Effect of epoxidised liquid natural rubber on nitrile/butadiene rubber based mixes

Abstract

Epoxidised liquid natural rubber (ELNR) constitutes a new family of polymers chemically derived from natural rubber. It is a highly viscous rubber of low molar mass generally used as plasticiser or processing aid, especially during processing of natural rubber and styrene/butadiene rubber stocks.

The effect of incorporating this polymer rather than a standard plasticiser in a nitrile/butadiene rubber based mix has been investigated. The retention in mechanical properties following air and oil aging of the vulcanisates was also studied. Satisfactory processability of compounded stocks, mechanical properties, and aging resistance was maintained following incorporation of ELNR into nitrile/butadiene rubber formulations even at the lowest plasticiser concentrations. The improvement in aging behaviour was more pronounced when 25 mol-% ELNR was used at concentrations above 15 pphr.     

Viscosity behavior of PVC-modified liquid natural rubber blends

Compatibility of poly(vinyl chloride) (PVC) with liquid natural rubber (LNR) and epoxidized liquid natural rubber (ELNR) has been studied by solution viscometric methods. The relative viscosity versus composition plots for PVC/LNR and PVC/ELNR-20 blends are found to be nonlinear. The corresponding intrinsic viscosity values show negative deviation from ideal behavior when plotted against composition. The modified Krigbaum and Wall parameter, Δb, also shows negative values for all compositions of these blends studied. The results indicate that PVC/LNR and PVC/ELNR-20 blends are incompatible systems. On the other hand, PVC/ELNR-50 blends yielded linear plots when relative viscosity was plotted against composition. The intrinsic viscosity composition plots for this system showed positive deviation from ideal behavior. The δb values are positive for all compositions of these blends studied. These results are characteristic of a compatible blend system. Hence it is concluded that liquid natural rubber can be made compatible with PVC when the former is epoxidized to a sufficient level. © 1996 John Wiley & Sons, Inc.     

Cure efficiency of dodecyl succinic anhydride as a cross‐linking agent for elastomer blends based on epoxidized natural rubber

Blends of a highly epoxidized natural rubber (ENR50) with unmodified natural rubber (NR) and ethylene propylene elastomers (EPDM) were produced to evaluate the mixing and curing characteristics. Dodecyl succinic anhydride was used to cross‐link the ENR50 component and the reactivity was assessed by monitoring the evolution of the torque in an oscillatory co‐axial cylinder rheometer, as well as by DSC thermal analysis. A physical model was used to obtain a single parameter for the reactivity of the system, which corresponds to the rate constant for first order curing reactions. Although the blends were thermodynamically immiscible, displaying no significant change in T_g, the components were well dispersed at microscopic level. Better mechanical properties were obtained for blends with EPDM. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41448.     

Quaternary phosphonium modified epoxidized natural rubber: effect of reaction time,reaction mechanism,thermal property and antimicrobial activity

Herein we endow epoxidized natural rubber with antimicrobial activity by chemical modification. The rubber is firstly ring-opened by bromoacetic acid and then modified by antimicrobial group quaternary phosphonium salt. Using the hydrogen nuclear magnetic resonance spectroscopy (¹H NMR) and the ICP atomic emission spectrometry (ICP-AES), the degree of epoxidation, the convert ratio of epoxy groups, and the phosphorus content of the products are measured, and then the effects of reaction time on the structure of products are investigated. The possible reaction mechanism and side reactions in ring-opening procedure are discussed through the comparison of data with different reaction time, and the ring-expansion reaction is supposed to be dominated in the side reactions. The thermal properties of modified rubbers and the structural factors behind are also investigated using differential scanning calorimeter and thermogravimetric analyzer. Antimicrobial activities of modified rubbers with different ring-opening reaction time toward Escherichia coli are studied, and the activity may increase with the content of quaternary phosphonium salt groups. This research may have the benefit for optimizing the structure of chemically modified antimicrobial rubbers.     

Changes in morphology and properties of NR–NBR blends. Effect of viscosity ratio modified by liquid natural rubber and epoxidised liquid natural rubber

Abstract

Changes in rheological properties, morphology, and oil resistance in NR–NBR blends by viscosity ratio have been investigated. In this study, the viscosity ratio was modified by mechanical mastication and addition of liquid natural rubber (LNR) and epoxidised liquid natural rubber (ELNR). The results reveal that as viscosity ratio increased from 0·5 to 1·0, Mooney viscosity of the blends increased, and then decreased sharply as the viscosity ratio further increased from 1·0 to 2·0. The addition of LNR and ELNR for plasticising NR and NBR, respectively, does not significantly affect cure properties of the blends. The phase size of the NR dispersed phase depends strongly on the viscosity ratio. The high viscosity of the matrix and/or the low viscosity of the dispersed phase promote breaking up of the dispersed phase. Unexpectedly, a decrease in size of the dispersed phase by the modification of viscosity ratio via the use of low molecular weight rubber (i.e. LNR and ELNR) did not result in an improvement in oil resistance.     

