Cure behavior and antimicrobial performance of sulfur‐cured natural rubber vulcanizates containing 2‐hydroxypropyl‐3‐piperazinylquinolinecarboxylic acid methacrylate or silver‐substituted zeolite

This work used 2‐hydroxypropyl‐3‐piperazinylquinolinecarboxylic acid methacrylate (HPQM) or silver‐substituted zeolite (SSZ) as antibacterial agents for natural rubber (NR) compounds vulcanized by conventional vulcanization (CV), semi‐efficient vulcanization, and efficient vulcanization (EV) systems. The cure behavior and antibacterial performance of the NR vulcanizates were studied by varying the loadings of HPQM or SSZ, contact times, and vulcanization systems. The antibacterial performance of the rubber compounds was examined by halo test and plate‐count‐agar methods against Escherichia coli (E. coli, ATCC 25922) and Staphylococcus aureus (S. aureus, ATCC 25923) as the testing bacteria. The cure time and crosslink density were dependent on the vulcanization recipe used but were not affected by the addition of HPQM or SSZ. Diphenylguanidine at the level of 1.0 phr (parts by weight per hundred parts of resin) in NR vulcanized by the EV system had the ability to kill the E. coli and S. aureus bacteria. The NR vulcanized by the CV system showed the most pronounced antibacterial performance, as compared with the other two vulcanization systems, via migration and diffusion of HPQM or SSZ onto the NR surfaces, this being identified by the relatively large reduction of contact angle values. The HPQM showed the most preference for NR compounds vulcanized with the CV system with a contact time of 120 min or longer to achieve a bacteria‐killing efficacy of 99.0–99.9%, the efficacy being more pronounced for E. coli bacteria. J. VINYL ADDIT. TECHNOL., 19:123–131, 2013. © 2013 Society of Plastics Engineers     

Effect of 3‐aminopropyltriethoxysilane and N,N‐ dimethyldodecylamine as modifiers of Na+‐montmorillonite on SBR/organoclay nanocomposites

In this study, styrene butadiene rubber (SBR)/organoclay nanocomposites were manufactured using the latex method with 3‐aminopropyltriethoxysilane (APTES) and N,N‐dimethyldodecylamine (DDA) as modifiers. The layer‐to‐layer distance of the silicates was observed according to each manufacturing process for APTES as the modifier using the X‐ray diffraction (XRD) method. From the XRD results and the TEM images, the dispersion of the silicates impoved for both APTES‐MMT and DDA‐MMT, and the dispersion of the silicates with the DDA modifier improved more than the APTES modifier. The SBR/DDA‐MMT compound exhibited the fastest scorch time, optimal vulcanization time, and cure rate. The dynamic viscoelastic properties of the SBR/APTES‐MMT compound were measured according to the change in the strain amplitude in order determine if a covalent bond was formed between APTES and bis(triethoxysilyl‐propyl)tetrasulfide (TESPT). The mechanical properties of the SBR/DDA‐MMT nanocomposite improved more than the SBR/APTES‐MMT composite because the vulcanization effects of alkylamine and the dispersion of silicates within the rubber matrix were relatively good. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Sulfur vulcanization of polyisoprene accelerated by benzothiazole derivatives. III. The reaction of 2-bisbenzothiazole-2,2′-disulfide with sulfur and ZnO in polyisoprene

The sulfur vulcanization of polyisoprene accelerated by 2-bisbenzothiazole-2,2′-disulfide (MBTS) was investigated. Rubber compounds were heated in a DSC and removed at various temperatures along the DSC thermal curve. The rubber vulcanizate was analyzed for crosslink density and for residual reactants and extractable reaction products. MBTS reacts readily with sulfur, and the polysulfidic accelerator complexes react with the rubber chain to form pendent groups. Crosslinking results from hydrogen abstraction, by the benzothiazole pendent group, from a neighboring chain. 2-Mercaptobenzothiazole, a product of crosslinking, also acts as an accelerator in the later stages of the reaction. MBTS has been shown not to react with ZnO and the higher crosslink densities obtained when ZnO is present are attributed to ZnO aiding the abstraction of the benzothiazole pendent group to give zinc mercaptobenzothiazole. A mechanism for the MBTS acceleration of sulfur vulcanization is proposed. © 1996 John Wiley & Sons, Inc.     

