Urethane‐forming reaction kinetics and catalysis of model palm olein polyols: Quantified impact of primary and secondary hydroxyls

Model palm olein natural oil polyols (NOPs) with varying ratios of primary to secondary hydroxyls were synthesized, characterized, and evaluated in reaction kinetics study with isocyanate in formation of polyurethanes. Reaction rate constants and activation energies associated with primary and secondary hydroxyls of NOPs were quantified. The kinetic study in toluene shows that the NOP containing primary hydroxyls have three times higher reaction rate constants in noncatalyzed reaction with 4,4′‐diphenylmethane diisocyanate (4,4′‐MDI) compared to the model NOP containing only secondary hydroxyls, which is associated with higher activation energy of secondary hydroxyls. However, the difference in reaction rate constants of primary and secondary hydroxyls in NOPs diminished in the reactions catalyzed with dibutyltin dilaurate. Bulk polymerization reaction confirms the kinetics results in toluene, showing that the model NOP containing primary hydroxyls reached gel time at a faster rate. Evaluation of elastomers from bulk polymerization shows low degree of phase separation of hard and soft segments for elastomers based on the model NOPs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42955.     

Thermoplastic rubber/PP elastomers toward extremely low thermal expansion

Fine regulation of the microstructure of rubber/polypropylene (PP) alloys could remarkably reduce the coefficient of linear thermal expansion (CLTE) while retaining the mechanical properties similar to those of thermoplastic elastomers. Rubber/PP elastomers with different morphologies were successfully prepared by controlling the appropriate rubber type, viscosity ratio, and processing method. The CLTE of the polymer alloy parallel to the microlayer directions was considerably reduced when the rubber domains were deformed into microlayers and co‐continuous with plastic domains. The thickness of the PP layers played a crucial role on CLTE reduction. The CLTE considerably decreased with reduced thickness of the PP layer. The sample with a co‐continuous microlayer structure exhibited good flexibility, high elongation, low hardness, and permanent deformation. Thus, low‐thermal‐expansion elastomer materials may have wide applications. Stress relaxation and strain recovery of the ethylene–propylene–diene terpolymer/PP (70/30 wt %) blend were investigated to further clarify the influence of co‐continuous microlayer structure on mechanical properties. Anisotropic mechanical properties were consistent with the morphology. Results of the stress relaxation behavior test would provide further support to the mechanism of the low thermal expansion of blends with co‐continuous microlayer structure. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43902.     

Polyether‐based main‐chain‐type polytriazole elastomer with benzoxazine via a 1,3‐dipolar cycloaddition reaction

A novel functional polyether‐based elastomer with a benzoxazine structure in its main chain was successfully synthesized via a 1,3‐dipolar cycloaddition reaction. Benefitting from a facile one‐pot synthesis strategy, the elastomer was prepared at low temperature (80°C) and was characterized clearly afterward. The azide‐terminated polyether and acetylene‐terminated benzoxazine were used as the soft and hard segments, respectively, in the polymer chain. Because the triazole rings served as stable linkage between the soft and hard segments, the elastomer possessed good thermal stability (the 5% weight loss temperature could exceed 350°C) compared to traditional elastomers, such as polyurethane. The rigid benzoxazine rings provided the product with good mechanical properties (the tensile strength of the elastomer could exceed 30 MPa). Furthermore, the ring‐opening polymerization of oxazine rings in the structure gifted the elastomer with possibility of thermally induced structural transformation. The thermally induced structural transformation could conveniently realize the conversion of the elastomer to a thermosetting resin. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42820.     

Biobased hyperbranched shape‐memory polyurethanes: Effect of different vegetable oils

Hyperbranched polyurethanes were synthesized from poly(ε‐caprolactone) diol as a macroglycol, butanediol as a chain extender, a monoglyceride of a vegetable oil (Mesua ferrea, castor, and sunflower oils separately) as a biobased chain extender, triethanolamine as a multifunctional moiety, and toluene diisocyanate by a prepolymerization technique with the A₂ + B₃ approach. The structure of the synthesized hyperbranched polyurethanes was characterized by ¹H‐NMR and X‐ray diffraction studies. M. ferrea L. seed‐oil‐based polyurethane showed the highest thermal stability, whereas the castor‐oil‐based one showed the lowest. However, the castor‐oil‐based polyurethane exhibited the highest tensile strength compared to the other vegetable‐oil‐based polyurethanes. All of the vegetable‐oil‐based polyurethanes showed good shape fixity, although the castor‐oil‐based polyurethane showed the highest shape recovery. Thus, the characteristics of the vegetable oil had a prominent role in the control of the ultimate properties, including the shape‐memory behaviors, of the hyperbranched polyurethanes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39579.     

Effect of the compatibilizer,on the engineering properties of TPV based on Hypalon® and PP prepared by dynamic vulcanization

Elastomeric Chlorosulfonated polyethylene (Hypalon^®) and thermoplastic Polypropylene (PP) based thermoplastic vulcanizates (TPVs) were prepared in presence of different doses of compatibilizer, maleic anhydride grafted PP (PP‐g‐MA) by employing dynamic vulcanization technique. The effect of incorporation in different proportions of compatibilizer on mechanical, spectral, morphological, thermal, and rheological properties of such TPVs was studied and the same were compared to that of virgin PP and amongst themselves. The mechanical analysis of the prepared TPVs exhibited significant improvements in stress at 25% modulus, ultimate tensile strength (UTS), and hardness values. FTIR studies revealed that a chemical interaction had taken place between Hypalon^® and functionalized compatibilizer during the process of dynamic vulcanization which led to an enhancement of interfacial adhesion between them. The two‐phase morphologies were clearly observed by scanning electron microscopic studies. The T_g values of Hypalon^® was modified in the TPVs as exhibited by differential scanning calorimetric studies. TGA studies indicated the increase in thermal stability of all TPVs with respect to the elastomeric Hypalon^®. Rheological properties showed that the compatibilizer reduces the melt viscosity of TPVs and thus facilitates the processibility of such TPVs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40312.     

