Effect of [Mn(acac)3] and its combination with 2,2′-bipyridine on the autoxidation and oligomerisation of ethyl linoleate

Oyman, Z.O.; Ming, Weihua; Linde, R. van der; Gorkum, Remy van; Bouwman, Elisabeth

doi:10.1016/j.polymer.2004.12.045

Cited by 47 publications

(41 citation statements)

References 18 publications

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“…It appears that after a period of 8 h the formation of dimers and higher oligomers has taken place. The extent of peroxide formation and oligomerisation is comparable to that observed for the catalytic system of Mn(acac) 3 with bipyridine [23]. …”

Section: Sec Experimentssupporting

confidence: 72%

New manganese-based catalyst systems for alkyd paint drying

Liu

Kooijman

Spek

et al. 2007

Progress in Organic Coatings

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The autoxidation and oligomerisation of ethyl linoleate (EL) catalyzed by manganese salts in combination with several Schiff-base ligands has been studied making use of time-resolved FT-IR spectroscopy. The results indicate that several of the combinations exhibit relatively high catalytic activity for the autoxidation of EL. One of the catalyst systems was studied in more detail. The reaction between MnCl 2 ·2H 2 O and the Schiff-base ligand (L4) formed by the condensation of 2-pyridinealdehyde and 2-aminopyridine has been studied to clarify the catalytic reaction process. It was found that the Schiff-base ligand L4 reacts with water and the tridentate ligand (2-pyridyl)(2-pyridylamino)methanol (HOL4) is formed. A single crystal structure of [Mn III (OL4) 2 ]Cl·3H 2 O has been determined by X-ray diffraction methods.

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Section: Sec Experimentssupporting

confidence: 72%

New manganese-based catalyst systems for alkyd paint drying

Liu

Kooijman

Spek

et al. 2007

Progress in Organic Coatings

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“…All autoxidation reactions were performed using purified EL, that is, EL from which all hydroperoxides have been removed [7]. The EL autoxidation rates for each complex are collected in Table 2.…”

Section: Autoxidation Activity Determined With Ftir and Secmentioning

confidence: 99%

“…Some commercial paint formulations contain manganese carboxylate as a primary drier, even though these do not have the same performance as cobalt-based driers [3,4]. This has initiated a search to find alternatives for cobalt complexes as drying catalysts in alkyd paint [5][6][7][8][9][10]. Recently, our group reported on Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

“…An additional benefit of this ligand type is that the synthesis of the ligands is straightforward and variations on the ligand structure are readily possible. β-Diketonates were chosen as the "secondary" ligand because good autoxidation results have been obtained with simple, homoleptic manganese β-diketonate complexes [7,8]. We have synthesised and characterised a series of manganese(III) and iron(III) coordination compounds with one dianionic tripodal ligand and one auxiliary ligand (Schemes 1 and 2) [18].…”

Section: Introductionmentioning

confidence: 99%

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The autoxidation activity of new mixed-ligand manganese and iron complexes with tripodal ligands

Gorkum

Berding

Tooke

et al. 2007

Journal of Catalysis

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The activity of new manganese and iron complexes of dianionic tripodal ligands in the autoxidation of ethyl linoleate (EL) is reported. EL consumption rates were monitored using time-resolved FTIR and the degree of oligomerisation was determined by SEC. Almost all complexes showed the same trend in the autoxidation of EL. After a short induction time, the reaction started at a relatively high constant rate; later, this rate changes to a lower rate, which was again constant and on average was the same for all complexes studied. The observation that the autoxidation rate eventually became the same for all complexes can be explained with the assumption that a catalytic species was formed that was structurally similar for each complex. The crystal structure of a representative new complex, [Mn(papy)(acac)] (H 2 papy = N-(2-hydroxybenzyl)-N -(2-picolyl)-glycine; Hacac = acetylacetone), was elucidated, demonstrating a Jahn-Teller distorted octahedral geometry of the Mn(III) ion. To gain insight into the reaction mechanisms by which these manganese complexes react with peroxides, the reaction of [Mn(pppy)(dpm)] with alkyl hydroperoxides was studied using UV-vis and EPR spectroscopy (H 2 pppy = 2-[bis(2-hydroxybenzyl)aminomethyl]-pyridine; Hdpm = dipivaloylmethane). It is proposed that in a reaction of [Mn(pppy)(dpm)] with t-butyl hydroperoxide ( t BuOOH), the species [Mn(III)(pppy)(OH)( t BuOO · )] is formed. In analogy with the formation of that species, which is postulated to occur through a reduction to Mn(II), it is proposed that in the direct initiation reaction of EL with a manganese(III) complex, a 1 electron-1 proton transfer reaction leads to the formation of Mn(II) and an EL radical. Considering parameters such as autoxidation activity, complex solubility and ease of complex preparation, the compound [Mn(III)(tbpppy)(dpm)] (H 2 tbpppy = 2-[bis(2-hydroxy-3,5-di-tert-butylbenzyl) aminomethyl]pyridine) is expected to be the best potential alkyd paint drier.