Über die vernetzung eines ungesättigten äthylen-propylen-terpolymer-kautschuks

The various aspects of the sulfur vulcanization chemistry and mechanism of ?Nordel”? hydrocarbon rubber, an ethylene-propylene terpolymer, are discussed. The chemical nature of the reactions undergone by the accelerators has been found to be analogous to those observed for natural rubber and SBR. During vulcanization approximately 50% of the double bonds are saturated, and approximately one crosslink is formed for each two double bonds initially present. The type of crosslink formed has been examined and the vulcanization kinetics studied with the aid of a Monsanto rheometer.     

Vulcanization of 1-chlorobutadiene–butadiene rubber with diepoxy compound

Diepoxy vulcanization system of 1-chlorobutadiene–butadiene rubber(CB–BR) having hydroxyl groups with diglycidyl ether of bisphenol A (DGEBA) was studied in the presence of acid anhydrides. Phthalic anhydride (PAn), hexahydrophthalic anhydride (HAn), maleic anhydride (MAn), and succinic anhydride (SAn) were investigated as occuring agents. The results of this investigation indicated that the hydroxyl groups attached to the polybutadiene backbone react with DGEBA to afford a CB–BR vulcanizate rate depended on the kinds of acid anhydrides in the following order: PAn > MAn > SAn > HAn. It is assumed that the reaction between the hydroxyl group in CB–BR and acid anhydride was the rate-determining step. The vulcanization of CB–BR with a higher amount of DGEBA afforded resinous rubber vulcanizates. Thus, DGEBA was concluded to act not only as a curing agent, but also as a reinforcing agent for CB–BR. © 1995 John Wiley & Sons, Inc.     

Polymerization of lactides and lactones. III. Ring-opening polymerization of DL-lactide by the (η3-C3H5)2Sm(μ2-Cl)2(μ3-Cl)2Mg(tmed)(μ2-Cl)Mg(tmed) complex

Ring-opening polymerization of DL -lactide (LA) has been initiated with the (η³-C₃H₅)₂Sm(μ₂-Cl)₂(μ₃-Cl)₂Mg(tmed)(η₂-Cl)Mg(tmed) complex both in bulk and solution. The effects of reaction conditions, such as reaction time, reaction temperature, and monomer/initiator molar ratio on the polymerization has been discussed. The results showed that (η³-C₃H₅)₂Sm(μ₂-Cl)₂(μ₃-Cl)₂Mg(tmed)(μ₂-Cl)Mg(tmed) was more effective for the polymerization of LA, and high molecular weight of polylactide was obtained by this initiator. The solvent affected the polymerization significantly. The polymerization mechanism was in agreement with the coordination mechanism. The polymer was characterized by FTIR, ¹H-NMR, and DSC. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2857–2862, 1999     

Compatibilized and dynamically vulcanized thermoplastic elastomer blends of poly(butylene terephthalate) and ethylene propylene diene rubber

Compatibilized and dynamically vulcanized thermoplastic elastomer blends of poly(butylene terephthalate) (PBT) and ethylene propylene diene terpolymer (EPDM) can be prepared by using an EPDM rubber that contains reactive epoxy groups. During melt mixing the epoxy groups react with PBT endgroups to form graft copolymer. The compatibilized blends can be dynamically vulcanized by conventional vulcanization agents for EPDM such as peroxides or by vulcanization agents that react with residual epoxy groups on the EPDM such as diamines. This paper describes the effects of compatibilization and dynamic vulcanization on microstructure and mechanical properties.     

Dimethylammonium dimethyldithiocarbamate‐accelerated sulfur vulcanization. II. Vulcanization of rubbers and model compound 2,3‐dimethyl‐2‐butene

Rubber and model compound 2,3‐dimethyl‐2‐butene were vulcanized for various times with dimethylammonium dimethyldithiocarbamate [(dma)dmtc]‐accelerated sulfur formulations in the absence of ZnO. Model compound systems were analyzed by HPLC, and no reaction intermediates containing pendent groups were found. Crosslinked sulfides, characterized by ¹H‐NMR, were found to be essentially bis(alkenyl). Residual curatives were extracted from rubber compounds vulcanized for various times and analyzed by HPLC. Compounds, cured to various crosslink densities, were found to crystallize readily in a density column at subambient temperatures. This supports evidence from model compound systems that pendent groups are largely absent from vulcanizates. It is suggested that a reaction mechanism, similar to that applicable to zinc dimethyldithiocarbamate‐accelerated sulfur vulcanization, may be applicable with (dma)dmtc accelerated formulations. Very limited crosslinking occurred on heating compounds under vacuum, and this can be attributed largely to the rapid loss of (dma)dmtc from rubber at elevated temperatures. However, the slower rate of crystallization on cooling of the gels, compared to the rate in press‐cured vulcanizates of similar crosslink density, was interpreted as evidence that some pendent groups did form during heating with (dma)dmtc/sulfur. Crosslinking of such pendent groups may be inhibited by the loss of (dma)dmtc, that, like zinc dimethyldithiocarbamate, may catalyze their crosslinking, and/or to the loss under vacuum of dimethyldithiocarbamic acid that would form thiol pendent groups that would rapidly crosslink with thiuram pendent groups. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3074–3083, 2001     