High damping epoxized natural rubber/diallyl adiallyl phthalate prepolymer (ENR/DAP‐A) blends engineered by interphase crosslinking

While a great diversity of rubber/plastic damping blends have been reported, the damping trough resulted from phase incompatibility, which usually exists between the glass transition temperatures (T_g) of each component, remains an unsolved problem by separating the effective temperature range of damping blends. Herein, we reported a new and facile way of preparing rubber/plastic binary blends with high damping property by eliminating the inherent damping trough. Specifically, we envisaged that peroxides can trigger free radical reactions both within and between epoxidized natural rubber/diallyl phthalate prepolymer moieties, which serve as the co‐vulcanizer to generate interphase reactions thus enhancing phase compatibility. Accordingly, apart from the resulting high damping epoxidized natural rubber40/diallyl phthalate prepolymer binary blends with an effective (tan δ_min > 0.35) temperature range of 178 °C from −33 to 145 °C, the proposal has also been demonstrated via the support of broadband dielectric spectrometer testing, dynamic mechanical analysis, and differential scanning calorimetry. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46300.     

无卤阻燃型天然橡胶的研究

该文研究了阻燃剂种类和用量对天然橡胶硫化胶的阻燃性能、力学性能和硫化特性的影响。结果表明：单用氢氧化铝时,随着用量增加,硫化胶阻燃性能上升,但力学性能有所下降,氢氧化铝用偶联剂A151表面改性处理后,硫化胶力学性能有所改善;红磷作为阻燃剂用量比较少,在提高硫化胶阻燃性的同时可改善其力学性能;氢氧化铝、红磷和三氧化二锑并用可产生较好的阻燃协同效果,同时会加快橡胶的硫化速度。     

Nanocomposites based on epoxidized poly(styrene-co-butadiene) rubber and graphene nanoplatelets

Nanofillers play as reinforcing agents of the polymer matrix. The reinforcement and dynamic mechanical properties of nanocomposites based on filled epoxidized-poly(styrene-co-butadiene) rubber are investigated. The modification of the polymer matrix allows improvement in polymer–filler interaction, and thus the mechanical properties of the vulcanizates. Here, the rubber was modified by introducing the epoxy functional groups in the matrix. The quantification for epoxidation rate was analyzed by means of NMR and ~8.8% epoxidation was optimized. The nanocomposites were prepared by melt-mixing technique. The influence of rubber epoxidation in enhancing dynamic mechanical and thermal properties was demonstrated. Stable filler networking using exfoliated graphene nanoplatelets (xg C750) and carbon black (CB-N234) in epoxidized rubber is described through multihysteresis measurements. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47802.     

Miscible blends from plasticized poly(vinyl chloride) and epoxidized natural rubber

Miscible blends from plasticized poly(vinyl chloride), and epoxidized natural rubber having 50 mol% epoxidation level were prepared in a Brabender Plasticorder by the melt-mixing technique. Changes in Brabender torque and temperature, density, dynamic mechanical properties, and differential scanning calorimetry of the samples were examined as a function of blend composition. The plasticized poly(vinyl chloride)/epoxidized natural rubber blends behaved as a compatible system at all composition ranges as evident from their single glass-rubber transition temperature (T_g) obtained from dynamic mechanical analysis as well as from differential scanning calorimetry. Profound changes in the nature of the glass-rubber transition were noted with respect to blend composition. The T_g-width values of blends lie between those of plasticized poly(vinyl chloride) and epoxidized natural rubber.     

Effect of surface modification of silicon carbide nanoparticles on the properties of nanocomposites based on epoxidized natural rubber/natural rubber blends

Improvement of the properties of rubber nanocomposites is a challenge for the rubber industry because of the need for higher performance materials. Addition of a nanometer‐sized filler such as silicon carbide (SiC) to enhance the mechanical properties of rubber nanocomposites has rarely been attempted. The main problem associated with using SiC nanoparticles as a reinforcing natural rubber (NR) filler compound is poor dispersion of SiC in the NR matrix because of their incompatibility. To solve this problem, rubber nanocomposites were prepared with SiC that had undergone surface modification with azobisisobutyronitrile (AIBN) and used as a filler in blends of epoxidized natural rubber (ENR) and natural rubber. The effect of surface modification and ENR content on the curing characteristics, dynamic mechanical properties, morphology and heat buildup of the blends were investigated. The results showed that modification of SiC with AIBN resulted in successful bonding to the surface of SiC. It was found that modified SiC nanoparticles were well dispersed in the ENR/NR matrix, leading to good filler‐rubber interaction and improved compatibility between the rubber and filler in comparison with unmodified SiC. The mechanical properties and heat buildup when modified SiC was used as filled in ENR/NR blends were improved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45289.     

