Effect of carbon black on self‐crosslinking network structure of polychloroprene rubber and epoxidized natural rubber blends

The goal of this research is to improve poor network structure of polychloroprene rubber (CR)/epoxidized natural rubber (ENR) self‐crosslinking blends, which could substitute traditional vulcanizates in some application area. Carbon black (CB)–CR/ENR blends were prepared by reacting CR with ENR in the presence of CB. The structure of CR/ENR blends was characterized by attenuated total‐reflectance Fourier transform infrared spectroscopy (FTIR‐ATR). The effect of CB loading on curing characterization and mechanical properties of CR/ENR blends was investigated, and the interaction among CR, ENR, and CB was studied using differential scanning calorimetry. The effect of CB loading on the Payne effect of CR/ENR was investigated using rubber process analyzer. Scanning electron microscope was used to characterize the morphology of CB–CR/ENR blends. The results showed that CR/ENR blends were obtained by the ring‐opening reaction of epoxy groups in ENR and chlorine groups in CR. Mechanical properties of CR/ENR blends increased with the increase of CB loading. The Payne effect of CR/ENR became more remarkable with increasing CB loading. Morphology study indicated that interfacial compatibility between CR and ENR increased with the increase of CB loading because CB could strengthen the self‐crosslinking network structure of CR/ENR blends. The promoting effect of CB on self‐crosslinking reaction was verified by the assessment of crosslink density. POLYM. COMPOS., 38:463–471, 2017. © 2015 Society of Plastics Engineers     

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.     

Mooney scorch time of epoxidized natural rubber

The scorch property of accelerated sulfur vulcanization of three grades of expoxidized natural rubber (viz. ENR 10, ENR 25, and ENR 50) was studied by using Mooney Shearing Disk Viscometer in the temperature range of 100–180°C. Effects of accelerator types, concentration of accelerator, and carbon black on ENR 10 were also determined. Results obtained indicate a similar scorch behavior as that reported earlier for SMR L. However, some differences in the magnitude of scorch times in the temperature and concentration studies are observed between ENR and SMR L. These differences are attributed to the activation of a double bond by the adjacent epoxide group in ENR, the effect being more significant for a higher degree of epoxidation of natural rubber. In the case of ENR 50, differential scanning calorimetry measurement suggests that additional crosslink occurs via a ring-opening reaction at about 155°C. Based on first-order reaction kinetics, the apparent activation energy of vulcanization for the rubbers studied is estimated and discussed.     

Reactions between epoxidized natural rubber and palm oil‐based alkyds at ambient temperature

The reactions between epoxidized natural rubber (ENR) and a low‐molecular weight palm oil‐based alkyd (A1) have been investigated. Experimental results (FTIR and toluene swelling tests) showed that the alkyd having both hydroxyl and carboxylic groups could react with the epoxide groups of ENR at ambient temperature to cause crosslinking. To establish the predominant reaction, alkyd A1 was chemically modified to vary the amount of hydroxyl and carboxylic groups. A1 was treated with maleic anhydride under two different temperatures of 130 and 185°C. At 130°C, the anhydride has reacted partially with the hydroxyl groups to produce alkyd A2 with higher carboxylic content and lower hydroxyl content. On the other hand, at 185°C, the anhydride has reacted completely to produce alkyd A3 with similar carboxylic acid content as A1 but lower hydroxyl content. Subsequent reactions of A2 and A3 with ENR under similar conditions have demonstrated that the predominant reaction with epoxide groups was due to the carboxylic groups from the fact that A2 could form higher amount of crosslinkages than A3, which has lower carboxylic content similar to A1. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of foaming temperature and rubber grades on properties of natural rubber foams

