Studies on novel binary accelerator system in sulfur vulcanization of natural rubber

The synergistic activity of binary accelerator systems in rubber vulcanization is well known. Thiourea and its derivatives are important secondary accelerators in this context. It is suggested that thiourea containing binary systems of rubber vulcanization proceed by a nucleophilic reaction mechanism. Amidinothioureas (ATUs), which are derivatives of thiourea, have been investigated extensively as secondary accelerators. One of the aims of this study was to get further proof with regard to the theory of the nucleophilic reaction mechanism in such binary systems. In the present study phenyl substituted ATU was used as a secondary accelerator along with mercaptobenzothizyl disulfide, tetramethyl thiuram disulfide, or cyclohexyl benzthiazyl sulfenamide in the sulfur vulcanization of natural rubber. The results showed an appreciable reduction in the cure time for the mixes containing the ATU compared to the reference mixes. These results are indicative of a nucleophilic reaction mechanism in the vulcanization reaction under review. These vulcanizates also showed comparatively better tensile properties and good retention of these properties after aging. The optimum dosages of the secondary accelerator required for these vulcanization reactions were also derived. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1–8, 2001     

Studies on novel binary accelerator system in sulfur vulcanization of natural rubber

The synergistic activity of binary accelerator systems in rubber vulcanization is well known. Binary accelerator systems are being widely used in industry and are becoming increasingly popular because of the fact that such mixed systems can effectively prevent prevulcanization, permit the vulcanization to be carried out at a lower temperature in a shorter time, and produce a vulcanizate with superior mechanical properties compared to those of a stock cured with a single accelerator. Thiourea and its derivatives are important secondary accelerators in this context. It is suggested that thiourea containing binary accelerator systems cause rubber vulcanization to proceed by a nucleophilic reaction mechanism. In the present study 1‐phenyl‐5‐ortho, ‐meta, and ‐para‐tolyl derivatives of 2,4‐dithiobiurets, which are more nucleophilic than thiourea and vary in their nucleophilic reactivity, are used as secondary accelerators along with 2‐morpholinothiobenzothiazole in the vulcanization of natural rubber. The results show an appreciable reduction in the cure time for the mixes containing the dithiobiurets compared to the reference mix. These results are indicative of a nucleophilic reaction mechanism in the vulcanization reaction under consideration. These vulcanizates also demonstrate comparatively better tensile properties and good retention of these properties after aging. An attempt is also made to correlate the variation in physical properties to chemical crosslink formation in the various vulcanizates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3173–3182, 2003     

A new secondary accelerator for the sulfur vulcanization of natural rubber latex and its effect on the rheological properties

The vulcanization of natural rubber (NR) latex can be effectively carried out at low temperatures by using binary accelerator systems containing thiourea (TU) as a secondary accelerator. It was reported that sulfur‐containing nucleophiles such as thiourea enable the primary accelerator to become effective even at low temperatures, indicating a nucleophilic reaction mechanism in such vulcanization reactions. In the present study, a derivative of thiourea [viz. aminoiminomethyl thiourea (AMT)], which is more nucleophilic than thiourea, is used as a secondary accelerator in the sulfur vulcanization of NR latex. One of the aims of this study was to give conclusive evidence for a nucleophilic reaction mechanism. The synergistic effect of the above thiourea derivative with primary accelerators such as tetramethylthiuram disulfide (TMTD), zinc diethyldithiocarbamate (ZDC), and cyclohexylbenzthiazyl sulfenamide (CBS) was studied at two different temperatures (viz. 100 and 120°C). These binary systems were found to be very effective in reducing the optimum cure time of the different mixes compared to control formulations containing TU. The optimum amount of the secondary accelerator required was also determined. Mechanical properties such as tensile strength and tear strength of the vulcanizates were also evaluated. Chemical characterization of the vulcanizates was carried out by determining the total crosslink density. Values of the cure characteristics evaluated support a nucleophilic reaction mechanism in these vulcanization reactions under review. The effect of this secondary accelerator on the rheological behavior of compounded latex is also studied and was found not to affect adversely. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2781–2789, 2004     

Studies on a new binary accelerator system containing TMTD and amidinothiourea in sulfur vulcanization of natural rubber

