Kannika Sahakaro

COOPERATIVE EFFECTS OF EPOXIDE FUNCTIONAL GROUPS ON NATURAL RUBBER AND SILANE COUPLING AGENTS ON REINFORCING EFFICIENCY OF SILICA

Polar functionality attached onto natural rubber has a significant impact on the reinforcing efficiency of silica. Parallel studies involving various levels of epoxidation on natural rubber (ENR) in the absence of bis-(triethoxysilylpropyl) tetrasulfide (TESPT) coupling agent, as well as a combination of ENRs with different loadings of TESPT, provide a better understanding of the various factors that influence the properties of silica-filled ENR compounds. Based on the overall properties, the best possible combination to optimize processability, to reduce filler–filler interaction, and improve vulcanization rate as well as vulcanizate properties, is to use ENR with an epoxide content in the range of 20–30 mol%, together with a small portion of TESPT, that is, 2–4 wt% relative to the silica content. This leads to a reduction of approximately 60–80% of TESPT when compared with the conventional NR compounds, where the optimal loading of TESPT was 9.0 wt% relative to the silica content.

OPTIMIZATION OF RUBBER FORMULATION FOR SILICA-REINFORCED NATURAL RUBBER COMPOUNDS

The rubber formulation plays a significant role in the properties of NR compounds filled with silica. In this work, the influences of various silicas, silane coupling agents, and diphenylguanidine (DPG) on the properties of compounds and vulcanizates—that is, cure characteristics, Mooney viscosity, flocculation kinetics, bound rubber content, Payne effect, tan δ at 60°C, tensile properties, and tear properties—are investigated. The results demonstrate that compound viscosity and curing behavior, as well as vulcanizate properties of the silica-filled NR, are much improved by incorporating silane coupling agents. Bis-triethoxysilylpropyltetrasulfide clearly gives better overall properties than the disulfide-based silane bis-triethoxysilylpropyldisulfide, except for scorch safety. DPG acts as a synergist to sulfenamide primary accelerators, as well as activator for the silanization reaction. Highly dispersible (HD) silicas can significantly enhance the degree of dispersion and so lead to higher filler–rubber interaction. As a consequence, the HD silicas provide better dynamic and mechanical properties for filled NR vulcanizates compared with conventional counterparts. The optimal quantities of both silane coupling agent and DPG required in the formulation are correlated to the cetyl trimethylammonium bromide specific surface area of the silicas. Furthermore, the results reveal that the silica structure as characterized by the dibutylphthalate adsorption also strongly influences the reinforcing efficiency

Influence of Reaction Volume on the Properties of Natural Rubber-g-Methyl Methacrylate

Graft copolymer of natural rubber and poly(methyl methacrylate) was prepared using CHP/TEPA redox initiators at 50°C and a reaction time of 3 h. Various reaction volumes (i.e., 0.5, 100, and 200 L) were used to prepare the graft copolymer which was then characterized by Fourier transform infrared spectrophotometer and proton nuclear magnetic resonance spectrophotometer (1H-NMR) techniques. It was found that conversion of monomer to polymer and grafting efficiency slightly decreased with increasing reaction volumes. Quantity of grafted poly(methyl methacrylate) was calculated based on the integrated peak areas of the 1H-NMR spectra and quantitative analysis by extraction method. It was found that both techniques gave similar level of the grafted poly(methyl methacrylate) onto the natural rubber backbone. Furthermore, Mooney viscosities, glass transition temperature (Tg) and degradation temperature (Td) of the natural rubber and poly(methyl methacrylate) were slightly decreased with increasing the reaction volumes.

EPOXIDIZED NATURAL OILS AS THE ALTERNATIVE SAFE PROCESS OILS IN RUBBER COMPOUNDS

Abstract Due to the toxicity of aromatic oils derived from polycyclic aromatic hydrocarbons (PAHs), safe process oils are required for a replacement in rubber compounds. The properties of tire trea...

