橡胶硫化促进剂MBT绿色化工艺进展

<正>2-巯基苯并噻唑又称为促进剂MBT,在橡胶硫化促进剂体系中能与橡胶快速硫化,硫化特性好,硫化性能优良,用途广,消耗量大,是橡胶加工工业中广泛使用的一种通用型促进剂,同时也是生产目前使用量最大的次磺酰胺类促进剂的的母体原料。促进剂MBT的合成工艺有苯胺法、硝基苯法、邻硝基氯苯法等。目前国内主要采用苯胺法工艺进行合成。苯胺法是指苯胺和二硫化碳及硫黄在     

橡胶硫化促进剂的催化氧化合成工艺

硫化促进剂在橡胶硫化过程中起着非常重要的作用,它能大大加快橡胶与硫化剂的反应,提高生产率,同时也能改善硫化橡胶的物理机械性能,是目前橡胶工业必不可少的一类主要助剂。按化学结构分,硫化促进剂主要有噻唑类、次磺酰胺类、胍类、秋兰姆类、二硫化氨基甲酸盐类等。就合成工艺而论,新的催化氧化工艺可用于合成胍类、二硫化秋兰姆类和次磺酰胺类促进剂,近年国内外已有工业化生产装置建成投产或专利批准。这一新工艺比传统工艺具有三废少、经济效益高、产品质量好等优点,     

加强二环己胺的应用开发

二环己胺主要用于合成橡胶促进剂、金属缓蚀剂、表面活性剂、油田化学品、医药和农药等领域。随着科技进步 ,其新的应用不断被开发出来 ,而且以其合成的精细化学品大多是有发展前景的新产品。橡胶促进剂二环己胺与 2 -硫醇基苯并噻唑反应 ,可以制备N ,N -二环己基 -2 -苯并噻唑次磺酰胺(DZ)。橡胶促进剂DZ属于目前国家鼓励发展的高效安全次磺酰胺类橡胶硫化促进剂品种之一。在次磺酰胺类促进剂中 ,其焦烧时间最长 ,操作安全性高。此外 ,硫化胶力学性能和动态性能好 ,主要用于轮胎、翻胎、胶带和减震制品。目前国内已有生产 ,但规模极小。…     

我国橡胶促进剂发展现状

1环保型促进剂明显增产促进剂主要包括噻唑类、次磺酰胺类、秋兰姆类、胍类和二硫化氨基甲酸盐类。由于仲胺类促进剂(如NOBS)在硫化过程中会产生致癌物亚硝胺,发达国家已经禁止使用。在我国,作为NOBS的主要替代品,不产生亚硝胺的NS(N-叔丁基-2-苯并噻唑次磺酰胺)已形成较大的生产能力,2005年产量达1.4万t,占促进剂总量的10.1%,发展态势良好。近年来随着橡胶和轮胎工业的快速发展,橡胶促进剂产销两旺,2002～2005年产量统计见表1。2005年橡胶促进剂总产量达到13.8万t,同比增长31.4%。其中两大环保促进剂NS、CBS同比分别增长了94.4%和59…     

浅析硫化促进剂TBBS的合成

摘妻：硫化促进剂能够提高硫化速度,控制硫化过程中的温度,缩短硫化时间,同时起到降低硫磺成本的作用,在如今的橡胶生产中得到了十分广泛的应用。硫化促进剂TBBS（又名NS,化学名为N一叔丁基一2一苯并噻唑次磺酰胺）是一种重要的次磺酰胺类硫化促进剂。它在促进橡胶硫化的过程中不会生成致癌物质,符合绿色环保的发展观,随着可持续发展政策的实施与大力号召,促进剂T1jBs必将在未来得到广泛的应用,拥有极为广阔的发展前景。     

天然胶用的次磺酰亚胺类促进剂

在橡胶行业中能够满足具有较长有效期、较慢硫化速度的由仲胺衍生的苯并噻唑次磺酰胺促进剂已经应用了很多年。最近研究发现MBS(NOBS),N,N—二异丙基—2—苯并噻唑(DIBS)和N,N—二环己基—2—苯并噻唑(DCBS)均能产生有毒的N—亚硝基亚胺。在某些情况下,前硫化防止剂,如CPT以及用伯胺合成的苯并噻唑次磺酰胺,又如N—t—丁基—苯并噻唑次磺酰胺TBBS(NS),都与由仲胺合成的苯并噻唑次磺酰胺类促进剂具有相似的作用,但它     