Foaming temperature and grade of dry natural rubber were varied to evaluate their effects on the morphology and mechanical properties of natural rubber (NR) foams. Three different grades of NR were used; namely ENR‐25, SMR‐L, and SMR‐10. NR foams from these grades were produced at three different foaming temperatures, i.e. 140, 150, and 160°C. The study was carried out using formulated compositions containing sodium bicarbonate as the chemical blowing agent and were expanded using conventional compression molding technique via a heat transfer foaming process. The NR foams were characterized with respect to their relative foam density, density of crosslinking, cell size, compression stress, and compression set. Increase in foaming temperature resulted in lower relative density and larger cell size. It was also discovered that the crosslink density slightly decrease with increasing foaming temperature. For mechanical properties, the highest foam density resulted in the highest compression stress. Compression stress at 50% strain increased with increasing foaming temperature and ENR‐25 foam has the highest compression stress among the produced foams. The results showed that the morphology, physical, and mechanical properties of the rubber foams can be controlled closely by the foaming temperature and rubber grades. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermally induced crosslinking between polyacrylic acid and epoxidized natural rubber. III. Effect of carbon black filler and mixer rotor speed

High-temperature molding of Brabender-mixed blend of polyacrylic acid (PAA) and epoxidized natural rubber (ENR) causes thermally induced crosslinking between PAA and ENR. Studies on Monsanto rheometry of the blend and physical properties, solvent swelling, and dynamic mechanical properties of the molded blend show that both mixer rotor speed and carbon black filler influence the crosslinking between the component polymers. For example, the extent of crosslinking for the 50–50 PAA–ENR blend was found maximum when the component polymers were mixed at 40 rpm, but the same blend filled with 30 phr HAF carbon black filler showed maximum crosslinking when mixing was carried out at 120 rpm. The results have been explained on the basis of formation of network on the filler surface, which in turn depends on two competing factors: increase in bound rubber formation with increase in filler loading at a fixed rotor speed and enhanced degradation of ENR at higher mixer rotor speed at a fixed filler loading. © 1994 John Wiley & Sons, Inc.     

Effect of blend ratio on Mooney scorch time of rubber blends

The Mooney scorch times of three rubber blends [epoxidized natural rubber (ENR) 50/SMR L, ENR 50/styrene butadiene rubber (SBR), and Standard Malaysian Rubber SMR L/SBR] were studied in the temperature range of 120–160°C using an automatic Mooney viscometer. N-Cyclohexyl-2-benzothiazyl sulfenamide was used as the accelerator, and the rubber formulation was based on the conventional vulcanization system. Results for the blends investigated indicate that a negative deviation of scorch time from the interpolated value was observed, especially for temperatures lower than 130°C. This observation was attributed to the induction effect of the ENR 50 in the ENR 50/SMR L and ENR 50/SBR blends to produce more activated precursors to crosslinks, thus enhancing interphase crosslinking. To a lesser extent, SMR L also exhibited such an induction effect in the SMR L/SBR blend. At 120°C, maximum induction effect occurred at around a 40% blend ratio of ENR 50 and SMR L in the respective blends. For the filled stock at 140°C, carbon black exhibited less effect on the scorch property of the blends compared to silica. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1301–1305, 1998     

Electron beam irradiation of epoxidized natural rubber: FTIR studies

The effect of irradiation on the structure of epoxidized (50 %) natural rubber (ENR50) has been studied using Fourier transform infrared spectroscopy (FTIR). ENR50 was irradiated using a 3.0 MeV electron beam machine with doses ranging from 20 to 200 kGy. The influence of several additives such as trimethylolpropane triacrylate (TMPTA). Irganox®1010, and tribasic lead sulfate on the irradiation‐induced changes of ENR50 is investigated. Upon irradiation, ring opening of epoxide groups, and oxidation and crosslinking of residual double bonds occurred, leading to decreases in the intensities of epoxide and cis double bond bands and an increases in ether, furan and hydroxyl bands. Gel fraction and hardness values have been used to correlate changes in the structure of the rubber upon irradiation. The results show that the increase in gel fraction upon irradiation of pure ENR50 can be associated with irradiation‐induced crosslinking, ring opening side‐chain reactions of oxirane groups and oxidation at the cis‐double bonds. The addition of Irganox®1010 and tribasic lead sulfate inhibits irradiation‐induced reactions in ENR50 to a considerable extent. The importance of TMPTA in preventing intramolecular ring opening side‐chain reactions is also discussed. However, our studies do not reveal the exact nature of the irradiation‐induced reactions involved in ENR. © 2000 Society of Chemical Industry     