Carbon nanotubes‐filled thermoplastic polyurethane–urea and carboxylated acrylonitrile butadiene rubber blend nanocomposites

This article reports the preparation and characterization of multiwalled carbon nanotubes (MWCNTs)‐filled thermoplastic polyurethane–urea (TPUU) and carboxylated acrylonitrile butadiene rubber (XNBR) blend nanocomposites. The dispersion of the MWCNTs was carried out using a laboratory two roll mill. Three different loadings, that is, 1, 3, and 5 wt % of the MWCNTs were used. The electron microscopy image analysis proves that the MWCNTs are evenly dispersed along the shear flow direction. Through incorporation of the nanotubes in the blend, the tensile modulus was increased from 9.90 ± 0.5 to 45.30 ± 0.3 MPa, and the tensile strength at break was increased from 25.4 ± 2.5 to 33.0 ± 1.5 MPa. The wide angle X‐ray scattering result showed that the TPUU:XNBR blends were arranged in layered structures. These structures are formed through chemical reactions of ? NH group from urethane and urea with the carboxylic group on XNBR. Furthermore, even at a very low loading, the high degree of nanotubes dispersion results in a significant increase in the electrical percolation threshold. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40341.     

Cotton fibers reinforcement of HNBR: Control of fiber alignment and its influence on properties of HNBR vulcanizates

This article focuses on the reinforcement of hydrogenated acrylonitrile butadiene rubber (HNBR) by cotton fiber as natural reinforcing filler. The effect of fiber alignment on the properties of HNBR compounds and vulcanizates is investigated. Properties of interest include rheological behavior, cure, tensile, abrasion, and dynamic mechanical properties which are correlated to the magnitudes of state‐of‐mix, bound rubber content, crosslink density and fiber alignment. Results obtained reveal that mechanical properties of rubber composites are improved dramatically by the addition of cotton fiber due to the enhanced hydrodynamic effect in association with crosslink density. Furthermore, the degree of fiber alignment is found to depend strongly on shear strain. The results demonstrate the importance of fiber alignment controlled efficiently by shear strain. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41090.     

Dielectric strength of Al2O3/silicone composites after high‐temperature aging

Silicones are widely used for electrical insulation owing to their high dielectric strength and thermal stability. However, recent studies revealed insufficient stability of silicone for high‐temperature applications. To study the effect of Al₂O₃ fiber on silicone stability, we measured the dielectric strength of unfilled silicone and Al₂O₃/silicone composites as a function of aging time at 250°C in air and analyzed data by Weibull probability distribution to determine characteristic dielectric strength (E₀) and shape parameter (β). Prior to aging, unfilled silicone and composites had similar behavior, with E₀ at about 20 kV/mm and β > 15. During aging, unfilled silicone developed both micro‐ and macrocracks, with β dropped below five in 240 h and E₀ decreased significantly. Composites developed microcracks, with β dropped below 5 in longer time and E₀ remained almost constant. Addition of Al₂O₃ slowed down crack growth in silicone matrix, resulting in longer lasting high‐temperature dielectric materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41170.     

Meticulous analysis and consequences of microstructure changes on melt rheology and dynamic viscoelasticity of thermoplastic vulcanizates upon reprocessing

Thermoplastic vulcanizates (TPVs), which are a special class of elastomer alloy, prepared by dynamic vulcanization possess unique morphology of finely dispersed micron‐size cross‐linked elastomeric particles in a continuous thermoplastic matrix. The present study investigates the microstructure formation of elastomeric phase and its associated morphological changes during reprocessing of TPVs based on poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] triblock co‐polymer (S‐EB‐S) and solution polymerized styrene butadiene elastomer (S‐SBR) by scanning electron microscopy and atomic force microscopy. Semi‐efficient and efficient sulfur‐based curing systems have been adopted to cure the elastomeric phase and a comparative study has been made to demonstrate and explain the effect of reprocessing on the melt rheology and dynamic viscoelasticity of the TPVs. The present work also provides a better insight and guidance to control the microstructure of the cross‐linked elastomeric phase to prepare selectively co‐continuous or dispersed phase morphology. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41182.     

Enhancing the air impermeability of a biobased poly(di‐isoamyl itaconate‐co‐isoprene) elastomer via the cocoagulation of latex and natural layered silicates

The gas‐barrier properties of elastomer are of particular importance, especially for airtight applications. Poly(di‐isoamyl itaconate‐co‐isoprene) (PDII) is a newly invented and respectable biobased elastomer, but the barrier properties of PDII and its composites with carbon black and silica are not satisfying at all. Because there are abundant ester groups in PDII macromolecules and these groups can contribute to the homogeneous dispersion of layer silicates, we applied layered silicates, including montmorillonite (MMT) and rectorite (REC), into the PDII matrix to improve the air impermeability. MMT/PDII and REC/PDII composites were prepared by a cocoagulation method, and the air impermeability of the PDII elastomer was highly improved. The smallest gas permeability index reached 1.7 × 10^?17 m² Pa^?1 s^?1 at an REC content of 80 phr; this implied a reduction of 85.5%. A comparison of the two types of silicate/PDII composites showed that the MMT/PDII composites had better properties at low filler contents, whereas the REC/PDII composites had better mechanical and gas‐barrier properties at high filler contents. Other structures and properties of the composites were investigated by X‐ray diffraction, transmission electron microscopy, and dynamic mechanical rheology. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40682.