Effect of carboxyl on vulcanization and mechanical properties of carboxylated acrylic rubber prepared by 60Co‐γ‐ray‐induced polymerization

Acrylic acid carboxylated acrylic rubber (ACM) and itaconic acid carboxylated acrylic rubber were prepared by ⁶⁰Co‐γ‐ray‐induced emulsion copolymerization. The polymers were characterized using FTIR and ¹³C NMR spectroscopies. The acid value was determined with nonaqueous titration method. The molecular weight and the polydispersity index of the polymers were measured using gel permeation chromatography. The influence of the cure‐site (carboxyl) on the vulcanization and mechanical properties of the ACM was researched by means of rheometric study, gel fraction analysis, mechanical property tests, and dynamic mechanical thermal analysis. The results show that the crosslink density of polymers increases with amounts of the carboxyl cure‐site. The itaconic acid carboxylated ACM has better cure characteristics and mechanical properties than the acrylic acid carboxylated ACM has. In addition, the comparison of ACM prepared by ⁶⁰Co‐γ‐ray‐induced polymerization with ACM prepared by chemical‐initiator‐induced polymerization has been investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5587–5594, 2006     

厚壁橡胶制品非等温硫化过程模拟与实验研究

橡胶的硫化反应过程对制品的最终性能起决定性作用,而厚壁橡胶的硫化是典型的非等温硫化过程,通常难以通过实验测得的等温硫化曲线来直接确定制品的最佳硫化工艺。因此,利用数值模拟技术来研究硫化过程对于橡胶的成型加工具有重要意义。鉴于此,基于传统硫化动力学模型,通过引入初始硫化参数并将反应级数视为温度的二次函数,构建了精度更高的改进硫化模型,同时将橡胶热物性参数视为硫化度和温度的函数,基于C语言和FLUENT预定义宏编写了UDF子程序,实现了橡胶制品硫化过程传热与硫化的耦合模拟。针对典型厚壁橡胶制品的平板硫化成型,通过测温实验和不同硫化程度制品拉伸、DSC测试与断面形貌观测,验证了耦合算法对温度场和硫化度模拟的可靠性。该方法对指导厚壁且结构复杂橡胶制品硫化成型更具实际意义。     

橡胶助剂Silane-M对丁苯橡胶/白炭黑复合材料硫化性能的影响

用硫化仪考察了橡胶助剂3-苯并噻唑硫代-1-丙基-三乙氧基硅烷(Silane-M)对丁苯橡胶/白炭黑复合材料硫化性能的影响.结果表明,Silane-M可明显缩短丁苯橡胶/白炭黑复合材料的正硫化时间,但不影响其焦烧时间.Silane-M具有一定的促进作用,可以加快硫化速率.未添加和添加6份(质量)Silane-M的丁苯橡胶/白炭黑复合材料在135～160 ℃的硫化温度系数和硫化反应表观活化能均比较接近,2种复合材料的硫化性能对温度的依赖性基本一致.     

Nitrogen‐doped graphene as an alternative to ecotoxic zinc oxide in rubbers

Zinc oxide (ZnO) is an essential ingredient in industrial rubber production; it regulates the onset of vulcanization, accelerates the kinetics of vulcanization, and improves the mechanical properties of rubber. However, environmental pollution with ZnO is a concern because it is recognized to be significantly ecotoxic and might also have adverse effects on human health. One of the major sources of ZnO environmental pollution is rubber items, tires in particular. Nitrogen (N)‐doped graphene is a promising next‐generation catalyst. We show here that the replacement of 3 phr ZnO by just 0.1 phr N‐doped graphene in styrene–butadiene rubber reduced the vulcanization onset time by more than a factor of two while retaining the fast vulcanization kinetics and enhancing the tensile strength in comparison with rubber with just ZnO. A shorter vulcanization time implies energy savings, which, together with the nontoxicity of N‐graphene, should make the resulting rubbers substantially more environmentally friendly. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46116.     

