The effect of segment length on some properties of thermoplastic poly(ester–siloxane)s

A series of novel thermoplastic elastomers, based on poly(dimethylsiloxane) (PDMS) as the soft segment and poly(butylene terephthalate) (PBT) as the hard segment, were synthesized by catalyzed two‐step, melt transesterification reactions of dimethyl terephthalate and methyl esters of carboxypropyl‐terminated poly(dimethylsiloxane)s (M?_n = 550–2170 g mol^?1) with 1,4‐butanediol. The lengths of both the hard and soft segments were varied while the weight ratio of the hard to soft segments in the reaction mixture was maintained constant (57/43). The molecular structure, composition and molecular weights of the poly(ester–siloxane)s were examined by ¹H NMR spectroscopy. The effectiveness of the incorporation of the methyl‐ester‐terminated poly(dimethylsiloxane)s into the copolymer chains was verified by chloroform extraction. The effect of the segment length on the transition temperatures (T_m and T_g) and the thermal and thermo‐oxidative degradation stability, as well as the degree of crystallinity and hardness properties of the synthesized TPESs, were studied. Copyright © 2003 Society of Chemical Industry     

Development of polyurethane elastomer composite materials by addition of milled fiberglass with coupling agent

Polyurethane elastomer composites were developed using milled fiberglass and their mechanical properties were studied. In particular, the organically chemical treatment of the milled fiberglass was investigated in detail. It was demonstrated that both strength and toughness of the resulting elastomer composites were improved considerably with the addition content of fiberglass. Furthermore, it was indicated that the optimal properties can be achieved by the proper addition of milled fiberglass that was chemically treated using coupling agent.     

Structure and dynamics of dipolar fluids under strong shear

Molecular dynamical simulation has been carried out to investigate the structure and dynamics of a dipolar fluid under strong shear. Dipolar fluid consists of polarizable particles, which have an induced dipole moment in the applied field direction. Shear stress is perpendicular to the field direction. When shear stress is small, the flow has a flowing-chain structure. If shear stress increases to pass a critical value, flowing-chain structure changes to flowing layer structure. Each layer is parallel to the flow direction and shear direction. Within one layer, particles form strings in the flow direction.     

Development and characterization of magnetorheological polymer gels

Magnetorheological materials have been used in many applications in recent years. To develop new materials, polyurethane and silicone polymer gels were investigated. Rheology is qualitatively controlled for each system by controlling the concentration of reactants and diluents. The resulting polymers have solid, gel, or liquid states, depending on the crosslinking and dilution. The gels were characterized through kinetic analysis. Differential scanning calorimetry (DSC) was used with analysis methods to find the kinetic properties for diluted and undiluted polyurethane systems. Heat of reaction, order of reaction, preexponential constant, and activation energy were obtained from the experimental DSC data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2733–2742, 2002     

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     

Measuring interdiffusion at an interface between two elastomers with tapping-mode and contact-resonance atomic force microscopy imaging

Despite the common use of tapping-mode atomic force microscopy to image composites or polymer blends, very few studies have focused on the measurement of the interdiffusion at an interface between two polymers in contact. In this study, we show how to assess the interphase between two polymers with two methods. First, stable and robust tapping conditions are established, and the problem of the phase contrast is discussed. Second, a contact-resonance method is presented: the tip in contact with the sample is electrostatically excited at its resonance frequency by a self-controlled oscillator. The gain and frequency images allow us to measure the interdiffusion width. Both methods (using high and weak mechanical solicitation) give the same assessment of the interdiffusion width. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and thermomechanical characterization of polyurethane elastomers extended with α,ω‐alkane diols

