Hydrogenation of natural rubber latex in the presence of OsHCl(CO)(O2)(PCy3)2

Hydrogenation is an important method of chemical modification, which improves the physical, chemical, and thermal properties of diene elastomers. Natural rubber latex (NRL) can be quantitatively hydrogenated to provide a strictly alternating ethylene–propylene copolymer using a homogeneous osmium catalyst OsHCl(CO)(O₂)(PCy₃)₂. A detailed kinetic investigation was carried out by monitoring the amount of hydrogen consumption during the reaction using a gas‐uptake apparatus. The kinetic results of NRL hydrogenation indicated that this system had a second‐order dependence of the hydrogenation rate on hydrogen pressure and then decreased toward a zero‐order dependence for hydrogen pressures above 13.8 bar. The hydrogenation was also observed to be first‐order with respect to catalyst concentration and inverse first‐order on rubber concentration due to impurities present in the rubber latex. Additions of a controlled amount of acid demonstrated a beneficial effect on the hydrogenation rate of NRL. The temperature dependence of the hydrogenation rate was investigated and an apparent activation energy (over the range of 120–160°C) was calculated as 57.6 kJ/mol. Mechanistic aspects of this catalytic process are discussed on the basis of kinetic results. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 640–655, 2006     

Autoclaved aerated concrete waste (AACW): An alternative filler material for the natural rubber industry

Material waste from the production of autoclaved aerated concrete, a porous material, should be considered as a valuable byproduct for use as a filler material for the rubber industry. Natural rubber (NR) composites filled with different loading (over the range of 0–60 phr) of autoclaved aerated concrete waste (AACW) as a new eco‐friendly material were produced using two roll mills and then were studied for their cure characteristics, mechanical and aging properties, and morphology, and also compared with commercial fillers, calcium carbonate (CaCO₃), and silica (SiO₂). In most cases, the cure characteristics and mechanical and aging properties of the SiO₂‐filled NR composites were significantly better than those of the AACW‐ and CaCO₃‐filled NR composites. However, these properties for AACW‐filled composites appeared to be higher than CaCO₃‐filled composites. The reason for this could be due to a larger surface area which is both porous and of an irregular shape of the AACW filler used. Scanning electron microscope images showed that the morphology of the rubber filled with SiO₂ was finer and more homogenous compared with the rubber filled with AACW or CaCO₃. Overall results revealed that the reinforcement ability of AACW‐filled NR composites was generally better when compared with CaCO₃‐filled NR composites; therefore, AACW can be used effectively as a cheaper filler for production of rubber products where end‐use properties of a rubber product is specifically required. POLYM. COMPOS., 36:2030–2041, 2015. © 2014 Society of Plastics Engineer     

Ablation properties of aluminum silicate ceramic fibers and calcium carbonate filled silicone rubber composites

The ablative performance of aluminum silicate ceramic fiber (ASF) and calcium carbonate (CaCO₃) filled silicone rubber composites prepared through a two‐roll mill was examined. The properties of the composites were investigated by thermogravimetry, thermal conductivity measurements, and oxyacetylene torch testing. After the material was burnt, the structure and composition of the char were analyzed by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy (SEM). The results of the ablation test showed that the ablation resistance improved greatly in an appropriate filler scope. Combined with SEM, it was proven that a firm, dense, and thermal insulation layer, which formed on the composites surface during the oxyacetylene torch test, was a critical factor in determining the ablation properties. Thermogravimetric analysis revealed that the thermal stability of the composites was enhanced by the incorporation of ASF and CaCO₃. The thermal conductivity measurements showed that the silicone rubber composites had a very low thermal conductivity ranging from 0.206 to 0.442 W m^?1 K^?1; this significantly prevented heat from transferring into the inner matrix at the beginning of the burning process. The proportion of 20/40 phr (ASF/CaCO₃) was optimum for improving the ablation resistance of the silicone rubber composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41619.     

Imparting antimicrobial properties to natural rubber latex foam via green synthesized silver nanoparticles

The green synthesis of silver nanoparticles (AgNPs) in centrifuged natural rubber latex (NRL) by in situ reduction of silver nitrate by NRL is described. The synthesis of AgNP within NRL was successfully carried out without the addition of any reducing agent or stabilizers. The modified AgNP incorporated with centrifuged NRL (GAgNP_NRL) was used to make NRL foam (NRLF) by the Dunlop production method. An ultraviolet–visible (UV‐Vis) spectrophotometer analysis, Zeta potential analysis data and transmission electron micrograph analysis proved that the modified centrifuged NRL consisted of stable nanometer‐sized silver particles. A scanning electron microscopic (SEM)/energy‐dispersive X‐ray spectroscopy (EDX) analysis and UV‐Vis analysis of a latex film made out of the modified GAgNP_NRL compound showed nano‐sized silver particles inside the rubber matrix. The final product of the NRLF (GAgNP_NRLF) made out of the GAgNP_NRL compound was tested for antimicrobial properties against gram‐negative Escherichia coli, gram‐positive Staphylococcus aureus and Staphylococcus epidermidis. The resultant GAgNP_NRLF strongly inhibited the bacteria. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40155.     

