新型橡塑硫化助剂的合成

以九水硫化钠、硫粉、γ-氯丙基三乙氧基硅烷为原料,甲苯、乙醇作溶剂,合成了双-(γ-三乙氧基硅丙基)二硫化物。讨论了反应物比例、溶剂用量、反应温度和时间等因素对产率的影响。结果表明,最佳工艺条件:硫与九水硫化钠的物质的量比为1.05:1,甲苯与九水硫化钠的物质的量比为36:1,γ-氯丙基三乙氧基硅烷与过硫化钠的物质的量比为2.1:1,无水乙醇与过硫化钠的物质的量比为5.0:1,反应温度为80℃,反应时间为4 h。最终制得的产品外观为淡黄色,类乙醇香味,产率为95.63%,含硫量达13.8%,产品贮存时间长。     

A new binary accelerator system for the sulfur vulcanization of natural rubber latex

Vulcanization of latex products are usually carried out at lower temperatures compared to dry rubber products. It has been suggested that, in latex vulcanization systems where thiourea is used as a secondary accelerator, it acts as a nucleophilic reagent facilitating the cleavage of the sulfur bonds in the primary accelerator like TMTD or CBS at lower temperature. But no conclusive proof is given to such a postulate. In the present study 1-phenyl-2,4-thiobiuret (DTB II) and 1,5-diphenyl-2,4-dithiobiuret (DTB III), which are more nucleophilic than thiourea and which vary in their nucleophilic reactivity, were studied as secondary accelerators along with tetramethyl thiuram disulphide (TMTD) and N-cyclohexylbenzothiazyl sulphenamide (CBS) in the vulcanization of natural rubber latex. These binary systems were found to be very effective in reducing the optimum vulcanization time. Also it was noted that 1-phenyl-2,4-dithiobiuret, which is more nucleophilic, is more reactive (as observed from the reduction in optimum cure time) as a secondary accelerator, indicating a nucleophilic reaction mechanism in the vulcanization reactions under review. The optimum dosages of the secondary accelerators required were derived. Physical properties like tensile strength, 300% modulus, and elongation at break of the latex vulcanizates were also studied. There is a definite advantage with respect to many of these properties for dithiobiuret systems compared to the systems containing TMTD alone or TMTD/thiourea. DTB III gives higher values in many of these physical properties than DTB II. Chemical characterization of the vulcanizates was also carried out to correlate the physical properties with the type of chemical crosslinks formed. © 1993 John Wiley & Sons, Inc.     

Some factors affecting the electrical properties of carbon-black-loaded butyl rubber during vulcanization

Butyl rubber mixtures loaded with 70 phr general purpose furnace black (GPF) and tetramethyl thiuram disulphide (TMTD)/S as vulcanizing system were prepared. The kinetics of their electrical conductivity development during the vulcanization process were followed by using an especially devised system. It was found that the increase in the electrical conductivity during vulcanization obeys an exponential growth function with time constant τ, which markedly decreases with increasing vulcanization temperature as well as with the efficiency of the vulcanizing system. After completion of the vulcanization process, about 80 min, the samples obtained possess reasonable stability and reproducibility of electrical conductivity.     

橡胶硫化反应动力学研究概况

综述橡胶硫化反应的各种动力学机理和硫化反应动力学的研究方法和手段。介绍各种不同的硫化反应机理及其相应的动力学模型方程．列举了等温和不等温条件下的橡胶硫化反应动力学方程。硫化反应动力学的研究方法有物理化学法、硫化仪法和热分析法等．这些方法各有利弊．研究中应将它们结合起来，并对结果进行综合分析。     

A comparison of tetraethylthiuram and tetramethylthiuram disulfide vulcanization. II. Reactions in rubber

The reactions of tetraethylthiuram disulfide (TETD) with polyisoprene were investigated under vulcanization conditions. Samples of polyisoprene compounded with various combinations of TETD, sulfur, and ZnO were heated in a differential scanning calorimeter to various degrees of vulcanization. The crosslink density of the compounds was determined by swelling, and the extractable residual curatives and reaction products were analyzed with high‐performance liquid chromatography. TETD caused crosslinking to occur in the absence of added sulfur, as did tetramethylthiuram disulfide (TMTD), both sulfur donors. In the presence of sulfur, the formation of TETD polysulfides occurred immediately before the crosslinking reaction started. The TETD polysulfides were the initial crosslinking agents. The ready reaction between TETD and zinc oxide to form zinc diethyldithiocarbamic acid resulted in considerably higher crosslink densities. This greater reactivity between TETD and zinc oxide, compared with that between TMTD and zinc oxide, did not lead to any noticeable differences in the vulcanizate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1119–1127, 2002     