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“…Metal catalysts enhance the decomposition of hydroperoxide which increases the overall paint drying rate [9]. We have studied several transition metals and found that the most effective catalyst for the peroxide decomposition and polymerisation reaction is cobalt(II) nitrate, followed by manganese nitrate and finally, cerium nitrate is the least effective [7].…”

Section: Introductionmentioning

confidence: 99%

Linseed Oil and its Tendency to Self-Heat

Dlugogorski¹,

Kennedy²,

Mackie³

2011

Fire Safety Science - Proceedings of the 10th International Sym

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Several varieties of linseed oil are commercially available, and they have been used for many applications especially in decorative furniture finishing and as an oil painting medium. The addition of metallic driers to the linseed oil is a common practice, as it improves the drying rate of the paint. Several cases of fires have been reported, often involving rags soaked with linseed oil which have not been disposed of properly, and it is generally agreed that metal salts in the linseed oil play an important role in the spontaneous ignition of the oil. This paper investigates several types of linseed oil sold in the market and their tendency to cause self-heating of cotton which has been impregnated with linseed oil obtained from various sources.Experiments were performed in two reactors; a plug flow reactor for measurement of gaseous oxidation products and in a batch system for the determination of metal composition in the oil. Both plug flow and batch systems employ fifty percent of oxygen and nitrogen mixtures for several hours in each experiment. Emission of gaseous products during the reaction was quantified by micro gas chromatography (µGC), and identified by Fourier transform infrared spectroscopy (FTIR) and gas chromatography-mass spectrometry (GC-MS). Oil samples from batch system were digested using microwave and the metal composition was determined by inductively coupled plasma-optical emission spectrometer (ICP-OES).Boiled linseed oil is the most reactive oil studied, followed by raw linseed oil and refined linseed oil which display similar reactivity, while the least reactive is stand linseed oil. ICP analysis confirmed the presence of cobalt in the boiled linseed oil, which enhances the rate of oxidation reaction. For boiled linseed oil, the cobalt in the oil enhances the decomposition of peroxide resulting in the formation of various radicals which oxidize the oil and the cotton wool, therefore the emission of gaseous products is higher during oxidation on the cotton wool support compared to glass wool and thus boiled linseed oil has the highest tendency to self heat, especially if soaked on the cotton or rags.A kinetic model of peroxide formation and decomposition has been developed based on the experimental data. The reaction rate constant of the decomposition of peroxide has been found to be higher in the reaction using cobalt compared to that of without cobalt, confirming the role of cobalt in catalysing the peroxide decomposition reaction. Abstraction reactions by the radicals during oxidation lead to subsequent reactions which are generally very exothermic. Accumulation of sufficient heat, can ultimately lead to the temperature reaching the ignition point of the oil and causing the self-heating and even ignition of the oil.

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Effect of [Mn(acac)3] and its combination with 2,2′-bipyridine on the autoxidation and oligomerisation of ethyl linoleate

Cited by 47 publications

References 18 publications

New manganese-based catalyst systems for alkyd paint drying

New manganese-based catalyst systems for alkyd paint drying

The autoxidation activity of new mixed-ligand manganese and iron complexes with tripodal ligands

Linseed Oil and its Tendency to Self-Heat

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