In Situ Formation of Particulate Silica in Natural Rubber Matrix by the Sol-Gel Reaction

The sol-gel reaction of tetraethoxysilane was conducted in natural rubber (NR) matrix to obtain NR/in situ silica mixtures. In other words, in situ filling of silica onto NR was conducted. The mixtures were compounded with curing regents, and their viscosities were evaluated. The in situ silica with a coupling agent afforded the lowest viscosity compared not only with a conventional silica (VN-3) but also with a carbon black (HAF). The curing behaviors were most favorable for in situ silica compound. Physical properties of the vulcanizates were also evaluated, and again in situ silica stock gave the best result.     

Latex‐state NMR spectroscopy for quantitative analysis of epoxidized deproteinized natural rubber

Method of quantitative analysis through latex‐state ¹³C NMR spectroscopy was established for in situ determination of epoxy group content of epoxidized natural rubber in latex stage. The epoxidized natural rubber latex was prepared by epoxidation of deproteinized natural rubber with freshly prepared peracetic acid in latex stage. The resulting epoxidized deproteinized natural rubber (EDPNR) latex was characterized through latex‐state ¹³C NMR spectroscopy. Chemical shift values of signals of latex‐state ¹³C NMR spectrum for EDPNR were similar to those of solution‐state ¹³C NMR spectrum for EDPNR. Resolution of latex‐state ¹³C NMR spectrum was gradually improved as temperature for the nuclear magnetic resonance (NMR) measurement increased to 70°C. Signal‐to‐noise ratio of latex‐state ¹³C NMR measurement was similar to that of solution‐state ¹³C NMR measurement at temperature above 50°C. The epoxy group content determined through latex‐state NMR spectroscopy was proved to be the same as that determined through solution‐state NMR spectroscopy. Copyright © 2017 John Wiley & Sons, Ltd.     

Transport of benzene and methyl‐substituted benzenes through carbon black‐filled epoxidized natural rubber

Sorption and diffusion of benzene and methyl‐substituted benzenes were investigated through epoxidized natural rubber (ENR) reinforced with four types of carbon black: superabrasion furnace (SAF), intermediate superabrasion furnace (ISAF), high‐abrasion furnace (HAF), and semireinforcing furnace (SRF). Kraus equation has been used to investigate the extent of reinforcement for the different types of carbon black used in the experiments. Effect of the type and concentration of the carbon black on solvent uptake and mechanism of diffusion were studied in detail. The rate constant for diffusion of the solvents in epoxidized natural rubber vulcanizate based on different carbon black type, and loading was investigated. Diffusion constant was found to decrease with increase in the degree of reinforcement. The interaction constant values were experimentally determined. The sorption data were used to determine the activation energy for the diffusion process and the enthalpy and entropy of the sorption process. The experimental results were compared with theoretical predictions. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 415–427, 1999     

Preparation and characterization of acidified chitosan immobilized in epoxidized natural rubber

Biocomposites comprising chitosan (CTS) trapped in an epoxidized natural rubber (ENR) was prepared by homogenizing CTS in ENR50 (ENR with about 50% epoxy content) latex in the presence of curing agents and acetic acid. Micrographs of CTS-t-ENR reveal no phased-out entity. Infrared spectra of CTS-t-ENR show only vibrational bands belonging to CTS and ENR, affirming that the former was not bonded but immobilized in the matrix of the latter. CTS loading up to 5 phr resulted in the increase in the tensile strength and elongation at break, modulus of the CTS-t-ENR. Thermal stability of CTS-t-ENR is higher than that of CTS but lower than that of ENR. Increase in CTS loading from 2.5 to 20 phr resulted in the decrease in toluene absorbency but increase in water uptake of CTS-t-ENR.     

Thermoplastic elastomer based on epoxidized natural rubber/thermoplastic polyurethane blends: influence of blending technique

Epoxidized natural rubber (ENR) and thermoplastic polyurethane (TPU) blends were prepared by simple blend and dynamic vulcanization. The main objective was to prepare a low‐hardness TPU material with good damping and elastic and mechanical properties. It was found that the incorporation of ENR into the blend shows a reduction in Young's modulus, hardness (i.e. <70 Shore A), damping properties (i.e. tan δ < 0.3), and tension set (i.e. <20%) compared with the pure TPU. This indicates the formation of softer TPU materials with superior damping and elastomeric properties. However, incorporation of ENR sacrificed mechanical properties in terms of tensile strength and elongation at break, but these still remain in the range of applicability for industrial uses. It was also found that dynamic vulcanization caused enhancement of mechanical properties, relaxation, damping, rheological properties, and elasticity of the blends. Temperature scanning stress relaxation measurements revealed an improvement in stress relaxation properties and thermal resistance of the dynamically cured ENR/TPU blend. Copyright © 2011 John Wiley & Sons, Ltd.     