It is well known that the use of binary accelerator systems in rubber vulcanization provide better physical and chemical properties to the vulcanizates. The present work reports the results obtained on the study of amidinothiourea as a secondary accelerator along with tetramethyl thiuram disulfide (TMTD) in the sulfur vulcanization of natural rubber. Vulcanizates containing amidinothiourea have an appreciable increase in mechanical properties and better retention of these properties after aging compared to the reference mixes used. These mixes containing amidinothiourea showed appreciable reduction in optimum cure time as well. This suggests a nucleophilic reaction mechanism in the vulcanization reactions under review. Mixes with varying concentrations of amidinothiourea were tried; and the optimum level of amidinothiourea required has been derived based on the cure characteristics of the mixes and physical properties of the vulcanizates. © 1994 John Wiley & Sons, Inc.     

Comparison and evaluation of the thermooxidative stability of medical natural rubber latex products prepared with a sulfur vulcanization system and a peroxide vulcanization system

This article deals with our study of the thermooxidative degradation of medical natural rubber latex tubes prepared with sulfur‐prevulcanized latex (sample I) and peroxide‐prevulcanized latex (sample II) in a dynamic air atmosphere by the use of the thermogravimetry/differential thermogravimetry method as well as the evaluation of the thermooxidative stability of these two samples. The test results showed that an oxygen‐absorption mass‐gain process occurred after a slight mass loss; the mass‐gain rate decreased with an increase in the temperature rising rate (β), and this was more prominent in sample II than in sample I. The maximum mass‐gain rate of sample II was 1.43% when β was 5°C/min, which was 5.02 times that of sample I; the thermooxidative stability of sample II was also lower than that of sample I. Because the oxygen absorption of sample II clearly caused serious oxidation, the balanced initial temperature, the temperature of the balanced degradation peak, and the balanced final temperature of sample II in the first reaction stage were obviously lower than those of sample I. The apparent activation energy (E_o = 143.6 kJ/mol) of sample I was significantly higher than that of sample II, and the stability of sample I was also higher than that of sample II. The temperature of the balanced degradation peak of sample II in the second reaction stage was higher than that of sample I, and E_o (154.0 kJ/mol) of sample II was significantly higher than that of sample I; the stability of sample II was also higher. Thermogravimetry curves of the two samples at various β values intercrossed each other, and the temperature at the crosspoint and the degradation rate increased linearly as β increased. On the temperature segment from the initial temperature to the crosspoint, the degradation rate of sample II was higher than that of sample I when the temperature of the two samples was the same, but on the segment from the crosspoint to the final temperature, the degradation rate of sample II was lower than that of sample I when the temperature of the two samples was the same. The degradation rate of the samples at 600°C was 99.2–99.5%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 591–597, 2005     

天然胶乳橡胶手套硫化问题的探讨

<正>一、引言胶乳硫化能充分改变或改善胶乳胶料性能,通常在胶乳配料时提高温度的情况下进行,硫化后的胶乳称为预硫化胶乳。胶乳硫化一般只适用于天然胶乳,是部分或完     

Radiation vulcanization of natural rubber latex with polyfunctional monomers

Natural rubber latex was irradiated with γ-rays from Co-60 in the presence of polyfunctional monomers to accelerate crosslinking of rubber molecules. Hydrophobic monomers were more effective in accelerating the vulcanization than were hydrophilic monomers. This was ascribed to high solubility of hydrophobic monomers in rubber particles. Among the hydrophobic monomers, neopentylglycol dimethacrylate (NPG) exhibited the highest efficiency in accelerating the vulcanization. Advantages of using NPG are (1) high colloidal stability of the irradiated latex and (2) high thermal stability of dried rubber film.     

A kinetic model for sulfur accelerated vulcanization of a natural rubber compound

Vulcanization kinetics for a natural rubber compound were studied by a kinetic approach using the cure meter and DSC methods. A simplified but realistic model reaction scheme was used to simulate induction, curing, and overcure periods continuously. Physically significant parameters of the model were extracted from isothermal experimental data using a cure meter. The calculation demonstrated a good correspondence with isothermal cure meter data over the temperature range studied. The length of induction time, variation of maximum modulus with temperature, and the reversion phenomena observed from cure curves can be predicted. DSC data were found to be incompatible with the cure meter test, because the complex vulcanization reaction system is multiexothermal and it is difficult to isolate the heat due to crosslinking. Hence, the cure meter technique is suggested for the study of crosslink formation. The kinetic approach provides a way to incorporate vulcanization kinetics into simulation of reactive processing operations. © 1996 John Wiley & Sons, Inc.     

