The influence of basic environment on the efficiency of Heck reaction applied for crosslinking chloroprene rubber

Celem przeprowadzonych badań było określenie wpływu trietanoloaminy (TEOA) na wydajność reakcji Hecka stosowanej do sieciowania kauczuku chloroprenowego (CR). Zaproponowany układ sieciujący jest nowym przykładem zastosowania, doskonale znanej w syntezie organicznej, reakcji Hecka [1]. Reakcja ta jest jedną z głównych metod tworzenia wiązań podwójnych węgiel–węgiel (C=C) w syntezie organicznej. Nie odnotowano jak dotąd żadnego wykorzystania reakcji Hecka w technologii elastomerów. Sporządzono mieszanki kauczukowe zawierające acetyloacetonian żelaza(II) (Fe(acac)2) jako nowy środek sieciujący z różną zawartością TEOA (1–5 cz. mas.). Dodatkowo mieszanki napełniono krzemionką (SiO2) pirogeniczną Aerosil 380 lub sadzą (CB) N550. Uzyskane wyniki wykazały, że zarówno ilość TEOA, jak i rodzaj napełniacza miały istotny wpływ na właściwości otrzymanych elastomerów. W przypadku kompozytów napełnionych CB aktywność Fe(acac)2 w procesie sieciowania wzrastała wraz z ilością TEOA. Potwierdziły to wysokie wartości przyrostu momentu obrotowego i stopnia usieciowania CR oraz krótsze czasy wulkanizacji. W przypadku mieszanek napełnionych SiO2 wpływ ilości TEOA na wydajność procesu sieciowania nie był tak jednoznaczny. Jednak biorąc pod uwagę przyrost momentu obrotowego, stopień usieciowania oraz optymalny czas wulkanizacji można stwierdzić, że użycie 3 cz. mas. TEOA skutkowało największą aktywnością Fe(acac)2.The aim of the study was to determine the effect of triethanolamine (TEOA) on the efficiency of Heck’s reaction used for the crosslinking of chloroprene rubber (CR). The proposed crosslinking system is a new example of the application of the Heck reaction, well known in organic synthesis [1]. This reaction is one of the main methods of creating carbon‑carbon double bonds (C=C) in organic synthesis. So far, no use of Heck’s reaction in elastomer technology has been reported. Rubber blends containing iron(II) acetylacetonate (Fe(acac)2) as a new crosslinking agent with different TEOA content (1–5 phr) were prepared. Additionally, the blends were filled with pyrogenic silica (SiO2) Aerosil 380 or carbon black (CB) N 550. The obtained results showed that both the amount of TEOA and the type of filler had a significant effect on the properties of the elastomers obtained. In case of composites filled with CB, the activity of Fe(acac)2 in the crosslinking process increased with the amount of TEOA. This was confirmed by high values of torque increment and degree of crosslinking of CR and shorter vulcanization times. In case of rubber compounds filled with SiO2, the effect of TEOA on the efficiency of crosslinking process was not so unambiguous. However, considering the increase in torque, the degree of crosslinking and the optimum vulcanization time, it can be stated that the use of 3 phr. TEOA resulted in the highest Fe(acac)2 activity

Manganese and Nickel Acetylacetonates as Curatives for Chloroprene Rubber Based on Heck’s Reaction

The commonly used curing system for chloroprene rubber (CR) is a combination of two metal oxides, such as magnesium oxide (MgO) and zinc oxide (ZnO). Application of MgO and ZnO enables to obtain a good balance between processability of rubber compounds and mechanical properties of the vulcanizates. Despite high activity in crosslinking reactions, ZnO is classified as ecotoxic to aquatic organisms, thus environmental legislation requires its quantity in technology to be limited. In our studies more environmentally friendly curing systems were applied, which enabled eliminating ZnO from CR compounds. These curing systems consisted of manganese acetylacetonate (Mn(acac)) or nickel acetylacetonate (Ni(acac)) and triethanolamine (TEOA) used as a base necessary to perform Heck’s reaction. Both metal acetylacetonates exhibited high activity in crosslinking reactions, which was confirmed by a great torque increment during rheometric measurements and high degree of elastomer crosslinking. The type of metal acetylacetonate and the amount of TEOA seemed to have less influence on the efficiency of the curing system than the filler used. Rubber compounds filled with carbon black (CB) were characterized by definitely shorter optimal vulcanization times and higher degree of crosslinking compared to CR composites filled with nanosized SiO2. Moreover, application of the proposed curing systems allowed to obtain CR vulcanizates with mechanical properties comparable with the benchmarks cured with metal oxides

Manganese and Nickel Acetylacetonates as Curatives for Chloroprene Rubber Based on Heck’s Reaction

