Natural rubber-graft-poly(2-hydroxyethyl acrylate) on cure characteristics and mechanical properties of silica-filled natural rubber composites

The grafting of poly(2-hydroxyethyl acrylate) onto natural rubber (NR-g-PHEA) was used to compatibilize NR composites with silica filler. The NR/silica compounds were prepared with various grafting percentages of NR-g-PHEA (0, 6.5, 10.5, and 14.5%) and fixed amounts of 3 parts per hundred of rubber (phr) NR-g-PHEA and 20 phr silica. The cure characteristics were examined using a moving die rheometer. The physicomechanical properties of NR/silica composites were determined in terms of tensile strength, bound rubber content, and dynamic mechanical analysis. Thermal properties were assessed with thermogravimetric analysis. The results showed that scorch time and cure time tend to decrease with the level of grafting in NR-g-PHEA. The NR-g-PHEA decreased tan δ, whereas bound rubber content in NR/silica compounds increased, which indicates improved silica dispersion in the NR matrix. The mechanical properties improved with level of grafting in NR-g-PHEA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48738.     

Characterization of barium titanate reinforced acrylonitrile butadiene rubber composites for flexible electronic applications: influences of barium titanate content

The aim of this study was to develop high dielectric constant flexible polymers with a highly efficient and cost‐effective approach using acrylonitrile butadiene rubber (NBR) as the polymer matrix and barium titanate (BT) as the high dielectric constant filler. The BT powder was synthesized with a solid‐state reaction and was characterized using a particle size analyzer, XRD, SEM and Fourier transform infrared spectroscopy. NBR/BT composites were fabricated using an internal mixer with various BT loadings up to 160 phr. The influence of BT loading on the cure characteristics and mechanical, dynamic mechanical, thermal, dielectric and morphological properties was determined. The incorporation of BT in the NBR matrix shortened scorch time and increased delta torque. The mechanical properties, thermal stability and dielectric constant were greatly improved and increased with BT loading. The results suggest that the reinforcement effect was achieved due to strong hydrogen bonding or polar–polar interactions between NBR matrix and BT filler. This is further corroborated by the good dispersion of BT filler in the NBR matrix observed with SEM imaging. These findings can be applied to produce high‐performance dielectric elastomers. © 2020 Society of Industrial Chemistry     

Synthesis and thermal properties of natural rubber grafted with poly(2-hydroxyethyl acrylate)

A novel modified natural rubber with grafted poly(2-hydroxyethyl acrylate) (NR-g-PHEA) was synthesized by emulsion polymerization in latex stage. Cumene hydroperoxide and tetraethylene pentamine were used as redox initiators (1:1 M ratio). The influences of reaction temperature, reaction time, initiator concentration and monomer concentration on percent grafting and grafting efficiency were investigated. Transmission electron microscopy was used to observe the NR-g-PHEA particles, which exhibited core-shell morphology. Chemical structure of purified NR-g-PHEA was confirmed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy. The thermal properties were examined by thermogravimetric analysis and by differential scanning calorimetry. The modified NR had improved thermal stability, and the NR-g-PHEA also presented slightly higher glass transition temperature than virgin NR.     

Synthesis and characterization of elastomeric,biobased, nonisocyanate polyurethane from natural rubber

Linear and crosslinked polyhydroxyurethanes (PHUs) based on natural rubber (NR) were synthesized by a polyaddition reaction without a solvent or catalyst to exploit the reactivity of diamines or triamines with dicyclic carbonate groups. Oligo‐isoprenes were obtained from the controlled oxidative degradation of NR and successive modifications of the chain ends. The syntheses of linear PHU were carried out with two approaches. The first one consisted of a reaction between amino telechelic oligo‐isoprenes and aromatic or aliphatic dicyclic carbonates. The second approach proceeded through a reaction between oligo‐isoprenes bearing cyclic carbonate chain ends and difunctional or trifunctional amines. The evolution of these reactions was studied by Fourier transform infrared spectrometry. The influence of the carbonate‐to‐amine molar ratio, the chain length of the oligo‐isoprenes, and the reaction temperatures were investigated. The thermal properties of the PHUs were studied by differential scanning calorimetry and thermogravimetric analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45427.     

Influences of the grafting percentage of natural rubber‐graft‐poly(2‐hydroxyethyl acrylate) on properties of its vulcanizates

The graft copolymerization of 2‐hydroxyethyl acrylate (HEA) monomer onto natural rubber (NR) latex was successful using cumene hydroperoxide and tetraethylene pentamine as redox initiators. The grafting of poly(2‐hydroxyethyl acrylate) (PHEA) on the NR particles was confirmed by Fourier transform infrared spectroscopy, ¹H NMR spectroscopy and TEM. The NR‐g‐PHEA with various grafting percentages (0%, 8.7%, 14.3% and 18.7%) was compounded on a two‐roll mill with a sulfur vulcanization system. The effects of grafting percentage on the cure characteristics, dielectric properties, thermal properties and physical properties of NR‐g‐PHEA vulcanizates were investigated. It was found that increased grafting caused NR‐g‐PHEA vulcanizates to have reduced water contact angle, scorch time and cure time, while the dielectric constant and dissipation factor increased. The NR‐g‐PHEA vulcanizate with 8.7% grafting exhibited the highest delta torque (M_H ? M_L), crosslink density, tensile strength, moduli at 100%, 200% and 300% strains, and hardness, with insignificant loss of elongation at break in comparison to the other cases. © 2018 Society of Chemical Industry     