High‐performance natural rubber latex composites developed by a green approach using ionic liquid‐modified multiwalled carbon nanotubes

The effect of multiwalled carbon nanotubes (MWCNTs) modified by a hydrophilic ionic liquids (ILs), including 1‐ethyl‐3‐methylimidazolium bromide and 1‐hexyl‐3‐methylimidazolium bromide, was studied. The obtained water‐suspensible carbon nanotubes (CNTs) were still homogeneously distributed in water a month after sonication. The microstructural development of filler networks and the uniform dispersion of MWCNTs in the presence of IL were analyzed by TEM. The apparent physical (cation–π/π–π) interaction between the MWCNTs and the IL was characterized by Raman spectroscopy, DSC, and TGA. Furthermore, high‐performance composites of natural rubber latex (NRL) and CNTs modified with IL were obtained by the liquid latex blending method. The CNTs were homogeneously distributed in the matrix and CNT–ILs improved the fatigue resistance and mechanical properties of the NRL/CNT–IL composites. This study demonstrates a simple and eco‐friendly approach to develop multifunctional advanced materials based on IL‐modified MWCNT elastomer composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46588.     

Enhancing the thermal stability of natural rubber/recycled ethylene propylene diene rubber blends through the use of bio‐compatibilizers

Recycling of rubber waste and searching for alternative routes to prolong the service life of rubber products are of significant concern. One of the ideas to reduce the rubber waste is to blend it with the virgin rubber to gain synergistic properties from its own advantages. In this study, natural rubber (NR) and recycled ethylene propylene diene rubber (R‐EPDM) were blended as a way to combine the mechanical properties and oxidative resistance given by NR and R‐EPDM, respectively. New approaches in enhancing the thermal stability were observed through the use of bio‐compatibilizers that is, alkanolamide (AKA)‐based refined, bleached, and deodorized palm stearin (RBDPS) and NR latex (NRL). The thermal stability of the blends was monitored through two techniques: thermo‐oxidative aging and thermogravimetric Analysis. Results indicated that the aging resistance of the blends was improved by addition of AKA and NRL as bio‐compatibilizers. This is confirmed by the enhancement of thermal decomposition temperature and the activation energies of the blends. The obtained TG profiles and the calculated kinetic parameters indicated that introducing AKA and NRL enhanced their thermal stability, especially at higher contents of AKA and NRL. J. VINYL ADDIT. TECHNOL., 25:E155–E165, 2019. © 2018 Society of Plastics Engineers     

Noncatalytic hydrogenation of natural rubber latex

Hydrogenation is an important method of chemical modification, which improves the physical, chemical, and thermal properties of diene‐based elastomers. Natural rubber latex (NRL) could be hydrogenated to a strictly alternating ethylene–propylene copolymer using diimide generated in an in situ system. The diimide generated using the in situ technique for hydrogenation of NRL was accomplished by thermolysis of p‐toluenesulfonyl hydrazide (TSH). A molar ratio of TSH to double bonds equal to 2 : 1 was found to be the optimum ratio to provide a high percentage of hydrogenation. 95% Degree of saturation of NRL was achieved in o‐xylene. Hydrogenated products are characterized by FTIR and NMR spectroscopy. The thermal stability of hydrogenated rubber was improved as shown from the results of thermogravimetric analysis. From the differential scanning calorimetry measurement, the glass transition temperature of the hydrogenated product did not appear to change. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2885–2895, 2007     

Effect of Nano CaCO<Subscript>3</Subscript> on thermal properties of Styrene Butadiene Rubber (SBR)