Thermoplastic natural rubber based on polyamide‐12: Influence of blending technique and type of rubber on temperature scanning stress relaxation and other related properties

Thermoplastic natural rubber based on polyamide‐12 (PA‐12) blend was prepared by melt blending technique. Influence of blending techniques (i.e., simple blend and dynamic vulcanization) and types of natural rubber (i.e., unmodified natural rubber (NR) and epoxidized natural rubber (ENR)) on properties of the blends were investigated. It was found that the simple blends with the proportion of rubber ～ 60 wt % exhibited cocontinuous phase structure while the dynamically cured blends showed dispersed morphology. Furthermore, the blend of ENR exhibited superior mechanical properties, stress relaxation behavior, and fine grain morphology than those of the blend of the unmodified NR. This is attributed to chemical interaction between oxirane groups in ENR molecules and polar functional groups in PA‐12 molecules which caused higher interfacial adhesion. It was also found that the dynamic vulcanization caused enhancement of strength and hardness properties. Temperature scanning stress relaxation measurement revealed improvement of stress relaxation properties and thermal resistance of the dynamically cured ENR/PA‐12 blend. This is attributed to synergistic effects of dynamic vulcanization of ENR and chemical reaction of the ENR and PA‐12 molecules. Furthermore, the dynamically cured ENR/PA‐12 blend exhibited smaller rubber particles dispersed in the PA‐12 matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study on peroxide vulcanization thermodynamics of ethylene–vinyl acetate copolymer rubber using 2,2,6,6,‐tetramethylpiperidinyloxyl nitroxide

A step forward in the understanding of rubber vulcanization with organic peroxides is provided by combining a proper arrangement between polymer, vulcanizing agent and cure conditions. For this purpose, an ethylene–vinyl acetate copolymer with a high content of vinyl acetate (70 mol%) was used since a fully saturated polymer backbone allows its vulcanization via peroxide. For the range of conditions analysed here, it is shown that the predominant process taking place is crosslinking via radical recombination, minimizing or even avoiding undesirable secondary reactions such us polymer degradation. Once conditions had been optimized, peroxide vulcanization was analysed in more depth in the presence of 2,2,6,6‐tetramethylpiperidinyloxyl, which is a mediating stable free radical commonly used in controlled radical polymerization. Consequently, it was possible to differentiate the termination reaction from the initiation and propagation steps, allowing the determination of the enthalpy of formed C–C crosslinks as measured using calorimetry. It was possible to isolate and determine the contribution of the crosslinking pathway from the global vulcanization reaction by means of calorimetric methods at optimum conditions. In fact, this simple methodology could be an important tool for understanding in detail the complex peroxide vulcanization of elastomers since reactions involved in this process determine the final network structure, and thus the final elastic properties of these compounds.     

New binary systems containing TMTD‐amidino phenyl thiourea and CBS–amidinophenyl thiourea for the vulcanization and rheological behavior of natural rubber latex

The use of accelerators in rubber latex is basically different from their use in dry rubber. In the present study, N amidino N'phenyl thiourea (APT) which is more nucleophilic than thiourea was studied as a secondary accelerator along with tetra methyl 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 vulcanization time. The optimum dosages for this non‐toxic secondary accelerator required were derived. Rheological studies of the compounded latex show that the introduction of APT in these systems does not have adverse effect in processing in comparison with the thiourea systems. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of modified silica on the co-vulcanization kinetics and mechanical performances of natural rubber/styrene–butadiene rubber blends

Rubber blends are widely used for combining the advantages of each rubber component. However, to date, how to determine and distinguish the vulcanization kinetics for each single rubber phase in rubber blends during the co-vulcanization process is still a challenge. Herein, high-resolution pyrolysis gas chromatography–mass spectrometry (HR PyGC-MS) was employed for the first time to investigate the vulcanization kinetics of natural rubber (NR) and styrene–butadiene rubber (SBR) in NR/SBR blends filled with modified silica (SiO₂). The reaction rates of crosslinking of each rubber phase in NR/SBR were calculated, which showed that the crosslinking rates of NR were much lower than those of SBR phase in the unfilled blends and blends filled with unmodified and silane modified silica. Interestingly, the vulcanization rates of NR and SBR phase were approximately same in the vulcanization accelerator modified silica filled blends, showing better co-vulcanization. In addition, the vulcanization accelerator modified silica was uniformly dispersed and endowed rubber blends with higher mechanical strength compared to the untreated silica. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48838.     