Use of epoxidized natural rubber as a toughening agent in plastics

At present, the rubber toughening of plastics has become an attractive field of study in polymer science and technology because brittleness is known to be a drawback in many engineering plastics; it can cause premature failure during application. Among existing rubber materials, epoxidized natural rubber (ENR) has been widely used as an impact modifier or toughening agent in a large number of engineering plastics; in particular, it enhances the impact strength, which deteriorates with the incorporation of other additives, such as fillers and flame retardants. ENR is a modification product from natural rubber produced via an epoxidation reaction. ENR also has good chemical resistance. In this review, we aim to provide a concise current status in the field of ENR toughening agents for plastics with a brief discussion of their associated problems and potential applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42270.     

Self‐crosslinkable lignin/epoxidized natural rubber composites

Self‐crosslinkable lignin/epoxidized natural rubber composites (SLEs) were prepared through a high‐temperature dynamic heat treatment procedure followed by a postcuring process. Because of the ring‐opening reaction between lignin and epoxidized natural rubber (ENR), lignin as a crosslinker and reinforcing filler was uniformly dispersed into the ENR matrix and was highly compatible with the polymer matrix; this was confirmed by scanning electron microscopy. The curing behavior, mechanical properties, and dynamic mechanical properties of the SLEs were studied. The results show that the crosslinking degree, glass‐transition temperature, modulus, and tensile properties of the SLEs substantially increased with the addition of lignin. A physical model was used to verify the strong interactions between lignin and ENR. Stress–strain curves and X‐ray diffraction suggested that the reinforcement effect on the SLEs mainly originated from lignin itself rather than from strain‐induced crystallization. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41166.     

Thermodynamically and kinetically favored locations of rice husk ash particles in the phase structure,and the properties of epoxidized natural rubber/thermoplastic polyurethane blends

This article aims to study the influences of the selective location of rice husk ash (RHA) particles on morphological, mechanical, and dynamic properties of epoxidized natural rubber and thermoplastic polyurethane blends (ENR/TPU). Thermodynamic aspects, that is, interfacial tension and work of adhesion were assessed from estimates based on surface tension. It was found that the RHA particles had stronger interactions with the ENR than the TPU, of the co‐continuous phases. The phase structure was mainly controlled by kinetic factors, particularly by the mixing sequence, and to a lesser degree by thermodynamics. Furthermore, the microstructure with RHA particles dispersed in the ENR co‐continuous phase was found to give enhanced mechanical properties. This might be attributed to the higher work of adhesion between ENR and RHA that stabilized the encapsulated RHA particles against shear and elongational stresses, during melt mixing and in the final products. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46681.     

环氧化天然杜仲橡胶在丁苯橡胶/白炭黑复合体系中的应用

本文主要研究了环氧化天然杜仲橡胶的应用对丁苯橡胶/白炭黑复合体系物理机械性能的影响,并与传统白炭黑分散剂进行分析比较。结果表明,白炭黑分散剂B-52、FS-79和环氧化天然杜仲橡胶均能改善白炭黑引起的硫化延迟,减轻填料聚集导致的Payne效应;与白炭黑分散剂B-52、FS-79相比,环氧化天然杜仲橡胶改性丁苯橡胶(SBR)/白炭黑硫化胶的力学性能更高、耐磨性更好、压缩温升适中,且具有更好的动态力学性能。     

Impact,Thermal, and Morphological Properties of Poly(Lactic Acid)/Poly(Methyl Methacrylate)/Halloysite Nanotube Nanocomposites

Poly(lactic acid)/poly(methyl methacrylate) blends containing halloysite nanotube (2 and 5 phr) and epoxidized natural rubber (5–15 phr) were prepared by melt mixing. The impact strength of poly(lactic acid)/poly(methyl methacrylate) blend was slightly improved by the addition of halloysite nanotube. Adding epoxidized natural rubber further increased the impact strength of poly(lactic acid)/poly(methyl methacrylate)/halloysite nanotube nanocomposite. Single T_g of poly(lactic acid)/poly(methyl methacrylate) is observed and this indicates that poly(lactic acid)/poly(methyl methacrylate) blend is miscible. The addition of halloysite nanotube into poly(lactic acid)/poly(methyl methacrylate) slightly increased the T_g of the blends. The epoxidized natural rubber could encapsulate some of the halloysite nanotube and prevent the halloysite nanotube from breaking into shorter length tube during the melt shearing process.     