Modeling the vulcanization reaction of silicone rubber

Characterization of the vulcanization process of silicone rubber was achieved through the modeling of dynamic DSC tests. The Kissinger equation and the Kamal‐Sourour model were used to determine kinetic parameters that fit the experimental data. The technique allows for the determination of the activation energy through Kissinger's model, which is then used to mathematically determine the other five parameters for the Kamal‐Sourour model. This novel technique finds a physically meaningful activation energy. The method generates a single set of parameters that accurately models all scanning rates tested (1, 2.5, 5, and 10 K/min). Five formulations of liquid silicone rubber as well as one solid silicone rubber were tested and modeled. For each material, the models generated fitting parameters that were in agreement with the dynamic DSC scans. The models were used to compare the processing of the liquid and solid silicone rubber. The characterization of both materials demonstrates the lower processing time, temperatures, and energy consumption when processing liquid silicone rubber, as compared to processing of hard silicone rubber. POLYM. ENG. SCI., 47:675–683, 2007. © 2007 Society of Plastics Engineers.     

氟橡胶双酚AF/BPP硫化体系硫化特性的研究

研究了双酚AF硫化体系中硫化剂双酚AF、促进剂BPP对氟橡胶硫化特性的影响以及硫化温度对硫化特性的影响.结果表明：硫化剂双酚AF的用量主要影响胶料的交联密度以及硫化时间,并且可以改善胶料的加工性能;促进剂BPP的用量主要影响胶料的硫化时间,对加工性能有一定的影响;硫化温度的提高会使交联密度下降.     

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     

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     

A benzoxazole sulfenamide accelerator: Synthesis,structure, property,and implication in rubber vulcanization mechanism

A benzoxazole sulfenamide and its related zinc compound were synthesized and characterized, which are shown to be useful accelerators for sulfur vulcanization. In comparison with the benzothiazole accelerator, the benzoxazole sulfenamide revealed nearly no reversion, an improved feature that is desirable for tire industry. Through the synthesis of the zinc complex 9 , which was assumed to be an accelerator‐activator for vulcanization, the study aimed to shed some light on the vulcanization mechanism. The crystal structure of the zinc complex 9 showed that two benzoxazole‐2‐thiol ligands were attached to the zinc center in different isomeric forms, with one in the thio form (linked via sulfur atom) while the other in thio–keto form (linked via nitrogen atom). Lack of the vulcanization accelerator activity from 9 led to the assumption that the sulfurating species might be zinc complexes containing only one benzoxazole‐2‐thiol ligand. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39699.     

加成型有机硅反应过程的实时监测

用实时傅里叶变换红外光谱仪（FTIR）对乙烯基硅橡胶和含氢硅油的加成聚合过程进行了表征,得到了基团浓度消耗比反应时间变化的曲线,结果表明,在反应过程中,硅氢基与乙烯基的浓度减少呈非线性关系,这可能是硅氢基在反应过程中与空气中的物质进行了反应,从而在消耗量上较乙烯基多的缘故。     

Optimization of the vulcanization process of rubber products

Selection of the optimum conditions for the vulcanization of rubber products, particularly of bulky ones, often is quite difficult. Especially in cases of high demand, it is unavoidable to destruct expensive prototypes in order to check important properties of the rubber at various locations throughout the product. Finite element calculations can be used to predict the flow of heat during the vulcanization process. By converting the total heat input at a selected location during a certain time into a so-called “effective vulcanization time” at a fixed reference temperature, it becomes possible to predict the properties of the rubber at that location. An example of such a procedure is given. However, to secure optimum conditions in this way would require repetitive (expensive) calculations. In this article a method is developed in which the vulcanization conditions are derived from the required properties of the rubber compound. The idea behind it is that optimal vulcanization is reached when at each location within the rubber product the effective vulcanization time at a selected reference temperature lies within predefined limits. The choice of the limits can be derived from the dependence of each of the properties chosen on the vulcanization time at the reference temperature.     