Photocrosslinking of functionalized rubber. II. Photoinitiated cationic polymerization of epoxidized liquid natural rubber

Low molecular weight epoxidized natural rubber has been crosslinked within seconds by UV irradiation in the presence of a triarylsulfonium salt. The photoinitiated cationic ring-opening polymerization was studied quantitatively by infrared spectroscopy and shown to proceed with surprisingly long kinetic chains in such solid medium. The high conversion (60%) needed for complete insolubilization, together with the presence of tetrahydrofuran structures, argue in favor of an intramolecular polymerization process involving neighboring epoxy groups. The photoinitiator concentration has a strong influence on the rate and extent of the reaction, as well as on the depth of cure profile. Because of an efficient dark process, close to 100% conversion was reached upon storage of the irradiated elastomer at ambient, with a concomitant increase of the gel fraction and the polymer hardness. The grafting of pendent acrylate groups onto the polymer chain leads to a three-fold decrease of the initial rate of polymerization of the epoxide. The photocuring of natural rubber bearing both epoxy and acrylate groups generates a dual polymer network which combines the properties of the two moieties. © 1995 John Wiley & Sons, Inc.     

Depolymerization and ionic conductivity of enzymatically deproteinized natural rubber having epoxy group

Preparation of liquid epoxidized natural rubber (ENR) was made by oxidative depolymerization of ENR in latex stage without loss of epoxy group. Epoxidation of fresh natural rubber latex, which was purified by deproteinization with proteolytic enzyme and surfactant, was carried out with freshly prepared peracetic acid. The glass transition temperature (T_g) and gel content of the rubbers increased after the epoxidation, both of which were dependent upon an amount of peracetic acid. The gel content was significantly reduced by oxidative depolymerization of the rubber with (NH₄)₂S₂O₈ in the presence of propanal. The resulting liquid epoxidized rubber (M_n≈10⁴) was found to have well-defined terminal groups, i.e. aldehyde groups and α-β unsaturated carbonyl groups. The novel rubber was applied to transport Li⁺ as an ionic conducting medium, that is, solid polymer electrolyte.     

Effects of epoxidized natural rubber as a compatibilizer in melt compounded natural rubber-organoclay nanocomposites

Nanocomposites containing natural rubber (NR) as matrix, epoxidized natural rubber (ENR) as compatibilizer and organophilic layered clay (organoclay) as filler were produced in an internal mixer and cured using a conventional sulphuric system. The effects of ENR with 25 (ENR 25) and 50 mol% epoxidation (ENR 50), respectively, were compared at 5 and 10 parts per hundred rubber (phr) concentrations. The organoclay content was fixed at 2 phr. Cure characteristics, clay dispersion, (thermo)mechanical properties of the nanocomposites were determined and discussed. Incorporation of ENR and organoclay strongly affected the parameters which could be derived from Monsanto MDR measurements. Faster cure and increased crosslink density were attributed to changes in the activation/crosslinking pathway which was, however, not studied in detail. The organoclay was mostly intercalated according to X-ray diffraction (XRD) and transmission electron microscopic (TEM) results. The best clay dispersion was achieved by adding ENR 50. This was reflected in the stiffness of the nanocomposites derived from both dynamic mechanical thermal analysis (DMTA) and tensile tests. The tensile and tear strengths of the ENR 50 containing nanocomposites were also superior to the ENR 25 compatibilized and uncompatibilized stocks.     

Influence type of natural rubber on properties of green biodegradable thermoplastic natural rubber based on poly(butylene succinate)

Green biodegradable thermoplastic natural rubber (GB‐TPNR) based on simple blend of natural rubber (NR) and poly(butylene succinate) (PBS) was prepared using three NR alternatives: unmodified NR and epoxidized NR with 25‐ or 50‐mol% epoxide (ie, ENR‐25 or ENR‐50). It was found that ENR‐50/PBS blend showed the best compatibility, which resulted in superior mechanical and thermal properties with the highest crystallinity of the PBS phase, on comparing with the ENR‐25/PBS and NR/PBS blends. This might be attributed to stronger chemical interactions between the epoxide groups in ENR‐50 and the polar functional groups in PBS, which were confirmed by Fourier transform infrared (FTIR). Furthermore, scanning electron microscopy (SEM), atomic force microscopy (AFM), and polarizing optical microscopy (POM) micrographs of ENR‐50/PBS blend revealed phase separation with finer‐grained cocontinuous structure than in ENR‐25/PBS and NR/PBS simple blends. Furthermore, the chemical interactions in ENR‐50/PBS blend enhanced the resistance to accelerated weathering.     

