Thermoplastic elastomers-based natural rubber and thermoplastic polyurethane blends

Thermoplastic elastomers based on the blends of thermoplastic polyurethane (TPU) and natural rubber were prepared by a simple blend technique. The influence of the two different types of natural rubber (i.e., unmodified natural rubber (NR) and epoxidized natural rubber (ENR)) on properties of the blends was investigated. The main aim of this study was to improve heat resistance and damping properties, and also to prepare the TPU material with low hardness by blending with various amounts of natural rubber. It was found that the TPU/ENR blends exhibited superior modulus, hardness, shear viscosity, stress relaxation behavior and heat-resistant properties compared to the blends with TPU and unmodified NR. This was attributed to higher chemical interaction between the polar functional groups of ENR and TPU by improving the interfacial adhesion. It was also found that the ENR/TPU blends exhibited finer grain morphology than the blends with unmodified NR. Furthermore, lower tension set, damping factor (Tan ??) and hardness, but higher degradation temperature, were observed in natural rubber/TPU blends compared to pure TPU. This proves the formation of TPU material with high heat resistance, low hardness and better damping properties. However, the blends with higher proportion of natural rubber exhibited lower tensile strength and elongation at break.     

Thermoplastic vulcanizates based on epoxidized natural rubber/polypropylene blends: Effect of compatibilizers and reactive blending

Epoxidized natural rubber (ENR) was prepared using the performic epoxidation method. TPVs based on ENR/PP blends were later prepared by melt‐mixing processes via dynamic vulcanization. The effects of blend ratios of ENR/PP, types of compatibilizers, and reactive blending were investigated. Phenolic modified polypropylene (Ph‐PP) and graft copolymer of maleic anhydride on polypropylene molecules (PP‐g‐MA) were prepared and used as blend compatibilizers and reactive blending components of ENR/Ph‐PP and ENR/PP‐g‐MA blends. It was found that the mixing torque, apparent shear stress and apparent shear viscosity increased with increasing levels of ENR. This is attributed to the higher viscosity of the pure ENR than that of the pure PP. Furthermore, there was a higher compatibilizing effect because of the chemical interaction between the polar groups in ENR and PP‐g‐MA or Ph‐PP. Mixing torque, shear flow properties (i.e., shear stress and shear viscosity) and mechanical properties (i.e., tensile strength, elongation at break, and hardness) of the TPVs prepared by reactive blending of ENR/Ph‐PP and ENR/PP‐g‐MA were lower than that of the samples without a compatibilizer. However, the TPVs prepared using Ph‐PP and PP‐g‐MA as compatibilizers exhibited higher values. We observed that the TPVs prepared from ENR/PP with Ph‐PP as a compatibilizer gave the highest rheological and mechanical properties, while the reactive blending of ENR/PP exhibited the lowest values. Trend of the properties corresponds to the morphology of the TPVs. That is, the TPV with Ph‐PP as a blend compatibilizer showed the smallest rubber particles dispersed in the PP matrix, while the reactive blending of ENR/PP‐g‐MA showed the largest particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4729–4740, 2006     

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.     

环氧化天然橡胶共交联改性EPDM/NR共混物的性能

将三元乙丙橡胶(EPDM)与环氧化天然橡胶(ENR)共交联改性后,再与天然橡胶(NR)共混,考察了ENR共交联改性EPDM/NR共混胶的硫化特性、硫化胶的物理机械性能、溶胀指数和耐热空气老化性能,并对该硫化胶进行了差示扫描量热分析。结果表明,EPDM经过ENR共交联改性后与NR共混,ENR共交联改性EPDM/NR共混胶的交联程度明显提高,各相达到了同步交联,硫化胶的综合性能得到了显著改善。     

Nanoclay distribution and its influence on the mechanical properties of rubber blends

The distribution of modified and unmodified nanoclays inside the rubber phases of immiscible rubber–rubber blends composed of nonpolar–polar natural rubber (NR)/epoxidized natural rubber (ENR) and nonpolar–nonpolar NR/polybutadiene rubber (BR) was investigated for the first time. The distribution of clays at various loadings in the blends was calculated from the viscoelastic properties of the blends. For example, in the 50 : 50 NR/ENR blend, 42% Cloisite 30B migrated to the NR phase, and 58% went to the ENR phase. However, in the same blend, only 7% Cloisite Na⁺ was found in the NR phase, and 93% was found in the ENR phase. Again, in the 50 : 50 NR/BR blends, the NR phase contained 85% Cloisite 30B, whereas 55% Cloisite Na⁺ migrated to the NR phase. All these observations were explained with the help of viscosity, X‐ray diffraction, and morphology analyses. The effect of the distribution of the clay on the mechanical properties was also discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel thermoplastic natural rubber based on thermoplastic polyurethane blends: influence of modified natural rubbers on properties of the blends

