天然橡胶增韧聚氯乙烯的研究

采用未改性的标准天然橡胶(NR)作增韧剂,通过机械共混法制备增韧聚氯乙烯(PVC)复合材料,考察了NR和增容剂用量对PVC增韧效果以及力学性能的影响.结果表明:当NR用量为10份时,材料的冲击强度最高为24.87 kJ/m2;加入增容剂环氧化天然橡胶(ENR)后,材料的冲击强度随其用量的增加而增大,在ENR为5份时其冲击强度为69.86 kJ/m2;氯化聚乙烯(CPE)作增容剂时,其冲击强度先升后降,在4份时达到峰值103.93 kJ/m2;氯化橡胶(CNR)作增容剂在3份时,其冲击强度达到最佳值35.37 kJ/m2;增容增韧后共混物的拉伸强度普遍降低.     

Epoxidized natural rubber/epoxy blends: Phase morphology and thermomechanical properties

Epoxidized natural rubbers (ENRs) were prepared. ENRs with different concentrations of up to 20 wt % were used as modifiers for epoxy resin. The epoxy monomer was cured with nadic methyl anhydride as a hardener in the presence of N,N‐dimethyl benzyl amine as an accelerator. The addition of ENR to an anhydride hardener/epoxy monomer mixture gave rise to the formation of a phase‐separated structure consisting of rubber domains dispersed in the epoxy‐rich phase. The particle size increased with increasing ENR content. The phase separation was investigated by scanning electron microscopy and dynamic mechanical analysis. The viscoelastic behavior of the liquid‐rubber‐modified epoxy resin was also evaluated with dynamic mechanical analysis. The storage moduli, loss moduli, and tan δ values were determined for the blends of the epoxy resin with ENR. The effect of the addition of rubber on the glass‐transition temperature of the epoxy matrix was followed. The thermal stability of the ENR‐modified epoxy resin was studied with thermogravimetric analysis. Parameters such as the onset of degradation, maximum degradation temperature, and final degradation were not affected by the addition of ENR. The mechanical properties of the liquid‐natural‐rubber‐modified epoxy resin were measured in terms of the fracture toughness and impact strength. The maximum impact strength and fracture toughness were observed with 10 wt % ENR modified epoxy blends. Various toughening mechanisms responsible for the enhancement in toughness of the diglycidyl ether of the bisphenol A/ENR blends were investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39906.     

Compatibilization of poly(lactic acid)/epoxidized natural rubber blend with maleic anhydride

The objective of this work was to determine the compatibilization effect of different concentrations of maleic anhydride (MA) in poly(lactic acid) blended with epoxidized natural rubber (PLA/ENR). ENR-grafted MA [ENR-g-MA] was synthesized using four concentrations of MA: 0.15, 0.30, 0.45, and 0.60 phr. Using an internal mixer, binary (PLA/ENR, PLA/ENR-g-MA) and ternary (PLA/ENR/ENR-g-MA) polymer blends were prepared with a constant rubber content of 10 wt %. ENR impaired the mechanical properties of PLA, perhaps due to the relatively large size of the rubber particles. The compatibilization effect of MA was evaluated from the results of impact strength testing. ENR-g-MA was a toughening agent for PLA when the concentration of MA was in the range of 0.30–0.60 phr. MA increased miscibility between PLA and ENR. This effect was indicated in the blends by reductions in rubber particle size, the glass transition temperature of PLA, and the α-transition temperatures of PLA and ENR. In the binary polymer blends, the MA concentration in ENR-g-MA that produced the optimal mechanical properties of PLA was 0.60 phr. In the ternary blends, mechanical properties of PLA did not improve at any concentration of MA in ENR-g-MA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48297.     