橡胶促进剂NS的绿色合成工艺与应用研究进展

橡胶硫化促进剂按照化学结构可以分为醛胺类、秋兰姆类、硫脲类、二硫代氨基甲酸盐类、噻唑类、胍类、黄原酸盐类和次磺酰胺类等,其中次磺酰胺类促进剂具有抗烧焦时间长、硫化活性大、硫化平坦性高、力学性能优良等优点,应用最为广泛。促进剂NS（N-叔丁基-2-苯并噻唑次磺酰胺,TBBS）与其他次磺酰胺类促进剂相比,因在硫化过程中不产生致癌毒性物质亚硝胺,被誉为“标准促进剂”。本文回顾了以次氯酸钠为氧化剂合成促进剂NS的传统方法;综述了催化氧化法、氯气氧化法、电解氧化法和双氧水氧化法等绿色合成工艺;简要概述了微通道反应器在合成促进剂NS方面的工业应用。同时简介了促进剂NS在天然橡胶、丁苯橡胶、二氧化硅填充橡胶的改性剂以及合成氨基磷酸酯等领域的应用。     

High temperature vulcanization of elastomers: 3. Network structure of efficiently vulcanized natural rubber mixes

The effect of vulcanization temperature (140–200°C) and time on the structures of pure gum natural rubber vulcanizates with two different N-cyclohexyl-2-benzothiazylsulphenamide (CBS): sulphur ratios (A, 3·5:1·5; B, 6·0:0·4 CBS/S) has been determined. Analyses of vulcanizates were carried out as reported in Part 2. Results show that both mixes are efficient in crosslinking, resulting in mainly monosulphidic crosslinks and relatively few modifications of the rubber chains. Raising the cure temperature from 140°C reduces the density of chemical crosslinks, particularly those of monosulphidic crosslinks, obtainable in the vulcanizates. This decrease in crosslink density has been shown to be irreversible with respect to cure temperature. The formation of intramolecular sulphidic groups and zinc sulphide increases with rising cure temperature, but this increase is small compared with that reported for the conventional CBS-accelerated system. The main difference between mixes A and B is that mix A yields a higher level of crosslinks and a major proportion of cyclic sulphides as main-chain modification. Negligible chain scission occurs during vulcanization at 140–200°C. These network results are interpreted mechanistically, and essential network features for obtaining good physical properties in high temperature vulcanizates are deduced.     

Preparation of zinc‐oxide‐free natural rubber nanocomposites using nanostructured magnesium oxide as cure activator

The effect of sol–gel synthesized magnesium oxide (MgO) nanoparticles as cure activator is studied for the first time in the vulcanization of natural rubber (NR) and compared with conventional zinc oxide (ZnO) in terms of cure, mechanical, and thermal properties. The NR vulcanizate with 1 phr (Parts per hundred parts of rubber) nano MgO shows an excellent improvement in the curing characteristics and the value of cure rate index is about 400% greater for NR vulcanizate containing 1 phr nano MgO in comparison to the NR vulcanizate with 5 phr conventional ZnO. Both mechanical and thermal properties of NR vulcanizate are found to be satisfactory in the presence of 1 phr nano MgO as cure activator in comparison to conventional NR vulcanizate. This study shows that only 1 phr nano MgO can successfully replace 5 phr conventional ZnO with better resulting properties in the sulfur vulcanization of NR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42705.     

Properties of a new synthetic rubber: High‐trans 1,4‐poly(butadiene‐co‐isoprene) rubber

A high‐trans 1,4‐butadiene/isoprene copolymer (TBIP) was synthesized in a 5‐L autoclave with hydrogen as an effective molecular weight modifier. The effects of hydrogen on the catalyst efficiency and molecular weight of the copolymers were investigated. The processability and physicomechanical properties of TBIP and their relationship to the composition, composition distribution, and molecular weight of TBIP were examined in detail. Increasing the H₂ pressure effectively reduced the molecular weight of TBIP. The optimum Mooney viscosity of TBIP and the 1,4‐butadiene molar content in the feed were 30–50 and 5–25%, respectively. No cis–trans isomerization was observed during the roll processing procedure for TBIP. The vulcanization characteristics of TBIP were similar to those of general rubbers, and no reverse vulcanization was observed for TBIP. A high green strength was the typical characteristic of TBIP. Vulcanized TBIP (TBIR) with an optimum composition and molecular weight presented outstanding antifatigue properties and low heat buildup in comparison with general rubbers. Compared with general sidewall stock [natural rubber (NR)/butadiene rubber (BR) = 50/50], TBIR exhibited a greater than 15‐fold increase in its crack‐initiation resistance. The other mechanical properties of TBIR were similar to those of 50/50 NR/BR. The heat‐aging mechanism of TBIR was crosslinking aging. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2941‐2948, 2004