Three different forms of natural rubber: maleated natural rubber (MNR), epoxidized natural rubber (ENR) and natural rubber-graft-poly(methyl methacrylate) (NR-g-PMMA) were prepared. Degree of functional groups in rubber molecules was quantified using the integrated peak areas of ¹H NMR. It was found that the modified rubbers with similar level of functionality had been successfully prepared. Thermoplastic natural rubber (TPNR) based on blending of thermoplastic polyurethane (TPU) and various forms of rubber were then prepared using melt blending method. The properties of the blends were studied and compared together in relation to different types of natural rubbers prepared (i.e., unmodified NR, MNR, ENR and NR-g-PMMA). It was found that the blends with modified NR exhibited superior stiffness, entropy effect and damping factor compared to other blends with unmodified NR. This is attributed to the chemical interaction between the functional groups of modified NR molecules and polar functional groups in TPU molecules which facilitated higher interfacial adhesion between both phases. The chemical interaction was verified by ATR-FTIR and TSSR techniques. It was also found that the MNR/TPU blend showed the highest tensile modulus, mechanical and elastic properties with smallest and finer grain dispersion of co-continuous phase compared to ENR/TPU, NR-g-PMMA/TPU and unmodified NR/TPU blends, respectively. This might be due to higher chemical interactions between MNR and TPU phases. Furthermore, the incorporation of rubber did reduce hardness (i.e., <60 Shore A) with improvement of elasticity of the blends compared with the original TPU (i.e., ~85 Shore A).     

Novel ternary blends of natural rubber/linear low-density polyethylene/thermoplastic starch: influence of epoxide level of epoxidized natural rubber on blend properties

Novel degradable materials based on ternary blends of natural rubber (NR)/linear low-density polyethylene (LLDPE)/thermoplastic starch (TPS) were prepared via simple blending technique using three different types of natural rubber (i.e., unmodified natural rubber (RSS#3) and ENR with 25 and 50 mol% epoxide). The evolution of co-continuous phase morphology was first clarified for 50/50: NR/LLDPE blend. Then, 10 wt% of TPS was added to form 50/40/10: NR/LLDPE/TPS ternary blend, where TPS was the particulate dispersed phase in the NR/LLDPE matrix. The smallest TPS particles were observed in the ENR-50/LLDPE blend. This might be attributed to the chemical interactions of polar functional groups in ENR and TPS that enhanced their interfacial adhesion. We found that ternary blend of ENR-50/LLDPE/TPS exhibited higher 100 % modulus, tensile strength, hardness, storage modulus, complex viscosity and thermal properties compared with those of ENR-25/LLDPE/TPS and RSS#3/LLDPE/TPS ternary blends. Furthermore, lower melting temperature (T _m) and heat of crystallization of LLDPE (?H) were observed in ternary blend of ENR-50/LLDPE/TPS compared to the other ternary blends. Also, neat TPS exhibited the fastest biodegradation by weight loss during burial in soil for 2 or 6 months, while the ternary blends of NR/LLDPE/TPS exhibited higher weight loss compared to the neat NR and LLDPE. The lower weight loss of the ternary blends with ENR was likely due to the stronger chemical interfacial interactions. This proved that the blend with ENR had lower biodegradability than the blend with unmodified NR.     

Cure characteristics and mechanical properties of hydrogenated natural rubber/natural rubber blends

The cure characteristics and mechanical properties of blends consisting of hydrogenated natural rubber (HNR) and natural rubber (NR) blends were investigated. The HNR/NR blends at 50/50 wt ratio were vulcanized using various cure systems: peroxide vulcanization, conventional vulcanization with peroxide, and efficient vulcanization with peroxide. The HNR/NR vulcanizates cured by the combination of peroxide and sulfur donor (tetramethylthiuram disulfide, TMTD) in the efficient vulcanization with peroxide exhibited the best mechanical properties. It was also found that the hydrogenation level of HNR did not affect the tensile strength of the vulcanizates. The tensile strength of the blends decreased with increasing HNR content because of the higher incompatibility to cause the noncoherency behavior between NR and HNR. However, the HNR/NR vulcanizate at 50/50 wt ratio showed the maximum ultimate elongation corresponding to a co‐continuous morphology as attested to by scanning electron micrographs. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

