a low storage modulus in the rubber state and a glass‐transition temperature. The apparent average molecular weight between crosslink points and glass‐transition temperature were slightly higher for resin D than for resin M. The Fourier transform infrared spectra and molecular weight distributions were similar. However, resin M was tougher than resin D, and this may have been due to the closer structure in the fully cured state. Atomic force microscopy was performed for each cured resin and confirmed the difference in the nanostructures. The main reason for the differences in the developed structures was the use of an accelerator, which influenced the final morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3895–3903, 2006     

Use of pyrolyzed oil shale as filler in poly(ethylene‐co‐vinyl acetate) with different vinyl acetate contents

Pyrolyzed oil shale (POS) obtained from the pyrolysis of bituminous rock was used as filler in poly(ethylene‐co‐vinyl acetate) (EVA). The effects of the VA content of EVA and the particle size of POS on the mechanical properties were investigated. The composites were prepared in a rotor mixer at 180°C with a concentration of POS of up to 30 wt %. The stress–strain plots of the compression‐molded composites are similar to the EVA (18% VA content) behavior for low concentrations (1–5 wt %) of POS with a particle size lower than 270 mesh. It was observed that decreasing the POS particle size and increasing the VA content of EVA produced better compatibility between the polymer and filler. The mechanical properties, differential scanning calorimetry, and dynamic mechanical analysis also demonstrated the compatibility between EVA and POS under the increase of the VA content in the EVA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1544–1555, 2002; DOI 10.1002/app.10494     

Extensional viscosity measurements and characterization of poly (vinyl chloride‐co‐vinyl acetate) plastisols and foams

The foaming of PVC‐VA [Poly (vinyl chloride‐co‐vinyl acetate)] plastisols is a complex combination of processes involving the simultaneous curing of the paste with the evolution of gases caused by the decomposition of the chemical blowing agent. The extensional viscosity is a fundamental characteristic of the material, responsible for the behavior of the system when undergoing the extensional stress produced by the released gases. Nevertheless, such changes have not been considered to the same extent as the complex viscosity evolution or the thermal processes suffered by PVC‐VA plastisols. The objective of the present work is to study the extensional viscosity of the PVC‐VA plastisols prepared with three plasticizers of similar structure, but with different curing and rheological behavior in order to investigate its influence on the quality of the foams obtained. Extensional viscosity measurements under forced prestretch conditions revealed that depending on the structure and consequently on the compatibility of the plasticizer used, each plastisol develops its properties and structure accordingly. DINCH plasticizer (Diisononyl cyclohexane‐1,2‐dicarboxylate presenting alicyclic ring) seems to be the less compatible compared with the other two studied (both presenting aromatic rings) according to its behavior during the curing and foaming processes and may not be able to withstand the pressure evolved by the released gases during the foaming process yielding foams of poorer quality. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of posttreatment on morphology and properties of poly(ethylene‐co‐vinyl alcohol) microporous hollow fiber via thermally induced phase separation

Poly(ethylene‐co‐vinyl alcohol) (EVOH) hollow fiber membranes were prepared by thermally induced phase separation (TIPS) process. Water, methanol, and acetone were used to extract the diluents in the fibers, respectively. Bigger shrinkage of fibers during extractant evaporation was observed when water or methanol was used. Their interaction parameters with EVOH were calculated via Hansen solubility, respectively. The mechanism of hollow fiber volume shrinkage was discussed. It was found that affinity of the extractant with polymer was the critical factor except for the surface tension of extractant. Through the X‐ray diffraction analysis during extraction and evaporation, the crystallization behavior of the polymer was studied. From the SEM photos, it was observed that the volume shrinkage was derived from the collapse of porous structure. The fiber sample extracted by acetone had similar morphology with the sample freeze‐dried. The gas and water permeability were also measured and the results were coincident with the morphology of fibers and shrinkage data. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4106–4112, 2007