Effect of vulcanization temperature and vulcanization systems on the structure and properties of natural rubber vulcanizates

The effect of vulcanization temperature (150°–180°C) on the structure and technical properties of gum natural rubber vulcanizates with four different 2-(morpholinodithio)-benzothiazole: sulphur ratios (A, 0.6:2.4; B, 1.5:1.5; C, 2.4:0.6; D, 3.0:0.0) at the respective optimum cure times has been determined. The influence of cure temperature on (a) the chemical crosslink density; (b) the distribution of crosslink types; (c) the extent of sulphidic main chain modifications and (d) the zinc sulphide formation was investigated. Results show that elevated cure temperatures produce a network with lower crosslink density, in particular a lower polysulphidic crosslink density. The formation of intramolecular sulphidic groups and zinc sulphide increase with increasing cure temperatures. The possibility of chain scission during vulcanization, as examined by a quantitative analysis of the sol—gel data, was found to be negligible. The network results have been correlated with the technical properties.     

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。     

Contribution to the mechanism of the thiuram vulcanization. I. Polymerization of styrene in the presence of tetramethylthiuram disulfide and natural rubber

The influence of the concentration of tetramethylthiuram disulfide (TMTD) on grafting of natural rubber by styrene at 80°, 95°, 115°, and 130°C and constant molar ratio of rubber and styrene was studied. It was found that the dependence R_p = f([TMTD]^½) at all followed temperatures goes through a maximum and that TMTD substantially decreases the amount of bound rubber in the graft copolymer. The analysis of the kinetic data and the results of separation of polymer mixtures showed the significant role in the process of the termination reactions of the growing polymer and the rubber radicals with the RS radicals. The derived kinetic relation is in good agreement with the experimental, results and allows calculation of the transfer rate constants of RS radical on rubber.     

一种骨架／橡胶制品的硫化工艺装备

介绍了一种骨架／橡胶制品的硫化工艺装备情况,包括硫化成型模具的选择,硫化模具辅助机构以及装模工装和脱模工装的装备、硫化模具辅助机构的装备,介绍了防产品吸附上模的装置和辅助开模装置。硫化生产过程中,根据硫化工艺的需要,加强工艺装备可以极大的提高生产效率、降低劳动强度。     

橡胶硫化过程数值模拟研究进展

硫化作为橡胶制品成型过程中的关键工序,决定着制品的使用性能与尺寸精度,通过模拟仿真技术有助于实现对硫化过程的精确控制以及减少能量消耗。基于此,从微观尺度和宏观尺度两个层面综述了橡胶硫化过程数值模拟的研究进展,重点分析了理论与经验硫化反应动力学模型的发展现状。最后,指出了橡胶硫化过程数值模拟的发展方向与趋势。     

橡胶硫化反应活化能的测定

利用胶料的硫化仪试验数据组拟合直线方程，进行胶料硫化反应活化能计算，并以此为基础编制轮胎硫化测温仪系统的硫化反应活化能计算模块。利用系统模块计算活化能简便、快速，其结果与用阿累尼乌斯方程计算得到的结果基本相同。模块应用时数据点不得少于5个，参比温度须与测定温度接近。     

微波加热技术在橡胶硫化中的应用研究

本文针对橡胶微波加热硫化所存在的问题,应用ANSYS有限元分析软件,在分析比较了传统加热硫化和微波加热硫化胶料温升特点的基础上,提出了微波间歇加热的方法。根据硫化历程,设计了间歇加热的流程图,并模拟分析了微波间歇加热硫化胶料的温度变化趋势,模拟结果显示：采用微波间歇加热硫化能有效的解决微波连续加热硫化升温过快、焦烧时间不足、胶料不能很好充满模型,以及胶料内外温差逐渐加大的问题,对实际工程具有一定的实用价值。     

蛋白质对天然橡胶硫化动力学的影响

选用与天然胶乳中的d球朊结构类似的牛白蛋白,将其加入到经Alcalase蛋白酶处理得到的低蛋白天然橡胶中,通过硫化仪法研究了蛋白质对胶料硫化动力学的影响。结果表明：各胶样的硫化反应可按一级反应处理;在相同温度条件下,随着蛋白质用量的增加,焦烧时间（t10）和正硫化时间（t90）缩短,硫化反应速率提高,说明牛白蛋白能够提高天然橡胶的硫化速度;硫化速率随着温度的升高而显著提高,且都能很好地符合阿伦尼乌斯方程;反应活化能随着蛋白质用量的增加而提高。