后效性促进剂对高压胶管胶料性能的影响

分别采用复合硫化体系和低硫高促硫化体系,研究次磺酰胺类促进剂CZ,NS,NOBS和DZ以及噻唑类促进剂M和DM对高压胶管丁腈橡胶(NBR)胶料性能的影响。结果表明:含次磺酰胺类促进剂NBR胶料的综合物理性能、焦烧性能和粘合性能较含噻唑类促进剂NBR胶料好;含噻唑类促进剂NBR胶料的耐油性能与含次磺酰胺类促进剂胶料相当。     

后效性促进剂对高压胶管胶料性能的影响

分别采用复合硫化体系和低硫高促硫化体系,研究次磺酰胺类促进剂CZ,NS,NOBS和DZ以及噻唑类促进剂M和DM对高压胶管丁腈橡胶（NBR）胶料性能的影响。结果表明：含次磺酰胺类促进剂NBR胶料的综合物理性能、焦烧性能和粘合性能较含噻唑类促进剂NBR胶料好;含噻唑类促进剂NBR胶料的耐油性能与含次磺酰胺类促进剂胶料相当。     

次磺酰胺类硫化促进剂热裂解行为初探

采用热重分析法(TG)和裂解气质联用法(PGC-MS)对3种典型的次磺酰胺类橡胶硫化促进剂的热裂解行为进行初步研究。结果表明:在选定的分析条件下,TG法和PGC-MS法分析结果有一定的一致性;TG分析中,促进剂NS的质量损失初始温度、质量损失最快温度和质量损失终止温度均最低,促进剂CZ其次,促进剂DZ最高,促进剂CZ质量损失速率最大;PGC-MS分析中3种促进剂均可以检测到其原分子,小分子胺为区分3种次磺酰胺类硫化促进剂的主要标志物。     

氧气氧化法促进剂NS在橡胶中的应用

研究国家橡胶助剂工程技术研究中心采用氧气氧化法合成的促进剂NS在橡胶中的应用,并与用次氯酸钠法合成的促进剂NS合格品进行对比。试验结果表明:与次氯酸钠法促进剂NS相比,氧气氧化法促进剂NS的理化特性符合或优于国家标准指标;胶料焦烧时间略有延长,硫化速度相当,硫化胶的物理性能得到一定程度提高,耐老化性能略有提高。     

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     

Influence of sulfenamide accelerators on cure kinetics and properties of natural rubber foam

The effect of types of sulfenamide accelerator, i.e., 2‐morpholinothiobenzotiazole (MBS), N‐t‐butylbenzothiazole‐2‐sulfenamide (TBBS), and N‐cyclohexyl benzothiazole‐2‐sulfenamide (CBS) on the cure kinetics and properties of natural rubber foam was studied. It has been found that the natural rubber compound with CBS accelerator shows the fastest sulfur vulcanization rate and the lowest activation energy (E_a) because CBS accelerator produces higher level of basicity of amine species than other sulfenamide accelerators, further forming a complex structure with zinc ion as ligand in sulfur vulcanization. Because of the fastest cure rate of CBS accelerator, natural rubber foam with CBS accelerator shows the smallest bubble size and narrowest bubble size distribution. Moreover, it exhibits the lowest cell density, thermal conductivity and thermal expansion coefficient, as well as the highest compression set as a result of fast crosslink reaction. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44822.     

新型硫化促进剂TBSI在丁腈橡胶中的应用研究

研究了TBSI在丁腈橡胶中的硫化促进性能，并与NS，CZ，TMTD和DM促进剂进行了对比。结果表明，TBSI作NBR硫化促进剂时，焦烧时间长，硫化胶强度高，但硫化速度较慢。当TBSI与TMTD，DM或M组成活化的次磺酰胺并用体系时，不但保证了焦烧安全性，缩短了正硫化时间，而且还进一步提高了硫化胶的300％定伸应力。经4h过硫化反应后，TBSI／TMTD体系的300％定伸应力保持约80％，而NS不足60％。     

Dual Activity of Some Modified Thiocarbamyl Sulfenamides in the Vulcanization of NR Accelerated by Dibenzothiazyl Disulfide