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     

Strain‐induced crystallization behavior of polychloroprene rubber

The crystallization behavior of polychloroprene rubber (CR) has been studied in this work. Differential scanning calorimetry (DSC) was applied to characterize the crystallization behavior. And X‐ray diffraction was applied to determine the impact of crosslinking on the crystallization of CR. Synchrotron X‐ray diffraction (SXRD) method was applied to study the dynamic crystalline behavior. On the basis of the experimental results, it is found that crosslinking will hamper the crystallization of CR while large strain can restore this course. And this is in accord with the Mooney‐Rivlin analysis result. Detailed discussion was offered circling around this phenomenon. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

环氧化天然橡胶与白炭黑及Si 69之间的反应及其对白炭黑填充溶聚丁苯橡胶性能的影响

研究了环氧化天然橡胶(ENR)与白炭黑及改性剂Si 69之间的反应及其对白炭黑/溶聚丁苯橡胶复合材料中白炭黑的分散状况以及复合材料力学性能的影响。结果表明,ENR中的环氧基团开环与白炭黑发生反应,但不能开环与Si 69发生反应。由于ENR与白炭黑的反应速率较慢,导致ENR改性白炭黑在溶聚丁苯橡胶混炼胶与硫化胶中的分散状况有所不同。但是将ENR和Si 69同时加入到白炭黑/溶聚丁苯橡胶复合材料中后,与只用Si 69改性白炭黑填充的溶聚丁苯橡胶相比,硫化胶的拉伸强度基本不变,定伸应力、硬度和撕裂强度增大,扯断伸长率和拉伸永久变形减小,这是因为加入ENR和Si 69后即存在白炭黑与ENR及白炭黑与Si 69两种反应,并且ENR中的环氧基团可以活化其相邻的双键,加速硫化,从而导致硫化胶交联密度增大的缘故。     

Self-crosslinkable blend of zinc-sulfonated EPDM and epoxidized natural rubber

The zinc-sulfonated EPDM (SEPDM)–epoxidized natural rubber (ENR) blend is selfcrosslinkable in the sense that it undergoes crosslinking on molding at high temperatures without the aid of any external curing agents. This is evident from Monsanto rheometric, solvent swelling, and infrared spectroscopic studies. The sulfonate anion is believed to react with an epoxide ring, leading to the formation of sulfonate ester and ether crosslinks. The extent of crosslinking depends on the degree of sulfonation of SEPDM and epoxidation level of ENR, the blend ratio, molding time, and temperature. Dynamic mechanical analyses of the blends show the immiscibility of the blend components. The chemical interaction is also manifested in the shift of the glass transition temperature of ENR to the hightemperature region. © 1994 John Wiley & Sons, Inc.     

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.     

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。     

Effect of reinforcing carbon black filler on thermally induced crosslinking of polyacrylic acid-epoxidized natural rubber blend

That carbon black filler influences the thermally induced crosslinking between polyacrylic acid (PAA) and epoxidized natural rubber (ENR) is evident from Monsanto rheometric studies, dynamic mechanical analyses, and physical property measurements. Considerable shift in glass transition temperature, as well as broadening of the loss peak due to ENR, along with disappearance of the loss peak due to PAA, indicate that HAF carbon black, at 20 parts per 100 of total polymer, make the immiscible PAA/ENR blend behave as a compatible blend. © 1993 John Wiley & Sons, Inc.     