In situ dispersion and compatibilization of lignin/epoxidized natural rubber composites: reactivity,morphology and property

Lignin, a naturally occurring polymer, was viewed as a potential substitute of carbon black for reinforcing rubber materials. However, it shows no reinforcing effect if directly mixed with rubber. In this study, lignin was in situ dispersed at submicrometer size and highly compatible with epoxidized natural rubber (ENR) by using a high‐temperature dynamic heat treatment (HTDHT). Rheology analysis indicated that the ring opening reaction between lignin and ENR occurred at 160°C or above, which was further confirmed by infrared spectroscopy. Due to the consumption of acidic groups of lignin by ENR, the retardant vulcanization effect of lignin was weakened. Morphology observation and dynamic mechanical analysis demonstrated the perfect lignin dispersion and the strong interactions between lignin and ENR. The mechanical properties of the lignin/ENR composites were significantly improved by using HTDHT. Compared to the directly mixed rubber composites, the tensile strength and tear strength of the heat treated rubber composites filled with 40 phr lignin were increased by 114% and 23%, respectively. Especially, the 300% modulus of the heat treated rubber composite was increased by ca. 400%. X‐ray diffraction results indicated that the reinforcement of the composites originated from the presence of lignin rather than the strain‐induced crystallization of ENR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42044.     

Comparison of thermoset soy protein resin toughening by natural rubber and epoxidized natural rubber

Fully bio‐based soy protein isolate (SPI) resins were toughened using natural rubber (NR) and epoxidized natural rubber (ENR). Resin compositions containing up to 30 wt % NR or ENR were prepared and characterized for their physical, chemical and mechanical properties. Crosslinking between SPI and ENR was confirmed using ¹H‐NMR and ATR‐FTIR. All SPI/NR resins exhibited two distinctive drops in their modulus at glass transition temperature (T_g ) and degradation temperature (T_d ) at around ?50 and 215 °C, corresponding to major segmental motions of NR and SPI, respectively. SPI/ENR resins showed similar T_g and T_d transitions at slightly higher temperatures. For SPI/ENR specimens the increase in ENR content from 0 to 30 wt % showed major increase in T_g from ?23 to 13 °C as a result of crosslinking between SPI and ENR. The increase in ENR content from 0 to 30 wt % increased the fracture toughness from 0.13 to 1.02 MPa with minimum loss of tensile properties. The results indicated that ENR was not only more effective in toughening SPI than NR but the tensile properties of SPI/ENR were also significantly higher than the corresponding compositions of SPI/NR. SPI/ENR green resin with higher toughness could be used as fully biodegradable thermoset resin in many applications including green composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44665.     

Polymer blends of epoxy resin and epoxidized natural rubber

The aim of this research was to investigate the behaviors of epoxy resin blended with epoxidized natural rubber (ENR). ENRs were prepared via in situ epoxidation method so that the obtained ENRs contained epoxide groups 25, 40, 50, 60, 70, and 80 mol %. The amounts of ENRs in the blends were 2, 5, 7, and 10 parts per hundred of epoxy resin (phr). From the results, it was found that the impact strength of epoxy resin can be improved by blending with ENRs. Tensile strength and Young's modulus were found to be decreased with an increasing amount of epoxide groups in ENR and also with an increasing amount of ENR in the blends. Meanwhile, percent elongation at break slightly increased when ENR content was not over 5 phr. In addition, flexural strength and flexural modulus of the blends were mostly lower than the epoxy resin. Scanning electron microscope micrograph of fracture surface suggested that the toughening of epoxy resin was induced by the presence of ENR globular nodules attached to the epoxy matrix. TGA and DSC analysis revealed that thermal decomposition temperature and glass transition temperature of the samples were slightly different. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 452–459, 2006     

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     

Modification of epoxidized natural rubber as a PLA toughening agent

In the present study, the modification of epoxidized natural rubber (ENR) was investigated to improve toughness of PLA. ENR-PLA copolymers were synthesized by 2 steps reactions. Acid hydrolysis of ENR to prepare macroinitiator (ENR-OH) and copolymerization with lactide to obtain ENR-PLA copolymers. The reaction time of acid hydrolysis and the lactide monomer loading was investigated. The optimum conditions were 8 h acid hydrolysis with 5wt% lactide loading to obtain ENR8-PLA5 copolymers. A series of samples of PLA blended with ENR-PLA copolymers was prepared using melt-blending. The blend of PLA with ENR8-PLA5 copolymers at 1 phr substantially improved the tensile properties. The elongation at break was increased 67%, and toughness was increased 64% compared to neat PLA. These results indicate that ENR8-PLA5 has potential as toughening agent for PLA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48267.     