High‐performance bio‐based poly(lactic acid)/natural rubber/epoxidized natural rubber blends: effect of epoxidized natural rubber on microstructure,toughness and static and dynamic mechanical properties

Attempts have been made to prepare high‐performance bio‐based blends through blending of poly(lactic acid) (PLA) with natural rubber (NR) in the presence of epoxidized natural rubber (ENR) as a compatibilizer. The prepared samples were characterized using differential scanning calorimetry, measuring the tensile properties and impact resistance, scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy and dynamic mechanical analysis (DMTA). Morphological studies revealed a matrix‐dispersed morphology for all blends, in which the average droplet size significantly decreased with the use of ENR. The elongation at break and impact strength of the blend containing 3 wt% ENR were 45 and 16 times those of neat PLA, respectively. These values are significantly higher than those previously reported for various simple and dynamically vulcanized rubber‐toughened PLAs. The influence of ENR on compatibility was confirmed by rheological tests, FTIR spectra and DMTA. DMTA also showed a marked increase in elastic modulus for the blend in the presence of 3 wt% ENR. The tensile properties and impact resistance were directly dependent on the ENR content and rubber droplet size. © 2018 Society of Chemical Industry     

Thermoplastic vulcanizates based on poly(methyl methacrylate)/epoxidized natural rubber blends: Mechanical,thermal, and morphological properties

Epoxidized natural rubbers (ENRs) with epoxide levels of 10, 20, 30, 40 and 50 mol % were prepared. The ENRs were later used to prepare thermoplastic vulcanizates (TPVs) by blending them with poly(methyl methacrylate) (PMMA) using various formulations. Dynamic vulcanization, using sulfur as a vulcanizing agent, was performed during the mixing process. The mixing torque increased as the ENR contents and epoxide molar percentage increased. This was because of an increasing chemical interaction between the polar groups of the blend components, particularly at the interface between the elastomeric and thermoplastic phases. The ultimate tensile strength of the TPVs with ENR‐20 was high because of strain‐induced crystallization. ENRs with epoxide levels >30 mol % exhibited an increase of tensile strength because of increasing levels of chemical interaction between the molecules and the different phases. The hardness of the TPVs also increased with increased epoxide levels but decreased with increased contents of ENRs. Two morphology phases with small domains of vulcanized ENR particles dispersed in the PMMA matrix were observed from scanning electron microscopy micrographs. The TPVs based on ENR‐20 and ENR‐50 showed smaller dispersed rubber domains than those of the other types of ENRs. Furthermore, the size of the vulcanized rubber domain decreased with increasing amounts of PMMA in the blends. The decomposition temperature of the TPVs also increased as both the levels of ENRs in the blends and the epoxide molar percentage increased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1251–1261, 2005     

Toughness enhancement of poly(lactic acid) by melt blending with natural rubber

Rubber toughened poly(lactic acid) (PLA) was prepared by blending with natural rubber (NR)‐based polymers. The blends contained 10 wt % of rubber and melt blended with a twin screw extruder. Enhancement of impact strength of PLA was primarily concernced. This study was focused on the effect of rubber polarity, rubber viscosity and molecular weight on mechanical properties of the blends. Three types of rubbers were used: NR, epoxidized natural rubber (ENR25 and ENR50), and natural rubber grafted with poly(methyl methacrylate) (NR‐g‐PMMA). Effect of viscosity and molecular weight of NR, rubber mastication with a two‐roll mill was investigated. It was found that all blends showed higher impact strength than PLA and NR became the best toughening agent. Viscosity and molecular weight of NR decreased with increasing number of mastication. Impact strength of PLA/NR blends increased after applying NR mastication due to appropriate particle size. DMTA and DSC characterization were determined as well. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical properties and blend compatibility of natural rubber –chlorosulfonated polyethylene blends

Natural rubber (NR) was blended with chlorosulfonated polyethylene (CSM) with various formulation and blend ratios (NR/CSM: 80/20 –20/80, wt/wt). Rubber blends were prepared by using a two‐roll mill and vulcanized in a compression mold to obtain the 2 mm‐thick sheets. Tensile properties, tear resistance, thermal aging resistance, ozone resistance, and oil resistance were determined according to ASTM. Compatible NR/CSM blends are derived from certain blends containing 20–30% CSM without adding any compatibilizing agent. Tensile and tear strength of NR‐rich blends for certain formulations show positive deviation from the rule of mixture. Thermal aging resistance depends on formulation and blend ratio, while ozone and oil resistance of the blends increase with CSM content. Homogenizing agents used were Stuktol®60NS and Epoxyprene®25. Stuktol®60NS tends to decrease the mechanical properties of the blends and shows no significant effect on blend morphology. Addition of 5–10 phr of epoxidized natural rubber (ENR, Epoxyprene® 25) increases tensile strength, thermal aging resistance, and ozone resistance of the blends. It is found that ENR acts as a compatibilizer of the NR/CSM blends by decreasing both CSM particle size diameter and α transition temperature of CSM. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 127–140, 2006     