Effect of the diisocyanate structure and the molecular weight of diols on bio‐based polyurethanes

Bio‐based polyurethanes (PU) containing poly(ε‐caprolactone) diol (PCL) and hydroxyl telechelic natural rubber (HTNR) were synthesized. The effect of the diisocyanate structure and the molecular weights of diols on the mechanical properties of PU were investigated. Three different molecular structures of diisocyanate were employed: an aliphatic diisocyanate (hexamethylene diisocyanate, HDI), an aromatic diisocyanate (toluene‐2,4‐diisocyanate, TDI) and a cycloalkane diisocyanate (isophorone diisocyanate, IPDI). Two molecular weights of each diol were selected. When HDI was employed, a crystalline PU was generated while asymmetrical structures of TDI and IPDI provided an amorphous PU. The presence of crystalline domains was responsible of a change in tensile behavior and physical properties. PU containing TDI and IPDI showed a rubber‐like behavior: low Young's modulus and high elongation at break. The crystalline domains in PU containing HDI acted as physical crosslinks, enhancing the Young's modulus and reducing the elongation at break, and they are responsible of the plastic yielding. The crystallinity increased the tear strength, the hardness and the thermal stability of PU. There was no significant difference between the TDI and IPDI on the mechanical properties and the physical characteristics. Higher molecular weight of PCL diol changed tensile behavior from the rubber‐like materials to the plastic yielding. Thermal and dynamic mechanical properties were determined by using DSC, TGA and DMTA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Evaluation of cure characteristic,physico-mechanical,and dielectric properties of calcium copper titanate filled acrylonitrile-butadiene rubber composites: Effect of calcium copper titanate loading

Calcium copper titanate (CCTO) has been synthesized by high temperature solid-state reaction from calcium carbonate, copper (II) oxide, and titanium dioxide as the starting materials. The formation and morphology of CCTO were confirmed by X-ray diffraction, Fourier-transformed infrared spectrophotometry, scanning electron microscopy (SEM), and particle size analysis. In order to develop flexible dielectric materials, acrylonitrile-butadiene rubber (NBR)-based composites were prepared with CCTO content varied from 0 to 120 phr (parts per hundred rubber). The cure characteristics of composites were assessed. High-dielectric constant CCTO particles were blended into NBR to make composites with improved dielectric constant. Results showed that the NBR/CCTO composites had a high dielectric constant (10–20) with low dielectric loss (<0.4) and low conductivity (<10⁻³ μS/cm) at frequencies up to 10⁶ Hz. However, the higher CCTO loadings had agglomeration in the NBR matrix, and thus tensile strength and elongation at break sharply deteriorated due to poor rubber-filler interactions. The results showed lower storage modulus E′ and a reduction in T_g with the incorporation of CCTO in NBR matrix. Moreover, improved thermal stability of the NBR/CCTO composites was achieved. SEM was used to observe the dispersion of CCTO particles in NBR matrix.     

Elaboration and properties of renewable polyurethanes based on natural rubber and biodegradable poly(butylene succinate) soft segments

Natural rubber (NR) is a renewable bio‐based polymer, while poly(butylene succinate) (PBS) belongs to the family of biodegradable renewable polymers. In this article, novel polyurethanes (PUs) were prepared using hydroxyl telechelic natural rubber (HTNR) and hydroxyl telechelic poly(butylene succinate) (HTPBS) as soft segments, and using toluene‐2,4‐diisocyanate (TDI) and 1,4‐butanediol (BDO) as hard segment. HTPBS oligomers of = 2000 and 3500 g mol^?1 were synthesized by bulk polycondensation of succinic acid (SA) with BDO. The polyurethane materials were obtained by casting process after solvent evaporation. The influence of the hard segment content and the molecular weight of HTPBS on the materials’ thermo‐mechanical properties were investigated by means of tensile testing, DSC, TGA, and DMTA. The obtained polyurethanes were amorphous with phase separations between hard and soft segments as well as between HTNR and HTPBS segments, and they exhibited good physical properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42943.     

Optimizing mechanical and morphological properties of biodegradable thermoplastic elastomer based on epoxidized natural rubber and poly(butylene succinate) blends

Biodegradable thermoplastic elastomer (BTPE) blends of epoxidized natural rubber (ENR) and poly(butylene succinate) (PBS) were prepared by the melt mixing process. Influences of the processing parameters mixing temperature, rotor speed, and mixing time on mechanical and morphological properties of BTPE were investigated. Taguchi method was applied to improve the mechanical and morphological properties by optimizing the processing parameters. That is, the experimental design adopted the L9 Taguchi orthogonal array with three manipulated factors (i.e., mixing temperature, rotor speed, and mixing time). Analysis of mean and analysis of variance were also exploited and the mixing temperature was found to be the most significant processing parameter regarding mechanical properties. The mixing temperature showed large contributions to Young's modulus, 100% modulus, tensile strength, and elongation at break, namely 45.33, 40.38, 49.31, and 36.04%, respectively. Furthermore, the optimum conditions found for mixing temperature, rotor speed, and mixing time were 140 °C, 100 rpm and 10 min, respectively. The result was confirmed by atomic force microscopy and scanning electron microscopy micrographs showing fine‐grained co‐continuous phase morphology of the ENR/PBS blends. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46541.