Improving adhesion properties between rubber compound and brass-plated steel cord by the addition of epoxidized natural rubber to rubber compound

The adhesion between a rubber compound containing epoxidized natural rubber (ENR) and a brassplated steel cord was studied to shed light on the role of ENR for the improvement of adhesion. The addition of ENR in the rubber compound caused cure rate to decrease, and as ENR loading increased, modulus and hardness increased while tensile strength and elongation at break decreased. An improvement of adhesion was obvious with low loading of ENR at the range of 2 phr, while an adverse effect was observed with higher concentrations of 10 phr. Since the ratio of sulfur to copper at the interphase of the rubber compound/brass film adhesion sample increases with increased ENR loading up to 2 phr, the acceleration of sulfide formation by ENR could be proven. Adequate curing of rubber and the formation of high-molecular layer at the interphase by addition of small amount of ENR improve adhesion. However, the toughening of the rubber caused by the addition of larger amounts of ENR degrades the adhesion due to the poor physical properties of the rubber compound.     

Effects of in‐situ functionalization of carbon nanotubes with bis(triethoxysilylpropyl) tetrasulfide (TESPT) and 3‐aminopropyltriethoxysilane (APTES) on properties of epoxidized natural rubber–carbon nanotube composites

Composites of carbon nanotubes (CNT) and epoxidized natural rubber (ENR) were prepared by in‐situ functionalization of CNT with two alternative silane coupling agents: bis(triethoxysilylpropyl) tetrasulfide (TESPT) and 3‐aminopropyltriethoxysilane (APTES). The reactions of ENR molecules with the functional groups on CNT surfaces and with the silane molecules were characterized by Fourier transform infrared. Furthermore, cross‐link density, relaxation behaviors, curing, mechanical, electrical, and morphological properties of pristine ENR and the ENR composites were investigated. Very low percolation thresholds, at CNT concentrations as low as 1 phr, were observed in the ENR–CNT and the ENR–CNT–TESPT composites. This might be attributed to improvements in the chemical linkages between ENR molecules and functional groups on CNT surfaces that led to a homogenous dispersion of CNTs in the ENR matrix, with loose CNT agglomerates. POLYM. ENG. SCI., 55:2500–2510, 2015. © 2015 Society of Plastics Engineers     

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.     

Cure and mechanical properties of filled SMR L/ENR 25 and SMR L/SBR blends

The effect of blend ratio of natural rubber/epoxidized natural rubber (SMR L/ENR 25) and natural rubber/styrene‐butadiene rubber (SMR L/SBR) blends on scorch time (t₂), cure time (t₉₀), resilience, hardness, and fatigue properties were studied in the presence of carbon black and silica. An accelerated sulfur vulcanization system was used throughout the investigation. The scorch and cure times of the rubber compound were assessed by using a Moving‐Die Rheometer (MDR 2000). Resilience, hardness, and fatigue life were determined by using a Wallace Dunlop Tripsometer, a Wallace Dead Load Hardness Tester, and a Fatigue to Failure Tester, respectively. The results indicate that t₂ and t₉₀ decrease with increasing ENR 25 composition in the SMR L/ENR 25 blend whereas both values increase with increasing SBR content in the SMR L/SBR blend. This observation is attributed to faster cure in ENR 25 and higher saturation in SBR. Resilience decreases with increase in % ENR and % SBR but hardness shows the reverse behavior in their respective blends. The fatigue life increases with % ENR, but it passes through a maximum with % SBR in the respective blends. In all cases, aging lowers the fatigue life, a phenomenon that is caused by the breakdown of crosslinks in the vulcanizate. Differences in all the observed values between carbon black‐filled and silica‐filled blends are associated with the varying degrees of interaction and dispersion of the two fillers in the rubber blend matrix. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 47–52, 2001     

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.     