Compatibilization of silica-filled natural rubber compounds by combined effects of functionalized low molecular weight rubber and silane

Epoxidized low molecular weight natural rubber (ELMWNR) with 28 mol% epoxide groups and weight average molecular weight of 49,000 g mol−1 was prepared by oxidative degradation of epoxidized natural rubber (NR) using periodic acid in the latex state. ELMWNR-28 was used at 10 parts per hundred parts of rubber (phr) loading in combination with bis-(triethoxysilylpropyl) tetrasulfide (TESPT) as the silane coupling agent in the range of 0–4.5 phr in silica-reinforced NR compounds. The use of TESPT in combination with ELMWNR-28 gives lower mixing torques and compound viscosities compared with the use of TESPT alone and the system without any compatibilizer. The bound rubber content, modulus, and tensile strength of the compounds with only TESPT strongly depend on the TESPT loading. The use of ELMWNR-28 as a compatibilizer clearly improves such properties compared with the non-compatibilized systems. By adding TESPT into the compound with ELMWNR-28, the properties further improve with increasing TESPT loading. The combined effect of ELMWNR-28 at 10 phr with a small amount of TESPT at 1.5 phr results in compounds with superior processability (i.e. low Mooney viscosity and Payne effect), and only slightly lower modulus and reinforcement index (M300/M100) compared with the use of the optimum content of TESPT. This compatibilizer/TESPT combination has the environmental benefits that the ELMWNR is a naturally based product, and that the reduced amount of TESPT silane coupling agent emits a greatly reduced amount of ethanol during processing.

Surface Modification of TiO2 Nanoparticles by Grafting with Silane Coupling Agent

Titanium dioxide (TiO2) possesses excellent photocatalytic activity and provides UV protection for polymeric materials. The nanosized TiO2 particles with larger surface area to volume ratio and an increased surface reactivity shall impart better photocatalysis and UV protection efficiency to the rubber compounds, compared to the use of conventional micron-sized particles. Direct incorporation of TiO2 nanoparticles (n-TiO2) into non-polar rubbers faces incompatibility problem between the two phases. One of the solutions to overcome this problem is to treat the nanoparticle surface by using silane coupling agent such as bis-(3-triethoxysilylpropyl) tetrasulfide (TESPT). This work prepared n-TiO2 from commercial micron sized-TiO2 by ultrasonication technique. Particle size of TiO2 was measured by laser light scattering particle size analyzer. The morphology of TiO2 nanoparticles was characterized by field emission scanning electron microscope (FESEM). The grafting reaction of silane on TiO2 nanoparticles surface was studied at varying reaction temperatures and times. The purified grafted materials were characterized by energy dispersive X-ray analysis (EDX), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). The characterization data confirm a presence of grafted silane on the TiO2 nanoparticles surface. The result shows that ultrasonication technique can effectively decrease particle size and the grafting reaction of silane coupling agent onto TiO2 nanoparticles can be successfully carried out at 140°C for 8 h.

Property enhancement of silica-filled natural rubber compatibilized with epoxidized low molecular weight rubber by extra sulfur

The properties of both compounds and vulcanizates of silica-filled natural rubber (NR) compatibilized with epoxidized low molecular weight natural rubbers (ELMWNRs) consisting of 12 and 28 mol% epoxide are investigated. The ELMWNRs with a molecular weight range of 50,000 to 60,000 g/mol are produced by depolymerization of epoxidized natural rubber (ENR) latex using periodic acid, and then used as compatibilizer in a range of 0 to 15 phr in virgin NR. The compounds with LMWNR without epoxide groups, and with bis-(triethoxysilylpropyl) tetrasulfide (TESPT) coupling agent are also prepared for comparison purpose. Incorporation of ELMWNRs lowers Mooney viscosity and Payne effect to the level closed to that of silica/TESPT compound, and clearly enhances the modulus and tensile strength of vulcanizates compared to the compounds with no compatibilizer and LMWNR. The higher epoxide groups content results in the better tensile properties but somewhat less than the compound with TESPT. Addition of extra sulfur into the compounds with LMWNR and ELMWNRs to compensate for the sulfur released from silane molecule in the silica/TESPT system shows small influence on Mooney viscosity, but remarkably enhances 300% modulus, tensile strength and loss tangent at 60°C as a result of the better network formation.