Styrene butadiene rubber (SBR) as matrix was reinforced separately with 9, 15 and 21 nm sizes of CaCO₃, which were synthesized by matrix mediated growth technique. The mixing and compounding was done on two-roll mill and sheets were prepared in compression molding machine. The effect of nature and loading of nano CaCO₃ on these rubber nanocomposites was investigated thoroughly by different characterizations such as DSC, TGA, XRD, and mechanical properties. An appreciable increase in glass transition temperature has been observed from DSC study. 9 nm sizes of CaCO₃/SBR composites show more increment in Tg as compared to pristine SBR as well as different sizes of CaCO₃ filled SBR. This increment in Tg is due to restricted mobility of nano CaCO₃ filled SBR nanocomposites. XRD study of nanocomposites showed that nano CaCO₃ dispersed uniformly throughout the matrix because of the small peak at lower 2θ. This uniform dispersion of nano CaCO₃ contributes towards the higher mechanical properties of rubber composites. From TGA study, it was observed that as the size of CaCO₃ reduces the thermal stability increases as compared to pristine SBR. The other results of these rubber nanocomposites were compared with commercial CaCO₃ filled SBR. Partly this research paper has been presented in International conference on ‘RubberChem 2006, Dec 5–6, 2006, Munich, Germany.     

Mechanical Properties and Thermooxidative Aging of a Ternary Blend,Pvc/Enr/Nbr,Compared with the Binary Blends of Pvc

In the quest to improve the thermooxidative aging of the poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blend, nitrile rubber (NBR) was incorporated into the blend to yield a ternary blend of PVC/ENR/NBR. A Brabender Plasticorder with a mixing attachment was used to perform the melt mixing at 150°C and 50 rpm followed by compression molding. The mechanical properties, dynamic mechanical properties, and thermooxidative aging behavior of the ternary blend were compared with those of the binary blends (i.e., PVC/ENR and PVC/NBR). It was found that the ternary blend exhibits mechanical properties which are superior to those of PVC/ENR. A single glass transition temperature (T _g) obtained from dynamic mechanical analysis coupled with synergism in the modulus and some other mechanical properties indicate that PVC, ENR, and NBR form a single phase (miscible system) in the ternary blend. Di-2-ethyl hexylphthalate (DOP) plasti-cizer improves the aging resistance of the blends generally, whereas the presence of CaCO₃ as a filler only imparts minor influences on the properties and aging resistance of the blends.     

Effect of surface modification of microcrystalline cellulose with ionic liquids on natural latex composites

As an environmentally friendly biomacromolecular material, microcrystalline cellulose (MCC) enhances the performance of natural rubber latex (NRL) composites. However, MCC has strong polarity, which weakens the interfacial interaction between MCC and the non-polar NRL matrix and reduces the reinforcing performance due to the many hydroxyl groups on its surface. In this paper, the ionic liquid (IL) modified MCC/IL material was prepared, and AIR-FTIR, x-ray diffraction, and XPS photoelectron spectroscopy were performed to detect it from the perspective of environmental protection. And natural latex/microcrystalline cellulose/ionic liquid (NRL/MCC/IL) composites with excellent properties were prepared by latex blending. The activation energy, vulcanization characteristics, basic mechanical properties, dynamic mechanical properties, and filler-rubber interfacial interactions of NRL/MCC/IL composites were investigated. The results showed that the vulcanization rate constant of NRL/MCC/IL composites increase, the activation energy decreases and the mechanical properties were significantly improved. At the same time, the matrix interface interaction of composites was quantitatively calculated using Ayala parameters. The results showed that the interfacial interaction force of the composite was stronger after an appropriate amount of IL pretreatment. The whole process is not only conformed to the concept of green development, but also broadens the application of MCC in rubber materials.     

不同割龄橡胶树RRIM600胶乳组份及性能的研究

本论文研究了割龄3年、割龄13年、割龄20年、割龄24年和割龄28年5种不同割龄的RRIM600天然胶乳的性能。主要研究了天然胶乳粒径,生胶性能,混炼胶的硫化特性以及硫化胶的力学性能。结果表明,割龄28年胶树所得天然胶乳平均粒径最小,胶粒的分布范围较窄,分散性较好;割龄20年橡胶树生胶的P₀和门尼黏度较大,割龄为20年和28年橡胶树所得天然橡胶拉伸强度和撕裂强度较大。     

Preparation and characterization of nano‐CaCO3 encapsulated by copolymerization of styrene and maleic anhydride