Epoxidized natural rubber toughened poly(lactic acid)/halloysite nanocomposites with high activation energy of water diffusion

Poly(lactic acid)/halloysite nanotube (PLA/HNT) nanocomposites were prepared using melt compounding followed by compression molding. Epoxidized natural rubber (ENR) was used to toughen the PLA nanocomposites. The properties of PLA/HNT nanocomposites were characterized by impact tests, thermal analysis (DSC), morphological analysis (FESEM, TEM), and Fourier transform infrared spectroscopy (FTIR). Water absorption tests were performed at three immersion temperature (30, 40, 50°C). The maximum water absorption (M_m), diffusion coefficient (D), and the activation energy of water diffusion (E_a) were determined. The impact strength of PLA/HNT6 nanocomposites was increased significantly to ～296% by the addition of 15 wt % ENR. The incorporation of HNT and ENR increase its nucleation effect and assist in the crystallization process of PLA. The HNT has good affinity with PLA and ENR, which was revealed by TEM and FTIR. The M_m of PLA was increased in the presence of HNT and ENR. Nevertheless, the D value and the E_a of the PLA nanocomposites were found to be affected by the HNT and ENR contents. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42850.     

Toughening of epoxy hybrid nanocomposites modified with silica nanoparticles and epoxidized natural rubber

Silica nanoparticles (SN) and epoxidized natural rubber (ENR) were used as binary component fillers in toughening diglycidyl ether of bisphenol A (DGEBA) cured cycloaliphatic polyamine. For a single component filler system, the addition of ENR resulted in significantly improved fracture toughness (K_IC) but reduction of glass transition temperature (T_g) and modulus of epoxy resins. On the other hand, the addition of SN resulted in a modest increase in toughness and T_g but significant improvement in modulus. Combining and balancing both fillers in hybrid ENR/SN/epoxy systems exhibited improvements in the Young’s modulus and T_g, and most importantly the K_IC, which can be explained by synergistic impact from the inherent characteristics associated with each filler. The highest K_IC was achieved with addition of small amounts of SN (5 wt.%) to the epoxy containing 5–7.5 wt.% ENR, where the K_IC was distinctly higher than with the epoxy containing ENR alone at the same total filler content. Evidence through scanning electron microscopy (SEM) and transmission optical microscopy (TOM) revealed that cavitation of rubber particles with matrix shear yielding and particle debonding with subsequent void growth of silica nanoparticles were the main toughening mechanisms for the toughness improvements for epoxy. The fracture toughness enhancement for hybrid nanocomposites involved an increase in damage zone size in epoxy matrix due to the presence of ENR and SN, which led to dissipating more energy near the crack-tip region.     

Influence of interfacial compatibilizer,silane modification,and filler hybrid on the performance of NR/NBR blends

The effects of epoxidized natural rubber (ENR) as a compatibilizer, silane in situ modification, and filler hybrid on the properties of natural rubber/acrylonitrile–butadiene rubber blends were systematically studied. Phase change with the incorporation of ENR was quantitatively characterized via atomic force microscope quantitative nanomechanics technique. The results show that ENR could greatly reduce the dispersed domain size and increase the interfacial thickness; however, this compatibilizing effect reached the limit when ENR content was 5 parts per hundred rubber (phr). If the content is further increased, the redundant ENR start to gather at the interface and thus form a third phase. The macroscopic dynamic performance measurement was well in accordance with the microscale observation; the blend with 5 phr of ENR presented the lowest heat generation. The results also revealed that silane modification could significantly improve the overall properties, which benefited from better filler dispersal as evidenced by transmission electron microscopy. Finally, the effect of filler hybrid [silica and carbon black (CB)] was studied. It turned out that the blend containing 20 phr silica and 32 phr CB synchronously possessed high wet grip property, low rolling resistance, and high wear resistance, which makes it very promising for the high-performance tire application. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47421.     