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.     

新型氟橡胶硫化剂

近年来,氟橡胶以其优异的耐热、耐油、耐溶剂、耐强氧化剂、阻燃等特性,以及良好的加工性能,越来越受到人们的重视,氟橡胶作为一种不可替代的高性能弹性体材料,不仅在需求上有了大幅度增加,而且其应用范围也正在不断扩大。氟橡胶的加工助剂也成为生产发展的一个重要环节,不少人     

Cure characteristics of unaccelerated sulfur vulcanization of epoxidized natural rubber

The curing characteristics of unaccelerated sulfur vulcanization of ENR 25 and ENR 50 were studied in the temperature range from 100–180°C. The range of sulfur loading was from 1.5 to 6.5 phr. The scorch time was determined by Mooney Shearing Disk Viscometer whereas the initial cure rate, maximum torque, and reversion properties were obtained from the Moving Die Rheometer (MDR 2000). Results shows that ENR 25 gives a longer scorch time than ENR 50, an observation similar to that in an accelerated system reported earlier. For temperature < 120°C, scorch time depends exponentially on sulfur loading for both rubbers. However, this dependence diminishes as temperature is increased. This observation is attributed to the availability of activated sulfur molecules for vulcanization. The initial cure rate and maximum torque increases with increasing sulfur loading. ENR 50, however, exhibits higher value than ENR 25, suggesting faster cure in the former. For a fixed sulfur loading, reversion is a time and temperature-dependent phenomenon. It decreases with increasing sulfur loading because of the increase of cross-linking density for both rubbers stuided. © 1996 John Wiley & Sons, Inc.     

Mechanism of radiation vulcanization of natural rubber latex sensitized by monoacrylates

The mechanism of radiation vulcanization of natural rubber with 2-ethyl hexyl acrylate (2EHA) monomer was investigated using electron spin resonance spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. The primary radicals formed in the arcylate molecule were found to abstract the allylic hydrogens of the polyisoprene. Crossliking may occur through the allylic radicals and/or main chain radicals formed on the polyacrylate. Acrylate was found to concentrate in the rigid regions of the crosslinked rubber indicating heterogeneity and a nonuniform distribution of the acrylate in the latex particles. The addition of the acrylate and the irradiation seems to effect the Brownian motion of the latex particles. Both the viscosity and the NMR peak widths are effected by the irradiation. Addition of 5% 2EHA increases the crosslinking by a factor of 3.6. The thermal stability of the rubber first increases with the dose in the presence of acrylate, but drops at higher doses due to peroxide formation. © 1995 John Wiley & Sons, Inc.     

N‐benzoyl‐N′N′‐disubstituted thioureas—A new binary accelerator system and its effect of nucleophilicity in sulfur vulcanization of natural rubber

The effect of several new binary accelerator systems were studied with special emphasis to the relationship of nucleophilicity to their rheological and mechanical properties. In this study, dialkyl/azacycloalkyl substituted benzoylthioureas (BTU 1‐5) were used as secondary accelerators (SA) along with three different primary accelerators (PA) viz., Cyclohexylbenzthiazylsulfonamide (CBS), Mercaptobenzothiazole (MBT) or Zincdithiocarbamate(ZDC) in the sulfur vulcanization of natural rubber. The effect of these secondary accelerators on the rheological and mechanical properties was found to be improved when compared to the reference mixes. It is noted that the N‐benzoyl‐N′N′‐piperidinylthiourea (BTU 4) is more effective as a secondary accelerator due to the higher nucleophilicity of the same when compared with the test compounds. The ZDC‐BTU gives the best result as binary accelerator system in natural rubber. Chemical characterization was carried out by determining the total crosslink density. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