The retarding and the accelerating activities of some modified thiocarbamyl sulfenamides—namely, N-cyclopentamethylene thiocarbamyl-N′-(cyclohexyl, thiocyclohexyl) sulfenamide (CPCTS), N-cyclopenta-methylenethiocarbamyl-N′-(cyclohexyl, N-cyclopentamethylene thio) sulfenamide (CPCCS), and N-cyclopentamethylenethiocarbamyl-N′-(cyclohexyl, N-oxydiethylene thio) sulfenamide (CPCOS)—have been studied in dibenzothiazyl disulfide (MBTS)-accelerated vulcanization of natural rubber (NR). It is found that CPCTS, CPCOS, and CPCCS delay the onset of cure and generate active accelerators during vulcanization. In addition to this, the accelerator systems are quite capable of producing age-resistant vulcanizates. The results indicate that thiocarbamyl sulfenamides modified chemically at the >NH functionality retain their accelerating property. Thus CPCTS, CPCOS, and CPCCS play the dual role of an accelerator and a retarder in the vulcanization of NR accelerated by MBTS.     

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.     

橡胶硫化促进剂的研究进展

概述了橡胶硫化促进剂的结构、类型、性能以及橡胶硫化反应机理的研究进展、硫化促进剂的性能表征方法。指出了国内外硫化促进剂的发展趋势。     

机场行李分拣输送机用橡胶鳞板的研制

以丁腈橡胶为主体材料研制高耐磨、阻燃的机场行李分拣输送机用橡胶鳞板。研究了促进剂CZ/TT并用的活化次磺酰胺类硫化体系和聚氯乙烯、氯化石蜡、三氧化二锑、硼酸锌并用阻燃体系对胶料物理性能和阻燃性能的影响。结果表明,当促进剂CZ/TT并用比为0.7/0.35时,胶料的物理性能较好;聚氯乙烯、氯化石蜡、三氧化二锑、硼酸锌并用比为30/25/12/9时,胶料的物理性能和阻燃性能最好。     

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 Cure Synergism. II,Effect of Diisopropyl Thiophosphoryl-N-Oxydiethylene Sulfenamide and Dibenzothiazyl Disulfide in the Vulcanization of NR

Thiazole sulfenamides as well as thiocarbamyl sulfenamides in the presence of dibenzothiazyl disulfide (MBTS) form synergistic combinations of rubber accelerators that provide technologically important rubber vulcanizates. The present investigation explores the feasibility of using thiophosphoryl sulfenamide with MBTS as a binary system of mutually activated accelerators in the vulcanization of rubber. The cure characteristics of the NR compound containing various proportions of diisopropyl thiophosphoryl-N-oxydiethylene sulfenamide (DIPTOS) and MBTS have been investigated keeping the total concentrations of the accelerators at 6 mmol per 100 rubber. The results indicated mutual activity of the mixed accelerators and significant enhancement of torque, modulus, and tensile strength of the resulting vulcanizates. The general character of the reaction of thiophosphoryl sulfenamide and MBTS has been established by replacing DIPTOS by diisopropylthiophosphoryl-N-cyclopentamethylene sulfenamide (DIPTCS), in the investigation. The mutual activity consequent upon the interaction of the accelerators can be demonstrated through isolation and identification of the reaction products formed in the early part of cure using the HPLC technique, which is also extremely helpful in explaining the cure behavior of the different stocks used in the investigation. The study reveals that diisopropylthiophosphoryl-2-benzothiazole disulfide (DIBDS), formed (in situ) as a result of interaction of DIPTOS and MBTS, plays an active part in improving the physical properties of NR vulcanizates. From the chemical analyses of the vulcanizates it is evident that the network structure obtained with the binary system of accelerators is highly rich in monosulfidic linkages that render the vulcanizates resistant to aging at 100°C.     

硫化胶中次磺酰胺类促进剂的鉴定

用高分辨及高度灵敏的裂解毛细管气相色谱－硫选择检测器和衍生－毛细管气相色谱联用分析技术，以添加了促进剂ＣＺ，ＮＯＢＳ，ＮＳ，ＤＺ的硫化胶为研究对象，进行了硫化胶中次磺酰胺类促进剂母体苯并噻唑及上述促进剂相应的残留胺的测定，然后综合两步的分析结果，准确有效地从硫化胺中鉴定出了上述４种次磺酰胺类促进剂。