Clay nanolayer reinforcement of cis‐1,4‐polyisoprene and epoxidized natural rubber

Conditions were established for dispersing clay nanolayers into both cis‐1,4‐polyisoprene (synthetic) natural rubber (NR) and epoxidized natural rubbers (ENR) having 25 or 50 mol % epoxide. The clay was a sodium montmorillonite and was used as a pristine layered silicate or as organically modified layered silicates to make the galleries more hydrophobic and thus more compatible with the elastomers. The chemical modifications were carried out using an ion‐exchange reaction with alkyl ammonium cations. Incorporation of the clays into the elastomers was achieved by mixing the components themselves in a standard internal blender or by mixing dispersions of them in toluene or methyl ethyl ketone. X‐ray diffraction results indicated intercalation of NR and ENR into the silicate interlayers, followed by exfoliation of the silicate layers into the elastomer matrices. Of primary interest was the effect of the intercalated and exfoliated clays on the mechanical properties of the elastomers. The reinforcing effects obtained were found to depend strongly on the extent of the dispersion of the silicate layers into the rubber matrices. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1391–1403, 2001     

炭黑并用对NR／ENR共混胶力学性能及减震性能的影响

对比N660研究了N330／N660、N660／N990炭黑填充体系对天然橡胶（NR）／环氧化天然橡胶（ENR）共混胶力学性能、压缩疲劳生热性能及减震性能的影响,并采用橡胶加工分析仪（RPA）对其加工性能进行了分析。结果表明：N660／N330和N660／N990两种填充体系硫化胶的力学性能,基本上是单用一种炭黑所得硫化胶力学性能的加权平均;不同粒径炭黑并用均能使共混胶的贮能模量E′下降,并且有利于拓宽NR／ENR减震材料的减震范围;不同粒径炭黑并用有利于改善NR／ENR共混胶料的加工性能。     

Functionalized liquid natural rubber and liquid epoxidized natural rubber: A promising green toughening agent for polyester

Toughened unsaturated polyester resins (UPRs) were prepared using two different reactive rubbers, namely, liquid natural rubber (LNR) and liquid epoxidized natural rubber (LENR). The effect of varying amounts of LNR and LENR on the morphology, thermal, and mechanical properties of UPR were evaluated. Fourier Transform Infrared spectroscopy was used to investigate the probable crosslinking reaction and changes in the functional groups on crosslinking. Field emission scanning electron microscopy and infinite focus microscopy were used to study the morphology of fracture surfaces. Tensile test showed that both the rubber‐modified resins (1.5 wt %) improved tensile strength. The viscoelastic properties and thermal stability of the toughened polyesters were evaluated using dynamic mechanical thermal analysis and thermogravimetric analysis, respectively. A slight reduction in the glass transition temperature (T_g) of the polyester was reported on the addition of both the rubbers. An increment in impact strength and fracture toughness was observed at 1.5 wt % for LNR and 4.5 wt % for LENR‐modified UPR. The results showed that both the liquid rubbers improved the mechanical properties of UPR. However, LENR‐modified UPR exhibited a more significant improvement in the mechanical properties compared to LNR‐modified UPR. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41292.     

Epoxidation and hydroxlation of rubber seed oil: one‐pot multi‐step reactions

Epoxidized and hydroxylated rubber seed oils were prepared by peroxyformic acid generated in situ by reacting formic acid and hydrogen peroxide with RSO, a renewable resource. The structural and physico‐chemical properties of RSO have been determined. The fatty acid composition showed a high content of polyunsaturated fatty acids. The modified products were characterized with regard to their structure and properties. The findings of this study revealed that both hydroxylated and epoxidized RSO can be prepared by one‐pot multi‐step reactions.     

Effect of reinforcement on the barrier and dielectric properties of epoxidized natural rubber–graphene nanocomposites

The influence of epoxidation level of natural rubber (i.e., ENR25, ENR50) on the dielectric and oxygen gas barrier properties of thermally reduced graphene oxide (GR) and graphite (GT) (with 2%·w/w) filled nanocomposites are investigated here. GR, GT filled epoxidized natural rubber (ENR) nanocomposites were fabricated by mechanical mixing using environment friendly two‐roll mill mixing method. Raman spectroscopy and Fourier transform infrared spectroscopy studies were carried out to investigate the extent of chemical interactions between GR and ENR. Morphological studies were done using transmission electron microscopy to evaluate the distribution of GR and GT in the ENR. The improved gas barrier and dielectric properties of GT‐ENR and GR–ENR composites synthesized by a novel green ecofriendly method is correlated with the chemical interactions among GT, GR, and ENR. POLYM. ENG. SCI., 55:2439–2447, 2015. © 2015 Society of Plastics Engineers