Processing characteristics and thermal stabilities of gel and sol of epoxidized natural rubber

The processing performances and aging behaviours of gel and sol separated from epoxidized natural rubber (ENR) using organic solvents were studied by using rubber processing analyzer (RPA), thermogravimetric analysis (TGA) and difference FT-IR method. As the gel with intermolecular ether structure is formed by the ring-opening reactions of a part of epoxy groups during the preparation and storage of ENR, the molar percentage of epoxy groups of gel is lower than that of sol. The gel shows higher elastic moduli to temperature and frequency responses, lower tan δ to frequency and strain response and higher elastic torque to strain response as comparing to those of sol. Therefore, the formation of gel will reduce processing performance of ENR. When the aging behaviours of gel and sol were analyzed by different methods, the aging reactions and their degrees were different because of the differences of aging conditions. Compared to gel, the sol is easy to be crosslinked, leading to a higher Δtan δ from the RPA analysis and it is also easy to be oxidized into small molecules, leading to lower onset temperature and apparent activation energy when being analyzed by TGA. However, the variations of functional groups of gel are more obvious than those of sol when analyzed by difference FT-IR method. As the mechanical properties of ENR will be varied with the variations of molecular structures, the formations of gel during preparation and storage of ENR will reduce the oxidative aging resistance of ENR.     

Natural Phenolic Compounds as Modifiers for Epoxidized Natural Rubber/Silica Hybrids

Silica is a popular filler, but in epoxidized natural rubber, can act as a cross-linking agent. Unfortunately, a high amount of silica is necessary to obtain satisfactory tensile strength. Moreover, a high amount of silica in ENR/silica hybrids is associated with low elongation at break. In our paper, we propose natural phenolic compounds, including quercetin, tannic acid, and gallic acid as natural and safe additional crosslinkers dedicated to ENR/silica hybrids to obtain bio-elastomers with improved mechanical properties. Therefore, toxic crosslinkers, such as peroxides or harmful accelerators can be eliminated. The impact of selected natural phenolic compounds on crosslinking effect, mechanical properties, color, and chemical structure of ENR/silica composite have been analyzed. The obtained results indicated that only 3 phr of selected natural phenolic compounds is able to improve crosslinking effect as well as mechanical properties of ENR/silica hybrids. Moreover, some of the prepared materials tend to regain mechanical properties after reprocessing. Such materials containing only natural and safe ingredients have a chance of becoming novel elastomeric biomaterials dedicated to biomedical applications.     

Compatibilized natural rubber/recycled ethylene-propylene-diene rubber blends by biocompatibilizer

Biocompatibilizer-based refined, bleached, deodorized palm stearin was successfully used as compatibilizer for natural rubber/recycled ethylene–propylene–diene rubber (NR/R-EPDM) blends. It seems effective in improving the state of cure, tensile properties, as well as the swelling resistance and morphology of the blends, indicating an improvement in compatibility between the NR matrix and R-EPDM rendered by biocompatibilizer. This was clearly verified by the dynamic mechanical properties of the blends. The dynamic responses obtained were clearly corresponding to the swelling result. It proves that the cross-link density plays a major role in the changes of storage modulus and degree of entanglement.     

Preparation and characterization of polymer electrolyte membrane from chloroacetate chitosan/chitosan blended with epoxidized natural rubber

Chitosan-based membranes are among the most effective and efficient PEMs for fuel cells, however their low proton conductivity needs to be improved. In this study, chitosan, chloroacetate chitosan (CCS), chitosan blend with epoxidized natural rubber (ENR), and CCS with ENR blend based membranes were prepared by solution casting, crosslinked with NaOH and H₂SO₄, and investigated for physical, chemical, electrical and ionic properties. The functional groups were identified by ATR-FTIR spectroscopy and the peaks matched improved membrane properties. The surface roughness of the membranes was determined by AFM, and it increased with the amount of ENR. The electrical properties measured with an LCR meter showed that the CCS, CS and CS-B had the highest conductance, conductivity, capacitance and dielectric constant, while the CCS10/ENR8, CS10/ENR8 and CS15/ENR3 showed the highest resistance and resistivity. Furthermore, the CCS gave the lowest dissipation factor, which indicates its suitability for use in a PEM. In addition, the contact angle was relatively high for CS-B, CS and CCS.     