Silica-Reinforced Natural Rubber Compounds Compatibilized through the Use of Epoxide Functional Groups and TESPT Combination

Epoxidized natural rubber (ENR) and bis-(3-triethoxysilylpropyl) tetrasulfide (TESPT) were used to improve the properties of silica-filled NR. The use of ENR containing 51 mol% epoxide groups (ENR-51) as a compatibilizer without TESPT was optimized at 7.5 phr, based on the results of Payne effect and tensile strength. By using 7.5 phr of ENR-51 with varying amounts of TESPT in a range of 2 to 5 wt% relative to the silica, the properties of compounds were compared to those of the ones with optimum TESPT content (i.e. 8.6 wt% relative to the silica) and without. The addition of TESPT to the ENR-51 compatibilized silica-filled NR compound had no effect on Mooney viscosity but lowered the Payne effect to the same level as that of the silica/TESPT compound, and significantly decreased both scorch and optimum cure times. The silica-filled NR with ENR and the small amount of TESPT combination showed a further increase in tensile strength to match that of the optimized silica/TESPT system, while maintained the elongation at break. This work demonstrates that the use of ENR as compatibilizer clearly enhances the properties of silica-filled NR compounds, and that such properties can be further improved by adding TESPT at a half or less amount of TESPT normally needed for silica-filled compounds.

Improving the Mechanical Properties of ENR/NBR Blends via Masterbatches with Initial Accelerator Concentration Gradients

Abstract Epoxidized natural rubber with 30 mol.% of epoxide (ENR-30) was blended with medium nitrile rubber (NBR) at the blend weight ratios of 30/70 and 70/30. Blend compounds were prepared via simple mixing and masterbatch techniques using TBBS as an accelerator. The masterbatches of ENR-30 initially consisted of higher accelerator concentrations compared with those of NBR, in order to compensate an effect of accelerator partition towards NBR phase. The initial accelerator concentration ratios in ENR-30 and NBR masterbatches before blending were at 50/50, 60/40, 70/30 and 80/20, respectively. The blend vulcanizates prepared by masterbatch mixing showed a significant improvement in tensile properties in comparison with those prepared by simple blend, and the initial accelerator concentration ratio in ENR-30/NBR masterbatches at 70/30 gave the highest ultimate tensile properties. The improvement in tensile properties was clearly observed for all the blends vulcanized with conventional, semi-EV and EV sulfur-vulcanization systems. The increase of tensile properties does suggest a better curative distribution, and hence a better crosslink distribution.

Photocatalytic Activity and Properties of Nanotitanium Dioxide-Filled Natural Rubber in the Presence of Coupling Agents

Titanium dioxide (TiO2) is normally added into the rubber compounds as a white pigment and inorganic filler for an improvement of thermal property. TiO2 is also known to have an outstanding photocatalytic activity. This work investigates the properties of natural rubber (NR) compounds filled with 5 phr of nanoTiO2 (n-TiO2). Since the direct incorporation of n-TiO2 into NR encounters incompatibility problem, therefore two types of coupling agent (i.e. bis-(3-triethoxysilylpropyl) tetrasulfide (TESPT) and isopropyl trioleyl titanate (ITT)) are used. The coupling agent loading is varied in a range of 0-20 wt% relative to the n-TiO2. Mooney viscosities and minimum cure torque (ML) of the compounds increase with increasing coupling agent content and the ones with ITT show higher viscosity than the mixes with TESPT. The use of TESPT leads to shorter optimum cure time and higher torque difference compared to the use of ITT. The addition of n-TiO2 results in the improved modulus, reinforcing index and tensile strength compared to the unfilled vulcanizate. The presence of both TESPT and ITT significantly reduces a photodegradation efficiency. The difference in the properties and photocatalytic activity of n-TiO2 filled NR having TESPT and ITT as coupling agent indicates their possible different level of dispersion and interactions at the interphases.