Exploring a highly dispersible silica–elastomer composite for tire applications

In this article, we provide an extensive analyses of various properties that are required for tire tread based on developed highly dispersible (HD) silica‐filled epoxidized natural rubber composites. Silica in an HD form has become a staple filler in tire tread applications because of its inherent advantages. In this study, epoxidized natural rubber with 25 mol % epoxide (ENR 25) and natural rubber were mixed with two different types of HD silica for superior reinforcement. A standard tire tread formulation was used as the base compound. The magic triangle properties were conspicuously influenced by the viscoelastic characteristics of the vulcanizates. The introduction of polar rubber (ENR 25) into the HD silica greatly improved rheological, physicomechanical, bound rubber content, and dynamic mechanical properties, and this led to a better, fuel‐efficient tire. We successfully achieved this, even in the absence of a silane coupling agent. ENR 25 played an imperative role in showing an extraordinary rubber–filler interactions and was primarily responsible for these observations. In this study, we explored the HD silica dispersion with transmission electron microscopy observations. Morphological studies revealed well‐dispersed HD silica with the formation of a rubber–filler network. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43531.     

The Curing Behavior and Adhesion Strength of the Epoxidized Natural Rubber Modified Epoxy/Dicyandiamide System

The curing properties and adhesive strengths of the epoxidized natural rubber (ENR, 25 mole percent epoxidation) modified epoxy systems are studied with differential thermal calorimetry (DSC), scanning electron microscopy (SEM), and lap shear strength (LSS) measurement. The results of DSC analyses indicate that the curing exotherm, the curing rate, the reaction order, and the glass transition temperature of the epoxy system are affected by the presence of reactive ENR. From SEM micrographs, it is obtained that a second spherical rubber phase is formed during cure and the particle size of the rubber phase is increased by increasing the curing temperature and the ENR content. The changes of the volume fraction of the rubber phase and the T_g of the cured systems indicate that the mutual dissolution between epoxy resin and ENR happens and which changes with the curing temperature and the ENR content. The LSS of adhesive joints prepared with the ENR modified adhesives are all lower than those of the unmodified epoxy system, and decrease with increasing the amount of ENR added because of the limited compatibility of the ENR with the epoxy matrix.     

Dependence of Peel Adhesion on Molecular Weight of Epoxidized Natural Rubber

The effect of molecular weight of two grades of epoxidized natural rubber (ENR)—i.e., ENR 25 and ENR 50—on the peel strength of an adhesive is studied using coumarone-indene resin, gum rosin, and petro resin as tackifiers. Toluene and polyethylene terephthalate (PET) film acted as the solvent and substrate, respectively. A SHEEN hand coater was used to coat the adhesive on the substrate to give coating thicknesses of 30, 60, 90, and 120 µm. The peel strength of adhesive was determined using a Lloyd Adhesion Tester operating at 30 cm/min. Results show that peel strength has a maximum value at a molecular weight of 6.8 × 10⁴ and 3.9 × 10⁴ for ENR 25 and ENR 50, respectively, an observation which is attributed to the combined effects of wettability and mechanical strength of the rubber at the respective optimum molecular weight of ENR. Peel strength increases with coating thickness for all the tackifiers investigated, with a gum rosin-based adhesive exhibiting the highest peel strength.     

Role of geopolymer as a cure activator in sulfur vulcanization of epoxidized natural rubber

Geopolymer (GP) was synthesized and used as activators in sulfur vulcanization of epoxidized natural rubber (ENR). Influences of GP on cure characteristics, crosslink density, mechanical, thermal, and morphological properties were investigated and compared to the conventional rubber formulation with ZnO activator. The ZnO is a hazardous chemical for the environment and has proclaimed that its application in rubber technology should be reduced and controlled. It was found that the GP-activated ENR compounds showed significantly higher vulcanization rate than cases with the conventional ZnO compound. This was indicated by the GP activated compounds having shorter scorch time, cure times, and lower activation energy but higher cure rate index (CRI). Also, the GP activated ENR compounded with stearic acid exhibited the highest conversion. This matches well the highest torque difference and crosslink density, observed by temperature scanning stress relaxation (TSSR) and swelling measurements. Furthermore, the GP-activated vulcanizate had better thermal stability than the ZnO-activated ENR material. In addition, the GP-activated ENR vulcanizate with stearic acid exhibited high 100% moduli, tensile strength, and hardness. This proves that GP has a high potential for use as activators in sulfur vulcanization of rubber compounds, as an alternative to the conventional ZnO. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48624.