The effect of epoxidized natural rubber on mechanical properties of siliceous earth/natural rubber composites

Siliceous earth (SE) is a kind of mineral consisting of lamellar kaolinite, muscovite (aluminum silicate) and corpuscular silica. Natural rubber (NR) composites containing NR as matrix, epoxidized natural rubber (ENR) as compatibilizer and SE as filler were produced by latex coagulating process and cured using a conventional sulfuric system. Monsanto measurements have shown that the ENR accelerates the vulcanization reaction and gives rise to a marked increase of the torque. The results of physico-mechanical properties of NR vulcanizates show that, when SE modified by silane coupling agent and in the meanwhile adding 4 phr of ENR as compatibilizer, maximum tensile strength, elongation at break, reinforcing index (M300/100) of NR/SE vulcanizates were obtained. The dynamic-mechanical properties exhibit the addition of ENR can enhance wet grip characteristics and reduce rolling resistance by lowering tan δ values at 60 °C and increasing tan δ values at 0 °C of NR compounds. The overall results show that properties of SE-reinforced NR substantially improved by adding ENR as compatibilizer. The addition of silane coupling agent and combining an appropriate amount of ENR would be better choice to improve the properties of NR/SE compounds.     

溶剂型橡胶系压敏胶的研究

采用自交联工艺合成溶剂型橡胶系压敏胶,讨论了增粘树脂的用量、软化剂的用量、交联剂的用量、聚合反应温度、烘胶温度和烘胶时间对压敏胶性能的影响。实验表明,增粘树脂可以有效地提高压敏胶的初粘性和剥离强度,交联剂能够全面调节压敏胶的性能,适当的烘烤温度和烘烤时间有利于提高压敏胶的粘接性能。得出了最佳工艺条件为:增粘树脂与天然橡胶的质量比为701∶00,软化剂含量为20%,交联剂为0.4%,接枝共聚的温度为80℃。     

Evidence of irradiation‐induced crosslinking in miscible blends of poly(vinyl chloride)/epoxidized natural rubber in presence of trimethylolpropane triacrylate

Electron‐beam initiated crosslinking of a poly(vinyl chloride)/epoxidized natural rubber blend (PVC/ENR), which contained trimethylolpropane triacrylate (TMPTA), was carried out over a range of irradiation doses (20–200 kGy) and concentrations of TMPTA (1–5 phr). The gelation dose was determined by a method proposed by Charlesby. It was evident from the gelation dose, resilience, hysteresis, glass‐transition temperature (T_g), IR spectroscopy, and scanning electron microscopy studies that the miscible PVC/ENR blend underwent crosslinking by electron‐beam irradiation. The acceleration of crosslinking by the TMPTA was further confirmed in this study. Agreement of the results with a theory relating the T_g with the distance between crosslinks provided further evidence of irradiation‐induced crosslinking. The possible mechanism of crosslinking induced by the irradiation between PVC and ENR is also proposed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1914–1925, 2001     

Long-time sulfenamide-accelerated sulfur vulcanization of natural rubber/chlorobutyl rubber compounds

Sulfenamide-accelerated sulfur vulcanization of natural rubber/chlorobutyl rubber compounds has been investigated at temperatures from 155 to 175°C over 0.1 to 400 min. Continuous measurements in a Cone Rheometer were used to estimate the extent of crosslinking, which was plotted against cure time. On the basis of a kinetic analysis, two first-order vulcanization reactions, crosslinking and degradation, have been evaluated. Over the temperature range studied, there is no significant difference between the values of activation energy for these reactions. The rate of the degradation is slower by a factor of 20 than the rate of crosslinking. The degradation reaction can be limited by increasing the “efficiency” of the vulcanizing system.     

Effect of electron‐beam irradiation on poly(vinyl chloride)/epoxidized natural rubber blend: dynamic mechanical analysis

The irradiation‐induced crosslinking in 50/50 poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blend was investigated by means of dynamic mechanical analysis. The influence of trimethylolpropane triacrylate on the irradiation‐induced crosslinking of PVC/ENR blends was also studied. The enhancement in storage modulus and T_g with irradiation dose indicated the formation of irradiation‐induced crosslinks. This is further supported by the decrease in tan δ_max and loss modulus peak. The compatibility of the blend was found to be improved upon irradiation. The Fox model was used to provide a further insight into the irradiation‐induced compatibility in the blend. Scanning electron microscopy studies on the cryofracture surface morphology of the blends as well as the homopolymer have been undertaken in order to gain more evidence on the irradiation‐induced crosslinking. © 2001 Society of Chemical Industry