Influence of the ethylene–(methacrylic acid)–Zn2+ ionomer on the thermal and mechanical properties of blends of poly(propylene) (PP)/ethylene–(vinyl alcohol) copolymer (EVOH)

The thermal and mechanical properties and the morphologies of blends of poly(propylene) (PP) and an ethylene–(vinyl alcohol) copolymer (EVOH) and of blends of PP/EVOH/ethylene–(methacrylic acid)–Zn²⁺ ionomer were studied to establish the influence of the ionomer addition on the compatibilization of PP/EVOH blends and on their properties. The oxygen transmission rate (O₂TR) values of the blends were measured as well. PP and EVOH are initially incompatible as was determined by tensile tests and scanning electronic microscopy. Addition of the ionomer Zn²⁺ led to good compatibility and mechanical behaviour was improved in all blends. The mechanical properties on extruded films were studied for 90/10 and 80/20 w/w PP/EVOH blends compatibilized with 10 % of ionomer Zn²⁺. These experiments have shown that the tensile properties are better than in the injection‐moulded samples. The stretching during the extrusion improved the compatibility of the blends, diminishing the size of EVOH domains and enhancing their distribution in the PP matrix. As was to be expected, the EVOH improved the oxygen permeation of the films, even in compatibilized blends. Copyright © 2004 Society of Chemical Industry     

Preparation and characterization of proton‐exchange hybrid membranes

Two types of composite were prepared, based on a thermoplastic polymer, polyvinylidene fluoride (PVDF), and an elastomer, ethylene‐propylene‐diene terpolymer (EPDM), respectively. We obtained both series by addition of an inorganic proton‐conducting antimonic acid derivative (HSb) and polystyrene crosslinked with a small percentage of divinylbenzene (PS‐co‐DVB). From these composites, membranes were obtained and subjected to a heterogeneous‐phase sulfonation reaction with chlorosulfonic acid. All experimental materials were characterized from a morphological and electrical point of view, by means of techniques such as differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), non‐isothermal crystallization and complex impedance analysis. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterisation of carboxylic acid and diphenylphosphine derivatives in the 1,3-diyne series: Spectral properties of polydiacetylene carboxylates

Symmetrically substituted 1,3-diynes containing hydroxyalkyl ( 1a-d ), bromoalkyl ( 1e-h ) (diphenylphosphinyl) ( 1i-k ) and carboxyalkyl ( 2a-d ) substituents have been prepared and characterised; the phosphine derivative ( 1k ) has been converted with alkyl iodides ( RI ; R = Me, Et) into bis(phosphonium) salts ( 1l and m ). During preparation of the diynedioic acid. ( 2a ), the non-centrosymmetrical diyne, HO₂CCH₂C?C—C?C(CH₂)₂OH ( 3 ), was also isolated. ⁶⁰Co γ-Irradiation of diacetylene monomers ( 2a – d ) and 10,12-tricosadiyn-1-oic acid gave the corresponding polydiacetylene derivatives ( 4a – d and 5 ), respectively. Rubidium salts of ( 4c ) and ( 4d ), a barium salt of ( 4c ), and a potassium salt of ( 5 ) were prepared and isolated; soluble potassium salts of the carboxylic acid polymers ( 4 ) were generated in aqueous solution. The effects of changes in pH on the UV/visible absorption spectra of aqueous solutions of selected carboxylic acid polydiacetylenes have been recorded, and are discussed.     

Asbestos replacement aspects: Modification of the fibre-matrix interphase in lonomer based composites

Asbestos fibres, of the chrysotile variety, and chopped carbon fibres were pretreated by an in-situ polycondensation technique eventually resulting in a polyamide coating on the fibre surface. Ionomer based composites containing either carbon or asbestos fibres in random in plane fibre orientation were prepared, and the influence of this coating process on the tensile properties was investigated. It was found that for the asbestos-filled composites the presence of the nylon 6,6 interlayer improves the tensile performance, especially at moderate polyamide depositions. This is not the case with the pretreated carbon-filled composites for which carbon fibres with higher polyamide contents are preferred. Combinations of the treated asbestos fibres with carbon and/or aramid fibres may be used to reduce the asbestos content in asbestos-only based engineering plastics.     

Synthesis and properties of novel amphiphilic sulfated ionomers by the ring‐opening reaction of an epoxidized styrene–butadiene–styrene triblock copolymer

