Preparation and properties of novel polyurethane insulating coatings based on glycerin‐terminated urethane prepolymers and blocked isocyanate

Novel polyurethane insulating coatings were prepared from the reaction of glycerin‐terminated polyurethane prepolymers (GPUPs) and a blocked isocyanate curing agent (BIC). The GPUPs were prepared from the reaction of one equivalent of polycaprolactone polyol (CAPA 210) with an excess amount of 4,4′‐methylene bis(phenyl isocyanate) (MDI) and subsequent reaction of the NCO‐terminated polyurethane with glycerin. The BIC was prepared from the reaction of trimethylol propane (TMP), toluene diisocyanate (TDI) and N‐methylaniline (NMA). The polyols and curing agent were characterized by conventional methods while the curing condition was optimized via gel content measurements. The curing kinetics of the polyurethane coating were investigated and the kinetic parameters derived. The crosslink densities of the samples were determined via the equilibrium swelling method, using the Flory–Rehner equation. The relationships between the crosslink density and the electrical, physical, mechanical and dynamic mechanical properties of the coatings were also studied. Copyright © 2005 Society of Chemical Industry     

Methacryloxyethyl phosphate‐grafted expanded polytetrafluoroethylene membranes for biomedical applications

Expanded polytetrafluoroethylene (ePTFE) membranes were modified by graft copolymerization with methacryloxyethyl phosphate (MOEP) in methanol and 2‐butanone (methyl ethyl ketone (MEK)) at ambient temperature using gamma irradiation. The effect of dose rate (0.46 and 4.6 kGy h^?1), monomer concentration (1–40 %) and solvent were studied and the modified membranes were characterized by weight increase, X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). XPS was used to determine the % degree of surface coverage using the C? F (ePTFE membrane) and the C? C (MOEP graft copolymer) peaks. Grafting yield, as well as surface coverage, were found to increase with increasing monomer concentration and were significantly higher for samples grafted in MEK than in methanol solution. SEM images showed distinctly different surface morphologies for the membranes grafted in methanol (smooth) and MEK (globular), hence indicating phase separation of the homopolymer in MEK. We propose that in our system, the non‐solvent properties of MEK for the homopolymer play a more important role than solvent chain transfer reactions in determining grafting outcomes. Copyright © 2005 Society of Chemical Industry     

In situ polymerization and characterization of polyester‐based polyurethane/nano‐silica composites

Polyester‐based polyurethane/nano‐silica composites were obtained via in situ polymerization and investigated by Fourier‐transform infrared spectroscopy (FTIR), or FTIR coupled with attenuated total reflectance (FTIR‐ATR), Transmission electron microscopy (TEM), atomic force microscopy (AFM), an Instron testing machine, dynamic mechanical analysis (DMA) and ultraviolet‐visible spectrophotometry (UV‐vis). FTIR analysis showed that in situ polymerization provoked some chemical reactions between polyester molecules and nano‐silica particles. FTIR‐ATR, TEM and AFM analyses showed that both surface and interface contained nano‐silica particles. Instron testing and DMA data showed that introducing nano‐silica particles into polyurethane enhanced the hardness, glass temperature and adhesion strength of polyurethane to the substrate, but also increased the resin viscosity. UV‐vis spectrophotometry showed that nano‐silica obtained by the fumed method did not shield UV radiation in polyurethane films. Copyright © 2003 Society of Chemical Industry     

Phase separation studies in RIM polyurethanes catalyst and hard segment crystallinity effects

Polyurethanes were prepared from pure 4,4′-diphenylmethane diisocyanate (MDI), 1,4-butane diol (BDO) or 1,2-ethane diol (EDO) and α,ω-hydroxyl poly(propylene oxide) (PPO) by reaction injection moulding (RIM). Hard segment (MDI + BDO or EDO) level was 45–50 wt%. The PPO had about 20% ethylene oxide copolymerized in at the chain ends to provide 80% primary OH end groups. M_n was varied from 2000 to 4000. Dibutyl tin dilaurate catalyst and mould temperature were varied. Dynamic mechanical, wide-angle X-ray, differential scanning calorimeter, molecular weight and tensile elongation measurements were made on the RIM polyurethanes. At low reaction rates (low catalyst or temperature) highly crystalline, well phase separated but low molecular weight polymers were produced. At high catalyst or temperature levels more poorly phase separated but high molecular weight, tough polymers resulted. Higher M_n PPO gave better phase separation and EDO gave higher melting temperatures. Preventing hard segment crystallinity by substituting asymmetric MDI or glycols resulted in phase compatibility.     

Hydrolytic stability and protective properties of polyurethane oligomers based on polyester/ether/polyols

The present study deals with effect of the type and chemical character of incorporated polyester/polyether blocks on the hydrolytic stability of crosslinked polyurethane oligomers. Diffusion parameters of the investigated polyurethane oligomers, giving information concerning chemical changes taking place in neutral, basic and acidic aqueous environments, have also been determined.     

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     

Novel blood-compatible waterborne polyurethane using chitosan as an extender

A series of novel block polymers of polyurethane (PU) and chitosan have been prepared in two steps. The first step is the preparation of PU prepolymer, obtained from polytetramethylene oxide glycol (PTMO, M_n = 1000), isophrone diisocyanate (IPDI), and 2,2′-dimethylol propionic acid (DMPA), followed by ionizing PU prepolymer with triethylamine (TEA). The second step involves PU chain-extended by water-soluble chitosan of low molecular weight (M_n = 5000) by self-emulsion polymerization method. The sizes of the latex particles, morphology, and copolymer architecture have been characterized by dynamic light scattering (DLS), general tensile test, infrared spectroscopy (IR), surface contact angle measurement, and transmission electron microscopy (TEM). Furthermore, it shows that the addition of chitosan remarkably increases anticoagulative property of PU elastomers confirmed by the recalcification time. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Pultruded fibre reinforced polyurethane composites II. Effect of processing parameters on mechanical and thermal properties

This paper presents a novel process for the fabrication of pultruded polyurethane (PU) composites. The effects of the processing parameters on the mechanical properties (flexural strength and flexural modulus, etc.) and thermal properties (HDT) of the fibre reinforced PU composites by pultrusion have been studied. The processing parameters investigated include pulling rate (in-line speed), die temperature, filler type and content, and post-cure time and temperature. Results show that the composites possessed various optimum pulling rates at different die temperatures. On the basis of the DSC diagram, the swelling ratio, the mechanical properties and the thermal properties of composites, the optimum die temperature can be determined. It is found that the mechanical and thermal properties increase with filler content for various types of filler. The mechanical and thermal properties increase at a suitable post-cure temperature and time. Furthermore, the properties which decreased due to the degradation of composite materials for a long post-cure time will be discussed.     

Study on phase behavior–impact strength relationship of unsaturated polyester/polyurethane hybrid polymer network

The phase behavior of a hybrid polymer network (HPN) composed of poly[(propylene glycol maleate)-co-(propylene glycol phthalate)] crosslinked with styrene and polyester–urethane crosslinked with methylene-bis-ortho-chloroaniline was examined. The correlation between phase separation and impact strength of the HPNs is discussed. The composition of HPNs has an effect on their properties.