促进剂M-La的合成及对天然橡胶的硫化促进作用

采用沉淀法用对氨基苯甲酸、氢氧化钠和硝酸镧在乙醇环境下合成了促进剂对氨基苯甲酸镧(M-La),研究了其对天然橡胶硫化的促进作用。通过红外光谱分析、热分析和元素分析等确定所合成促进剂M-La的分子式为La(C_7 H_6 NO_2)_3·2 H_2O。硫化性能测试结果表明,随着促进剂M-La用量的增加,天然橡胶的硫化速率指数由139增加至227,焦烧时间逐渐延长而正硫化时间基本维持不变,硫化胶的加工安全性不断增强;硫化胶交联密度由最初的1.95×10~(-4) mol/g逐渐增大至2.41×10~(-4) mol/g。促进剂M-La对天然橡胶硫化的促进作用比较明显。     

Physical,mechanical, and viscoelastic properties of natural rubber vulcanizates cured with new binary accelerator system

Natural rubber was vulcanized with a new binary accelerator system based on 1‐phenyl‐2,4‐dithiobiuret (DTB) and dicyclohexyl benzothiazyl sulfenamide. A significant reduction in cure time was observed with the addition of DTB. The cure kinetics was investigated and the activation energy was determined. The mechanical properties were improved by adding DTB, and the maximum values are shown at an optimum concentration. Estimates of the concentration of crosslinks and of the relative proportions of different types of crosslinks were made by the chemical characterization of the vulcanizates. The crosslink densities obtained from swelling measurements and stress–strain measurements were compared with those obtained from modulus measurements. All of them follow a similar trend and support the observed mechanical properties. A dynamic mechanical analysis of the mixes was carried out and the activation energy was determined from Arrhenius plots. The glass‐transition temperature was found to increase with the increase in crosslink density and frequency of measurements. The stress–strain curves were found to not deviate from the strain crystallizing nature of natural rubber. The mechanical properties, network characterization, and processing characteristics were used to optimize the DTB concentration. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2193–2203, 2003     

挤出用溴化丁基橡胶硫化体系的研究

溴化丁基橡胶几种典型硫化体系的对比实验,结果表明,用氧化锌体系硫化的溴化丁基橡胶具有良好的焦烧安全性,比较适宜于挤出用;加入促进剂HVA-2,可显著提高胶料的硫化速度和交联程度,并改善焦烧安全性;当氧化锌用量为4份,HVA-2用量为1.5份时,胶料具有较佳的综合物理性能和加工安全性。     

Effect of temperature on sulfur prevulcanization of natural rubber latex

Sulfur prevulcanization of natural rubber latex was conducted at 60, 70, 80, and 90°C for different periods. The extent of crosslinking was assessed. Tensile properties, water absorption, leaching, and stress-relaxation characteristics of the films were also evaluated. The volume fraction of rubber (Vr), which is a measure of crosslink density of the films, showed a maximum when prevulcanization was conducted at 80°C for 2 h or at 90°C for 1 h. At lower temperatures, the rate of reaction was slow. At each temperature, tensile strength and elongation at break decreased when the prevulcanization time increased, whereas the modulus increased up to a maximum crosslinking and thereafter decreased. Water absorption and leaching were more rapid in prevulcanized film than in postvulcanized film. The rate of stress relaxation slightly increased as the extent of prevulcanization increased. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1913–1920, 1997     

氯丁橡胶用快速硫化体系

该文研究了氯丁橡胶用快速硫化体系。结果表明,以4份氧化镁、5份氧化锌、1．5份TMU、0．5份TMTD、0．5份CZ为W型氯丁橡胶的硫化体系,可使胶料具备焦烧时间长、硫化速率快的特点,硫化胶的综合性能较好。     

硫化体系对天然橡胶性能的影响

采用常规硫化体系(CV)、半有效硫化体系(SEV)和有效硫化体系(EV)制备了不同的NR(天然橡胶)硫化胶。着重探讨了不同硫化胶的微观形貌、200%定伸强度、撕裂强度、拉伸强度、断裂伸长率和交联密度。研究结果表明:SEV硫化胶的微观形貌相对较好,填料能均匀分散在基体中;在其他条件保持不变的前提下,当w(NOBS)=w(硫)=2.0%(相对于NR质量而言)时,相应的未老化SEV硫化胶的撕裂强度(78 kN/m)相对最大;SEV硫化胶的交联密度大于CV硫化胶和EV硫化胶,并且适当增加交联密度能有效提高其综合性能,从而为开发新一代轮胎等复合材料奠定了基础。