The commonly used curing system for chloroprene rubber (CR) is a combination of two metal oxides, such as magnesium oxide (MgO) and zinc oxide (ZnO). Application of MgO and ZnO enables to obtain a good balance between processability of rubber compounds and mechanical properties of the vulcanizates. Despite high activity in crosslinking reactions, ZnO is classified as ecotoxic to aquatic organisms, thus environmental legislation requires its quantity in technology to be limited. In our studies more environmentally friendly curing systems were applied, which enabled eliminating ZnO from CR compounds. These curing systems consisted of manganese acetylacetonate (Mn(acac)) or nickel acetylacetonate (Ni(acac)) and triethanolamine (TEOA) used as a base necessary to perform Heck’s reaction. Both metal acetylacetonates exhibited high activity in crosslinking reactions, which was confirmed by a great torque increment during rheometric measurements and high degree of elastomer crosslinking. The type of metal acetylacetonate and the amount of TEOA seemed to have less influence on the efficiency of the curing system than the filler used. Rubber compounds filled with carbon black (CB) were characterized by definitely shorter optimal vulcanization times and higher degree of crosslinking compared to CR composites filled with nanosized SiO2. Moreover, application of the proposed curing systems allowed to obtain CR vulcanizates with mechanical properties comparable with the benchmarks cured with metal oxides.</jats:p

METAL COMPLEXES AS NEW PRO-ECOLOGICAL CROSSLINKING AGENTS FOR CHLOROPRENE RUBBER BASED ON HECK COUPLING REACTION

ABSTRACT The influence of new pro-ecological curing agents on the crosslinking process of chloroprene rubber (CR) was examined. The proposed curing system used a simpler recipe (no need to apply harmful products such as zinc oxide and ethylene thiourea) and cost less than standard metal oxides. It was expected that the mechanism of crosslinking would be similar to that of Heck-type reactions. Heck-type reactions are powerful tools for the creation of new C=C bonds. They provide the simplest and most efficient way to synthesize a variety of important compounds used in many areas, such as pharmaceuticals, antioxidants, ultraviolet absorbers, and industrial applications. However, despite their wide application, Heck-type reactions have not been used in the rubber industry so far. Rubber blends containing acetylacetonates with different transition metals as new crosslinking agents were filled with fumed silica Aerosil 380 or carbon black Corax N-550. It was found that metal complexes are active crosslinking agents of the CR composites. The obtained vulcanizates were characterized by a high degree of crosslinking and good mechanical properties. Considering the high tensile strength and degree of crosslinking, iron acetylacetonate was the most effective curing agent of the used metal complexes. Compared with the reference sample cured with metal oxides, the CR samples crosslinked using metal acetylacetonates had a higher activity.</jats:p

Thermal analysis of halogenated rubber cured with a new cross-linking system

Abstract The aim of this work was to examine the influence of new curing agents proposed for brominated butyl rubber (BIIR) on the cross-linking process of rubber compounds and the thermal behavior of the vulcanizates. Rubber blends that were filled with carbon black and contained acetylacetonates of different transition metals in the presence of triethanolamine (TEOA) as new cross-linking agents were prepared. The performed studies showed that metal acetylacetonates (Me(acac)) are effective cross-linking agents for BIIR, which was confirmed by high values of the torque increment (∆M) and significant cross-linking degree of the vulcanizates (α(T)). The most active curing agent seems to be iron acetylacetonate (Fe(acac)). Its application results in a shorter optimal vulcanization time, lower onset vulcanization temperature and similar vulcanization enthalpy compared to the BIIR cured with a sulfur curing system. The BIIR vulcanizates cured with Me(acac) reveal good mechanical properties with tensile strengths in the range of 9–14 MPa and better damping properties comparing to the sulfur-cured rubber. The proposed curing agents do not significantly affect the thermal stability of the BIIR vulcanizates.</jats:p

Reaction mechanism of halogenated rubber crosslinking using a novel environmentally friendly curing system

Iron (III) acetylacetonate (Fe (acac)) in the presence of triethanolamine (TEOA) was utilized as a novel crosslinking agent for halogenated diene rubber. Following the assumption that the mechanism of the crosslinking bases on the Heck-type reaction mechanism, which requires the presence of a halogen and an unsaturated carbon-carbon double bond, chloroprene rubber (CR) and brominated butyl rubber (BIIR) were utilized as rubber matrices. The results of FTIR spectra analysis confirm the proposed mechanism and indicate that a Heck-type reaction is feasible for performing a crosslinking of halogenated diene rubbers. The use of the Fe (acac)/TEOA curing system results in a significant torque increase during the vulcanization, which confirms the high activity of those compounds. The elimination of halogen from a rubber macromolecular structure or elimination of a basic environment of the crosslinking reaction results in a deactivation of the new curing system