A method for the synthesis of novel sulfated ionomer of styrene–butadiene–styrene triblock copolymer (SBS) was developed. SBS was first epoxidized by performic acid in the presence of a phase‐transfer catalyst; this was followed by a ring‐opening reaction with an aqueous solution of alkali salt of bisulfate. The optimum conditions for the ring‐opening reaction of the epoxidized SBS with an aqueous solution of KHSO₄ were studied. During the ring‐opening reaction, both phase‐transfer catalyst and ring‐opening catalyst were necessary to enhance the conversion of epoxy groups to ionic groups. The products were characterized with Fourier transform infrared spectrophotometry and transmission electron microscopy (TEM). After the potassium ions of the ionomer were substituted with lead ions, the lead sulfated ionomer exhibited dark spots under TEM. Some properties of the sulfated ionomer were studied. With increasing ionic groups or ionic potential of the cations, the water absorbency and emulsifying volume of the ionomer and the intrinsic viscosity of the ionomer solution increased, whereas the oil absorbency decreased. The sulfated ionomer possessed excellent emulsifying properties compared with the sulfonated SBS ionomer. The sodium sulfated ionomers in the presence of 10% zinc stearate showed better mechanical properties than the original SBS. When the ionomer was blended with crystalline polypropylene, a synergistic effect occurred with respect to the tensile strength. The ionomer behaved as a compatibilizer for blending equal amounts of SBS and oil‐resistant chlorohydrin rubber. In the presence of 3% ionomer, the blend exhibited much better mechanical properties and solvent resistance than the blend without the ionomer. SEM photographs indicated improved compatibility between the two components of the blend in the presence of the ionomer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects and properties of poly(arylene ether benzonitrile)s of various molecular weights blended with sulfonated poly(ether ether ketone)

Poly(arylene ether benzonitrile) (PAEBN) was synthesized with 2,6‐dichlorobenzonitrile and biphenol. PAEBNs with various molecular weights (MWs), 1,640,000 and 185,000 g/mol, were synthesized by control of the stoichiometry of the monomers and were blended with sulfonated poly(ether ether ketone) (SPEEK). The effects of MW on the water uptake, swelling, methanol permeability, and proton conductivity of the SPEEK/PAEBN blend membranes were investigated. The molecular mobility of the SPEEK/PAEBN blends was also examined in this study. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Toward Largely Enhanced Toughness and Balanced Strength in PA1012/EPDM Blends via Synergistic Effect of Sacrificial Bonds and Network Structure

Here, zinc-neutralized ethylene propylene diene monomer (EPDM) ionomers with different neutralization levels are prepared through melt blending, and are then incorporated with polyamide 1012 (PA1012) to fabricate PA1012/EPDM ionomer blends. Interestingly, complex crosslinking networks are formed in the blends due to the construction of sacrificial bonds (Zn²⁺-carboxyl, Zn²⁺-amide). The as-formed network structure and sacrificial bond endow the PA/EPDM blends with largely enhanced toughness (16 times higher than that of neat PA), as well as balanced strength and stiffness. Meanwhile, the rheological behaviors of PA1012/EPDM ionomer blends indicate their relative low melting viscosity, which can avoid the processing shortcomings of plastics toughened with rubber. Moreover, PA1012/EPDM ionomer blends show obvious gelation behavior, and a maximum notched Izod impact strength exhibited at the gel point, in which unique double network structure can be observed obviously, indicating that there is a corresponding correlation between the rheological and mechanical parameters. Furthermore, the supper-toughening mechanism of PA1012/EPDM ionomer blends at gel point is explored, which origins from the large deformation and cavitation of rubber particles and the destruction of special double network morphologies. This study provides a novel and effective strategy to fabricate PA materials with outstanding toughness and excellent strength simultaneously.     

Structure–property relationships for sulfonated poly(butylene terephthalate)

Structure–property relationships have been developed for sulfonated poly(butylene terephthalate) copolymers. The compositional variables investigated were sulfonate content, molecular weight, and polymer endgroup composition, and the fundamental polymer properties evaluated were melt viscosity, crystallization kinetics, and impact strength. It was found that all compositional variables significantly affect all of the polymer properties of interest. The most interesting effect is the influence of polymer endgroup composition on polymer properties. The trends indicate that the carboxylic acid endgroups form intermolecular interactions with sodium sulfonate groups, resulting in a decrease in the strength of intermolecular ionic interactions between sodium sulfonate groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4662–4771, 2006     

Polyurethane–poly(methyl methacrylate) block copolymer dispersions through polyurethane macroiniferters

Polyurethane macroiniferter/poly(methyl methacrylate) block copolymer dispersions with inverse core‐shell morphologies were obtained from 1,1,2,2,‐tetraphenylethane‐1,2‐diol, dimethylol propionic acid, 4,4′‐diphenylmethane diisocyanate, and poly(propylene glycol) via a living radical mechanism. Molecular weight, particle size and dispersion viscosity, and thermal, mechanical, and dynamic mechanical properties of the dispersion cast films are reported as a function of copolymerization time. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1971–1975, 2003     

High styrene–rubber ionomers,an alternative to thermoplastic elastomers

High styrene rubber ionomers were prepared by sulfonating styrene–butadiene rubber of high styrene content (high styrene rubber) in 1,2‐dichloroethane using acetyl sulfate reagent, followed by neutralization of the precursor acids using methanolic zinc acetate. The ionomers were characterized using X‐ray fluorescence spectroscopy, Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), dynamic mechanical analysis (DMA), and also by the evaluation of mechanical properties. The FTIR studies of the ionomer reveal that the sulfonate groups are attached to the benzene ring. The NMR spectra give credence to this observation. Results of DMA show an ionic transition (T_i) in addition to glass–rubber transition (T_g). Incorporation of ionic groups results in improved mechanical properties as well as retention of properties after three cycles of processing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2294–2300, 2002