Encapsulated nanometer calcium carbonate (nano‐CaCO₃) was prepared using styrene and maleic anhydride (MAH) copolymer in 2‐propanol or methanol–water mixture in the presence of different initiator systems. The particle morphology and physical properties of the encapsulated nano‐CaCO₃ particles, such as the interaction between the encapsulating polymer and the nano‐CaCO₃, and the thermal stability of encapsulated nano‐CaCO₃ were studied by Fourier‐transform infrared spectroscopy (FTIR), Soxhlet extraction experiments, thermogravimetric analysis banded with FTIR (TGA‐FTIR) and transmission electron microscopy (TEM). The encapsulating ratio and the stable encapsulating ratio of encapsulated nano‐CaCO₃ were characterized. The results showed that a strong interfacial interaction was obtained due to the formation of a chemical bond or ion‐dipole between the C?O group of MAH and Ca²⁺ ion of nano‐CaCO₃. The encapsulating ratio and stable encapsulating ratio of nano‐CaCO₃ initiated by AIBN was higher than that initiated by BPO. Addition of maleic anhydride increased the encapsulating ratio and the stable encapsulating ratio of encapsulated nano‐CaCO₃. For the encapsulated nano‐CaCO₃ prepared in methanol–water, the diameter of the encapsulated nano‐CaCO₃ particle increased from 60–70 nm to about 100 nm and the morphology changed from a cube with a sharp edge to spherical with a rough surface. Copyright © 2006 Society of Chemical Industry     

Crystallization properties of polycaprolactone composites filled with nanometer calcium carbonate

Polycaprolactone (PCL) composites filled with nanometer calcium carbonate (nano‐CaCO₃) were prepared by means of a twin‐screw extruder in this study. The nano‐CaCO₃ surface treated with stearate. The crystalline properties of the PCL/nano‐CaCO₃ composites were measured with a differential scanning calorimeter to identify the influence of the nanometer filler content on the crystalline properties. The results show that the crystallization onset temperature, crystallization temperature, and crystallization end temperature of the composites were obviously higher than those of the unfilled PCL resin, and the crystallization degree (χ_c) of the composites increased with increasing particle weight fraction (?_f) when ?_f was more than 1%. When ?_f was 1%, χ_c of the composite was less than that of the unfilled PCL resin. Moreover, the dispersion of the inclusions in the matrix was observed by means of scanning electron microscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal and mechanical behavior of natural rubber latex‐silica aerogel film

A major problem in most natural rubber latex (NRL) commonly encountered like other polymer is susceptibility to mechanical properties and thermal degradation; particularly in thin film due to the presence of double bonds in the main chain. Therefore, it is desirable to seek for ways of improving these properties. Silica aerogel is a material with extraordinary properties was believed to have potential enhance properties in NRL films because of its high specific surface area. Therefore, based on the unique character of silica aerogel, NRL‐silica aerogel film was developed by latex compounding and dry coagulant dipping to form thin film where silica aerogel acts as filler. Silica aerogel, synthesized from rice husk was dispersed in a ball‐mill using distilled water for NRL compounding. Results indicate that increasing silica aerogel loading enhances the mechanical properties of the NRL‐silica aerogel film. Effects of postvulcanization processes were also investigated, whereby the best reinforcing effect was obtained at 4 phr silica aerogel loading with leaching postvulcanization condition. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The influence of surface structure of low industrial grade seaweed and semi‐refined carrageenan on mechanical and physical properties of natural rubber latex composites

Composites consisting of natural rubber (NR) latex as their matrix and low industrial grade seaweed (LIGS) and its extractive (semirefined carrageenan, SRC‐LIGS) as the filler were prepared via normal prevulcanization process. An analysis regarding the particle size and morphology of seaweed (LIGS and SRC‐LIGS), as well as surface properties and mechanical properties (tensile and tear properties) of NR latex composites, was consequently generated. Furthermore, post‐processing treatment for NR latex composites have also been studied, specifically involving leaching, heat aging, water absorption, and soil burial. The particle size of LIGS and SRC‐LIGS obtained was recorded to be lower than 100 μm. Thus, the results are indicative of SRC‐LIGS's role in improving the thermal properties of NR latex composites. After 8 weeks of soil burial, the incorporation of LIGS and SRC‐LIGS into the NR latex composites has accelerated biodegradation processes, thus highlighting their advantage as biodegradable fillers. These properties have consequently contributed to SRC‐LIGS/NR latex composites as a potential composite for use in biodegradable applications, such as polybag for pottery and plants. J. VINYL ADDIT. TECHNOL., 25:278–286, 2019. © 2018 Society of Plastics Engineers     

Use of sodium and potassium butyl xanthate as accelerator for room temperature prevulcanization of natural rubber latex