A series of polyurethane (PU) elastomers was prepared by the reaction of poly(?‐caprolactone) and 4,4′‐diphenylmethane diisocyanate, which was extended with a series of chain extenders (CEs) having 2–10 methylene units in their structure. The completion of the reaction was confirmed by Fourier transform infrared spectroscopy. The chemical structures of the synthesized PU samples were characterized with Fourier transform infrared, ¹H‐NMR, and ¹³C‐NMR spectroscopy, and the thermal properties were determined by thermogravimetric analysis, DSC, and dynamic mechanical thermal analysis techniques. The mechanical properties were also studied and are discussed. The thermogravimetric analysis and DSC analysis showed that CE length had a considerable effect on the thermal properties of the prepared samples. The dynamic mechanical thermal analysis and damping peaks were also affected by the number of methylene units in the CE length. The elastomer extended with 1,2‐ethane diol exhibited optimum thermal properties, whereas the elastomer based on 1,10‐decane diol displayed the worst thermal properties. Tensile strength and elongation at break decreased with increasing CE length, whereas hardness showed the opposite trend. The glass‐transition temperature moved toward lower temperatures with increasing CE length. The decrease in the glass‐transition temperature and tensile properties were interpreted in terms of decreasing hard segments and increasing chain flexibility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of polyurethane elastomers hypercross-linked by partially hydrated polyhydroxylated C60

Utilization of polyhydroxylated C₆₀ (fullerenols) in a condensation reaction with diisocyanated oligo(tetramethylene oxide) led to the successful fabrication of elastomeric poly (urethane-ether) networks. These polymer networks exhibit interesting thermal behavior at low temperatures, improved tensile strength and elongation at ambient temperatures, and enhanced thermal mechanical stability at high temperatures, as compared with those of the parent linear polyurethane analogues; or with the conventional oligo (tetramethylene oxide)-derived polyurethane elastomers cross-linked by trihydroxylated reagents (1,I,1-trismethylol propane) or tetrahydroxylated reagents (pentaerythritol). The presence of a limited quantity of water molecules in the condensation reaction of fullerenols with diisocyanated prepolymers modified the physical properties of the resulting elastomeric products with a notable increase in tensile strength, modulus, and Ts over those of elasotmers prepared under anhydrous conditions. These water molecules contributed effectively to the increase of the number of cross-linking centers during the reaction.     

A Facile Approach toward Thermoplastic Triple-Shape Memory Polymers

In this work, a ternary blend of polyolefin elastomer (POE), lauric acid (LA), and poly(ε-caprolactone) (PCL) with triple-shape memory effect (triple-SME) is reported. LA and PCL exhibit distinct thermal transitions and construct two reversible switching networks capable of fixing and releasing different temporary shapes under a mild condition. The ternary blend shows excellent triple-shape memory properties and good toughness. Besides, the permanent shape can be reconfigured by a simple thermal treatment. These particular features make the novel blend a competitive candidate for diverse applications. And the creative combination of crystalline small molecule and semicrystalline polymer expands the freedom for producing triple-shape memory polymers (triple-SMPs).     

New conductive thermoplastic elastomers. Part II. Physical and chemical‐physical characterization

To overcome the problems relevant to the low processbility and scarce mechanical properties of polyaniline, in a previous work we have proposed the synthesis of elastomeric conducting copolymers prepared by grafting polyaniline (EB) or sulfonated polyaniline (SPAN) chains to the backbone of a carboxylated segmented polyurethane (PEUA). In the present work the physical and chemical‐physical properties of the copolymers are investigated. As evidenced by thermal (DSC) and dynamo‐mechanical (DMTA) characterization, the introduction of EB or SPAN in the matrix enhances the hard‐soft phase segregation effect, because of the strong tendency of the conductive polymer chains to aggregate. Moreover, the EB and SPAN chains, grafted to the polyurethane backbone, acting as reinforcing filler, give rise, compared with the mechanical properties of the insulating matrix, to an increase of the Young modulus and a decrease of the tensile set. When the copolymers are HCl doped their electrical conductivity increases many orders of magnitude, reaching values of about 10^?3 Ω^?1 cm^?1. The conductivity, measured along the deformation direction, may be further increased by stretching the copolymer films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1259–1264, 2002