氟橡胶/EPDM动态硫化共混物的研究

研究了动态硫化工艺条件和共混比对氟橡胶（ＦＫＭ）／ＥＰＤＭ共混物拉伸性能拉、热油老化性能和应力松弛性能的影响。结果表明：与直接静态硫化相比,动态硫化可避免两种硫化体系的相互影响;静态硫化共混物拉伸强度只有２ＭＰａ,而动态硫化共混物可达１０ＭＰａ以上;工艺条件对动态硫化共混物性能的影响不大;随共混物中ＥＰＤＭ用量的增大,共混物的热空气老化和热油老化性能均有所下降     

Thermoplastic vulcanizates based on epoxidized natural rubber/polypropylene blends: Effect of epoxide levels in ENR molecules

Epoxidized natural rubbers (ENR) with various levels of epoxide groups were prepared. Thermoplastic vulcanizates based on 75/25 ENRs/PP blends with Ph‐PP compatibilizer were later prepared by dynamic vulcanization using sulfur curing system. Influence of various levels of epoxide groups on rheological, mechanical morphological properties, and swelling resistance of the TPVs was investigated. It was found that the mixing torque, apparent shear stress, apparent shear viscosity, tensile strength, and hardness properties increased with increasing levels of epoxide groups in the ENR molecules. This may be attributed to increasing level of chemical interaction between the methylol groups of the Ph‐PP molecules and polar functional groups of the ENR molecules. Also, the PP segments in the Ph‐PP molecules are capable of compatibilizing with the PP molecules used as a blend composition. In SEM micrographs, we observed finer dispersion of vulcanized rubber domains as increasing levels of epoxide contents. This corresponds to increasing trend of strength and hardness properties of the TPVs. An increasing trend of tension set and a decreasing trend of elongation at break were observed as increasing levels of epoxide groups in the ENR molecules. This is because of higher rigidity of the vulcanized ENR phase with higher epoxide groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3046–3052, 2006     

Novel dynamic vulcanization of polyethylene and ozonolysed natural rubber blends: Effect of curing system and blending ratio

Dynamic vulcanization was studied in terms of the change in α‐relaxation temperatures of the LDPE matrix, morphology, and mechanical properties of LDPE/ozonolysed NR blends which were vulcanized at various blend ratios and with different curing systems, i.e., peroxide and sulfur systems. The ozonolysed NR with M _w = 8.30 × 10⁵ g mol⁻¹ and M _n = 2.62 × 10⁵ g mol⁻¹, prepared by the in situ ozonolysis reaction of natural rubber latex, was used in this study. The significant change in the α‐relaxation temperature of LDPE in the LDPE/ozonolysed NR, dynamically vulcanized using the sulfur system, suggested that sulfur vulcanization of the blend gave a higher degree of crosslink density than using peroxide and corresponded with the improved damping property and homogenous phase morphology. However, the peroxide cured blends of LDPE/ozonolyzed NR gave more improvement of tensile strength and elongation at break than the sulfur cured system. Furthermore, the mechanical properties of tensile strength, elongation at break, and damping were improved by increasing the ozonolyzed natural rubber content in both DCP and sulfur cured blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rheological behavior of reactive blending of epoxidized natural rubber with cassava starch and epoxidized natural rubber with natural rubber and cassava starch

Epoxidized natural rubbers (ENR‐25 and ENR‐45) were prepared using the performic epoxidation method. Two‐component (ENR–cassava starch) and three‐component (ENR–NR–cassava starch) blends were prepared. ENR‐25 and ENR‐45 were blended with various quantities of gelatinized cassava starch in the latex state. The pure ENR exhibited lower shear stress and shear viscosity than those of the blends with cassava starch. Furthermore, the shear stress and shear viscosity were increased with an increase in the cassava starch concentration. The chemical interaction between the epoxide groups in the ENR and the hydroxyl groups in the cassava starch molecules might be the reason for the increasing trends of the shear stress and shear viscosity. The blends are classified as compatible blends because of the strong chemical bonding between different phases. SEM micrographs were used to clarify the compatibility. Power law behavior with pluglike flow profiles was observed for all sets of ENR–NR–cassava starch blends. Very low power law index values (<0.34) and highly pseudoplastic fluid behavior were also observed. The log additive rule was applied to plots of zero shear viscosity (consistency index) and the shear viscosity versus the concentration of ENR‐25. Positive deviation blending was observed, which indicates compatible blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1752–1762, 2004     