Sodium and potassium butyl xanthates (Nabxt and Kbxt) were prepared in the laboratory. Characterization of these xanthates were done using Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (¹H NMR) spectroscopy, thermogravimetric analysis (TGA), and differential thermal analysis (DTA) techniques. These xanthates were used as accelerators for the prevulcanization of natural rubber latex (NRL) at room temperature. Optimization of prevulcanization time was done. Films were casted from these prevulcanized NRL. Tensile properties of latex vulcanisates were measured and potassium butyl xanthate gave superior properties to the NRL films compared with sodium butyl xanthate. Effect of thermal ageing on tensile properties of these prevulcanized NRL films was also investigated and these properties were found to be improved after thermal ageing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphology and mechanical properties of natural rubber latex films modified by exfoliated Na‐montmorillonite/polyethyleneimine‐g‐poly (methyl methacrylate) nanocomposites

Na‐montmorillonite/polyethyleneimine‐g‐poly(methyl methacrylate) (Na‐MMT/PEI‐g‐PMMA) nanocomposite latexes were prepared by soap‐free emulsion polymerization in the aqueous suspension of Na‐MMT. The exfoliated morphology of the nanocomposites was confirmed by XRD and TEM. With the aim of improving morphology and mechanical properties of natural rubber latex (NRL) films, the synthesized Na‐MMT/PEI‐g‐PMMA nanocomposites were mixed with NRL by latex compounding technology. The results of SEM and AFM analysis showed that the surface of NRL/Na‐MMT/PEI‐g‐PMMA film was smoother and denser than that of pristine NRL film while Na‐MMT was dispersed uniformly on the fracture surface of the modified films, which suggested the good compatibility between NRL and Na‐MMT/PEI‐g‐PMMA. The tensile strength of NRL/Na‐MMT/PEI‐g‐PMMA films was increased greatly by 85% with 10 phr Na‐MMT/PEI‐g‐PMMA when Na‐MMT content was 3 wt % and the elongation at break also increased from 930% to 1073% at the same time. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43961.     

The preparation of core‐shell CaCO3 particles and its effect on mechanical property of PVC composites

In this study, a novel mechanochemical route to prepare core‐shell structured particles was introduced. XPS, TEM, and dissolving experimental results indicate the formation of [(inorganic particle)/(elastomer)] core‐shell structured particles, and several kinds of calcium carbonate (nano‐CaCO₃) particles with various interfaces were obtained. The mechanical properties and morphological results indicate that the surface treatment of nano‐CaCO₃ particles and the existence of outer elastic layer will strengthen the interfacial interaction between nano‐CaCO₃ particles and PVC matrix, which results in improvement of mechanical properties of PVC/CaCO₃ composites. The theoretical calculations of the interfacial interaction and DMA results confirm these especially when the surface of nano‐CaCO₃ particles was treated by MMA and coated in succession by ACR through vibro‐milling. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1084–1091, 2006     

The Relationship between Microstructure and Properties in PP/Rubber Powder/nano‐CaCO3 Ternary Blends

Summary: A new kind of rubber powder with “salami” structure (RPS) was prepared by spray drying the mixture of styrene‐butadiene rubber latex and nano‐CaCO₃ slurry. It was found that RPS is an effective toughener with synergistic toughening effect on poly(propylene) (PP). The Izod impact strength of PP/RPS blend is not only higher than that of PP/rubber powder or PP/nano‐CaCO₃ blends, but also higher than that of a PP/rubber powder/CaCO₃ blend. TEM images show that the microstructure of the PP/RPS blend is an “island‐sea” structure with “salami” structure in RPS, in which nano‐CaCO₃ particles are embedded in styrene‐butadiene rubber particles. The relationship between properties and microstructure has been studied by using TEM, SEM, DSC, etc.

     

Development of biodegradable natural rubber latex composites by employing corn derivative bio-fillers

This study aims to investigate the viability of employing corn-based fillers (powdered corn grain [CG], corn flour [CF] and cornstarch [CS]) to improve the biodegradability of natural rubber latex (NRL) composites by varying filler loading from 0 to 50 phr. Notable variation in both physical and mechanical properties were observed for the different filler types, with CG-filled NRL demonstrating the better adhesion with NRL. Thus, CG-filled composites were selected for investigation of biodegradability. Increased CG loading in NRL compounds enhanced biodegradation; with over 70% degradation observed for 50 phr CG loading upon 15 weeks of soil burial. However, the trade-off between mechanical properties and biodegradability limits the CG loading in the NRL matrix to 20 phr for manufacturing NRL-based products. It was observed that NRL with CG filler loading of 20 phr conforms to the ASTM D3578 standard for manufacturing rubber gloves; with 50% biodegradation upon 15 weeks of soil burial.