Role of epoxidized natural Eucommia ulmoides gum in modifying the interface of styrene‐butadiene rubber/silica composites

Eucommia ulmoides gum (EUG) is a renewable and sustainable polymer, which could be used as rubber or plastic by altering its crosslinking density while the complicated extracting process and nonpolar molecular chains limited its application. In this effort, a novel extraction method was introduced, which could simplify the extraction process of EUG. Then, the extracted EUG‐chloroform (CHCl₃) solution was directly used to prepare epoxidized EUG (EEUG) with an epoxy degree of 40.0% to improve its polarity. The epoxidized natural EUG exhibiting both polar and nonpolar motives had an advantage in working as an interfacial compatibilizer for polymer composites, especially bio‐based composites due to its inherent biocompatibility. Accordingly, the role of EEUG in modifying the interface of styrene‐butadiene rubber (SBR)/silica composites were explored. The results showed that EEUG in SBR/silica composites acted not only as a compatibilizer but also as a constructure generating better mechanical properties than other compatibilizers, such as silane couplings, Si‐69 and KH‐550, and epoxidized natural rubber (ENR). The simplified extracting process and the epoxy modification of EUG would extend its application in rubber materials, medical materials, and biopolymer materials.     

sol-gel 法在有机-无机杂化体系中制备二氧化硅微粒

利用sol-gel法,通过正硅酸乙酯（tetraethyl orthosilicate（TEOS））在聚氧化乙烯／二甲基甲酰胺溶液中水解、缩聚,制备了粒径分布均匀的微米级二氧化硅粒子;利用扫描电子显微镜观测了制备条件对二氧化硅粒子的粒度和形貌的影响;研究了这一方法在制备无机粒子过程中的原理．     

New insights into the cold crystallization of filled natural rubber

This article is devoted to the cold crystallization of filled natural rubber with different types of filler such as carbon black, silica, and grafted silica. A large set of differential scanning calorimetry data is presented with various scanning rates, times, and temperatures of isothermal crystallization to display the factors affecting natural rubber (NR) crystallization. The crystallization kinetic measurements suggest that fillers can create a region with perturbed mobility where the kinetics of nucleation and/or growth are slowed down, the rest of the matrix being unperturbed. And, the final crystallization level indicates the existence of an excluded region for crystallization close to the filler surface. Furthermore, the presence of fillers appears less unfavorable to NR crystallization than chemical crosslinking. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 955–962, 2007     

Sol-Gel Particulate Float Process to Make Vitreous Silica Bodies

Particulate sol-gel technology uses larger particles than that of alkoxide-derived gels and provides larger pore sizes in the gelled object. This allows relatively rapid drying and fabrication of large rods or tubular shapes. However, the formation of more complex or flat shapes, which require extensive surface contact with a mold, is more difficult. The shrinkage during drying, with the significantly greater stress of surface friction due to adhesion, frequently leads to cracking.We have demonstrated a solution to this problem by floating the gel on the surface of a dense liquid. Dry silica panels up to 28 × 40 × 0.7 cm³ were prepared in this way. The use of patterning molds allowed the fabrication of more sophisticated shapes. These bodies were sintered to transparent vitreous silica articles of near net dimensions.     

Titania-Doped Silica Fibers Prepared by Electrospinning and Sol-Gel Process

Titania-doped silica fibers were prepared by electrospinning of the sol of silica containing titania. The electrospun fibers had ribbon type morphology. The fibers had significant quantities of hydroxyl groups of Si—OH and Ti—OH. The fibers did not have crystalline structure. Diameters of the fibers were reduced by solvent evaporation and calcination. The hydroxyl groups on the fibers disappeared by calcination. The hydroxyl groups, M—OH (MSi, Ti) were changed to M—O—M by intermolecular and intramolecular condensation reactions.     

Effects of methyl methacrylate grafting and in situ silica particle formation on the morphology and mechanical properties of natural rubber composite films

The effects of methyl methacrylate (MMA) grafting and in situ formation of silica particles on the morphology and mechanical properties of natural rubber latex (NRL) were investigated. MMA grafting on NRL was carried out using cumyl hydroxy peroxide/tetraethylene pentamine (CHPO/TEPA) as a redox initiator couple. The grafting efficiency of the grafted NR was determined by solvent extractions and the grafted NRL was then mixed with tetraethoxysilane (TEOS), a precursor of silica, coated by adherence to a glass surface to form a film and cured at 80°C. The resultant products were characterized by FT‐IR and transmission electron microscopy. The influence of varying the MMA monomer weight ratio on the surface morphology of the composites was investigated by scanning electron and atomic force microscopy. The PMMA (poly MMA) grafted NRL particles were obtained as a core/shell structure from which the NR particles were the core seed and PMMA was a shell layer. The silane was converted into silica particles by a sol–gel process which was induced during film drying at 80°C. The silica particles were fairly evenly distributed in the ungrafted NR matrix but were agglomerated in the grafted NR matrix. The root‐mean‐square roughness increased with an increasing weight ratio of MMA in the rubber. The in situ silica particles in the grafted NR matrix slightly increased both the modulus and the tear strength of the composite film. Copyright © 2008 John Wiley & Sons, Ltd.