Pervaporation of acetone‐chlorinated hydrocarbon mixtures through polymer blend membranes of natural rubber and epoxidized natural rubber

Transparent nonporous membranes were prepared by blending natural rubber (NR) with epoxidized NR (ENR). These blend membranes were evaluated for the selective separation of chlorinated hydrocarbons from acetone. The flux and selectivity of the membranes were determined both as a function of the blend composition and feed mixture composition. Results showed that polymer blending method could be very useful to develop new membranes with improved permselectivity. Pervaporation properties could be optimized by adjusting the blend composition. NR/ENR 70/30 and NR/ENR 30/70 composition showed a decrease in flux and selectivity, whereas the 50/50 composition showed increased flux and increased selectivity. Chlorinated hydrocarbons permeated preferentially through all the tested membranes. The feed mixture composition also strongly influenced the pervaporation characteristics of the blend membranes. Permselectivity was found to depend on the molecular size of the penetrants. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2365–2379, 1999     

Relationships among blending conditions,size of dispersed phase,and oil resistance in natural rubber and nitrile rubber blends

The rheological properties, morphology, and oil resistance in natural rubber and nitrile‐butadiene rubber (NR/NBR) blends are investigated as functions of the blending conditions. It is found that the Mooney viscosity of the blends depends more strongly on the blending time than the rotor speed. The size of the NR dispersed phase is approximately independent of the rotor speed, but it decreases with increasing blending time up to 25 min. With a further increase in the blending time the NR dispersed phase size decreases. The results for the relative tensile strength, which is an indicator of oil resistance, are in agreement with those of the blend morphology, indicating that the oil resistance in a 20/80 NR/NBR blend strongly depends on the phase morphology of the blend. The smaller the size of NR dispersed phase, the higher the blend resistance to oil. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1232–1237, 2001     

Morphology,mechanical and viscoelastic properties of nitrile rubber/epoxidized natural rubber blends

A new class of blend membranes from blends of nitrile rubber (NBR) and epoxidized natural rubber (ENR) has been prepared and their morphology, miscibility, mechanical, and viscoelastic properties have been studied. The ebonite method was used to study the blend morphology of the membranes. The morphology of the blends indicated a two‐phase structure in which the minor phase is dispersed as domains in the major continuous phase. The performance of NBR/ENR blend membranes has been studied from the mechanical measurements. The viscoelastic behavior of the blends has been analyzed from the dynamic mechanical data. An attempt was made to relate the viscoelastic behavior with the morphology of the blends. Various composite models have been used to predict the experimental viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by theoretical group contribution analysis. The homogeneity of the system was further evaluated by Cole–Cole analysis. Finally, a master curve for the modulus of the blend was generated by applying the time–temperature superposition principle. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1561–1573, 2005     

Development of novel elastomeric blends containing natural rubber and ultra-low-density polyethylene

This study sought to develop novel elastomeric compounds using natural rubber (NR) and ultra-low-density polyethylene (ULDPE). Blends were prepared by means of a two-roll mill for three ratios (70/30, 60/40, and 50/50 NR/ULDPE). Conventional vulcanization was performed in a compression mold. The physical and mechanical properties of the blend were determined according to ASTM standards. The results were compared with those obtained from NR blended with styrene-butadiene rubber (SBR). The morphological examinations with scanning electron microscopy indicated that ULDPE was compatible with NR; thus, the addition of a compatibilizer was not necessary. The cocontinuous phase was dominant in the NR/ULDPE blend containing 50 and 60 wt % NR. The tensile properties, tear resistance, and aging resistance of the NR/ULDPE blends were found to be superior to those of NR/SBR blends. On the other hand, the abrasion and flex cracking resistances of the NR/ULDPE blend were inferior to those exhibited by SBR blends but the Mooney viscosity and resilience of both blends fell in the same range. However, the addition of dicumyl peroxide appeared to have caused crosslinking of the ULDPE phase in the blend, which in turn increased the tensile properties and abrasion and aging resistance. The properties of the tertiary NR/SBR/ULDPE blend were investigated as well. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 650–660, 2001