ORIGIN OF ENERGETIC ELASTICITY AND ENTROPIC ELASTICITY OF NATURAL RUBBER WITH NANODIAMOND NANOMATRIX STRUCTURE

ABSTRACT The origin of energetic elasticity in conjunction with the entropic elasticity for natural rubber with a nanodiamond nanomatrix structure was investigated in terms of bound rubber formed between nanodiamonds, based on the interaction between natural rubber and nanodiamonds inside the nanomatrix. The natural rubber with a nanodiamond nanomatrix structure was prepared by reacting nanodiamonds with deproteinized natural rubber in the presence of tert-butylhydroperoxide/tetraethylenepentamine at 30 °C in the latex stage followed by drying. Morphology of the products was observed by two-dimensional and three-dimensional transmission electron microscopies. The effect of bound rubber on the mechanical properties of the products was investigated by measurements of the dynamic mechanical properties and differential scanning calorimetry. The contribution of bound rubber was estimated by combining the Takayanagi equation and modified Guth–Gold equation. A significant increase in complex modulus was attributed to the effect of the bound rubber.

DETERMINATION OF A SUITABLE CONDITION OF GRAFT COPOLYMERIZATION OF VINYLTRIETHOXYSILANE ONTO NR TO FORM NANOMATRIX STRUCTURE

ABSTRACT Graft copolymerization of vinyltriethoxysilane (VTES) onto NR particles in the latex stage is a unique reaction, since it occurs together with hydrolysis and condensation of the triethoxysilane group of VTES to form a colloidal silica linking to the rubber particles. These reactions may contribute to the formation of a silica nanomatrix structure that consists of a dispersoid of rubber particles as the major component and a silica matrix as the minor component. Here, the graft copolymerization of VTES followed by hydrolysis and condensation is investigated to determine a suitable condition to prepare NR with a silica nanomatrix structure. The mechanical properties of the resulting graft copolymer are discussed in relation to the morphology, silica content, and gel content of the rubber. Based on morphological observations, NR particles with an average diameter of approximately 1 μm are well dispersed in a nanomatrix consisting of silica nanoparticles. The thickness of the silica nanomatrix increases as the monomer concentration increases, and a long incubation time generates large silica nanoparticles. The tensile strength and viscoelastic properties are significantly improved by forming the silica nanomatrix structure, with its continuous structure that prevents the NR particles from merging.

NANOMATRIX STRUCTURE FORMED BY GRAFT COPOLYMERIZATION OF STYRENE ONTO FRESH NATURAL RUBBER

ABSTRACT Fresh NR was adopted to prepare rubber with a nanomatrix structure. The nanomatrix structure was formed by graft-copolymerization of styrene onto deproteinized fresh NR (fresh DPNR) in the latex stage using tert-butyl hydroperoxide/tetraethylenepentamine as an initiator. Graft-copolymer consisting of fresh DPNR and polystyrene (fresh DPNR-graft-PS) was characterized by 1H-NMR spectroscopy and transmission electron microscopy. Under a suitable condition of the graft-copolymerization, conversion and grafting efficiency of styrene was 98 and 80 mol%, respectively. Morphology of fresh DPNR-graft-PS was observed by transmission electron microscopy. The rubber particles of about 1 μm in diameter were found to be dispersed in polystyrene matrix of 10–30 nm in thickness. Tensile properties of fresh DPNR were dramatically improved by forming the nanomatrix structure, compared with DPNR.