Oxidative crosslinking of alkyd resins studied with mass spectrometry and NMR using model compounds

Muizebelt, W. J.; Donkerbroek, J. J.; Nielen, M.; Hussem, J. B.; Biemond, M. E. F.; Klaasen, R. P.; Zabel, Klaus

doi:10.1007/bf02720501

Cited by 76 publications

(37 citation statements)

References 31 publications

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“…The peroxide homolysis can be induced by temperature and may be assisted by metal catalysts (Van den Berg 2002;Mallégol et al 2000b;Black 1978;Bawn 1957;Morley-Smith 1957;Banks et al 1954). The degradation of unsaturated oils is fundamentally caused by the "-elimination (fragmentation reaction), which is the dominant reaction pathway at room temperature (Mallégol et al 2000b, c;Lazzari and Chiantore 1999;Chan 1987; Grosch 1987;Muizebelt 1978). The implication of this reaction can also be derived from the high content of oxalates, as oxalic acid is generated similarly by the decomposition of hydroperoxides of oxidised double bonds.…”

Section: Resultsmentioning

confidence: 97%

Derivatisation Technique for Infrared Spectroscopy – Characterisation of Oxidative Ageing Products in Modern Oil Paint

Zumbühl

Scherrer

Müller³

2014

Issues in Contemporary Oil Paint

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In conservation science the Fourier transformed based infrared spectroscopy (FTIR) is a standard technique to the study of historic paint layers. There are, however, clear limitations when analysing modern oil paint. The spectral information of aged oils is affected from overlapping signals of the binder, the oxidative ageing products, soaps formed during ageing, as well as several pigments and fillers. The distinction of the ageing products such as ketone and carboxylic acid functional groups pose the next problem, as these interfere with the triglyceride esters. Gaseous sulfur tetrafluoride SF 4 was used to discriminate overlapping signals in aged oil paint. This derivatisation technique makes it possible to convert carboxylic acids and carboxylate salts into acyl fluoride, while ketones and ester groups remain intact. IR spectra after SF 4 treatment show a characteristic splitting of the carbonyl band, allowing the characterisation of the different functional groups formed during oxidative ageing. Furthermore, it is possible to increase the spectral selectivity thanks to the successful elimination of spectral interferences caused by organometallic and inorganic compounds. This sample pre-treatment can be applied to both micro-samples and polished cross-sections, enabling 2D localisation of these compounds in aged oil paint samples using infrared imaging FTIR-FPA (focal plane array). Both artificially aged and real paint samples of twentieth century paintings were investigated to characterise degradation processes in oil paint, including the dripping phenomenon of modern oil paints.

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Section: Resultsmentioning

confidence: 97%

Derivatisation Technique for Infrared Spectroscopy – Characterisation of Oxidative Ageing Products in Modern Oil Paint

Zumbühl

Scherrer

Müller³

2014

Issues in Contemporary Oil Paint

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“…Since, in alkyd paint drying, most of the chemistry takes place at the unsaturated fatty acid tails of the binder compound, the entire binder resin can be modeled by using compounds that structurally or chemically resemble this fatty acid chain. Dienes such as 4,7-heptadiene, 9 3,6-nonadiene, 10 and 2,5-undecadiene, 11 as well as methyl and ethyl esters of the unsaturated fatty acids linoleic, linolenic, and ricinoleic acid, [12][13][14][15] have been used as model compounds for alkyd resin precursors. An advantage of this approach, besides having a much simpler system to study, is that when model compound mixtures become 'dried', they remain liquid and consequently are more easily studied using standard analytical techniques.…”

Section: Modeling Alkyd Paintmentioning

confidence: 99%

“…A wide range of analytical techniques has been used to study the autoxidation of alkyd paint model compounds. These techniques include 13 C-NMR, 10-13 GC, 13 HPLC, [9][10][11] FT-IR, 14,[16][17][18] SEC, 12,13 and SIMS. 15 To screen different metal complexes quickly for their ability to enhance the 'drying' of EL, the two more useful parameters to monitor are the rate of the autoxidation reaction and the extent of the crosslinking that takes place.…”

Section: Modeling Alkyd Paintmentioning

confidence: 99%

“…The EL peak does not disappear completely even after 48 h, which is because of the presence of about 8% of nonreactive saturated esters and the presence of 19% of the less reactive ethyl oleate 13,28 in the technical-grade EL. The peak appearing at 17 min is due to EL hydroperoxides 3,4,12 and to other oxygen-containing EL derivatives (for example, epoxide species). 12 The amount of hydroperoxides first increases and then decreases significantly over the course of the reaction, in agreement with the results obtained for the peroxide value determination.…”

Section: Oligomerization During El Oxidationmentioning

confidence: 99%

“…The peak appearing at 17 min is due to EL hydroperoxides 3,4,12 and to other oxygen-containing EL derivatives (for example, epoxide species). 12 The amount of hydroperoxides first increases and then decreases significantly over the course of the reaction, in agreement with the results obtained for the peroxide value determination.…”

Section: Oligomerization During El Oxidationmentioning

confidence: 99%

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A study of new manganese complexes as potential driers for alkyd paints

Bouwman

Gorkum

2007

J Coat Technol Res

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In the search for new autoxidation catalysts, the oxidative crosslinking of ethyl linoleate (EL) has been monitored using time-resolved FT-IR (Fourier transform IR spectroscopy), size-exclusion chromatography and GC/MS (gas chromotography/mass spectroscopy). These methods seem to be quite sensitive to changes in the structure of the catalyst. It has been found that the compound [Mn(acac) 3 ] (Hacac = 2,4-pentanedione) is an efficient catalyst for the oxidation and the oligomerization of EL, which is proposed to proceed not only via hydroperoxide decomposition, but also through substrate activation. The system [Mn(acac) , and the high reactivities of these two species with hydroperoxides and with EL, respectively, are proposed as an explanation for the observed high oxidation rate.

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Viscoelastic properties of alkyd ceramers

Sailer

Soucek

1999

J. Appl. Polym. Sci.

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ABSTRACT:The viscoelastic behavior of three alkyd ceramers was studied using dynamic mechanical thermal analysis (DMTA). A commercial product was compared to model alkyds. The model alkyds were prepared from phthalic anhydride, glycerol, and linseed or sunflower seed oil. Three sol-gel precursors, titanium tetra-i-propoxide, titanium di-i-propoxide diacetylacetonate, and zirconium tera-n-propoxide were investigated. The alkyd ceramers were evaluated as a function of both alkyd type and a sol-gel precursor content. The viscoelastic data showed that both EЈ and T g were affected by sol-gel precursor content. Both the crosslink density and T g demonstrated a minimum at low sol-gel precursor contents. After this minimum, both the crosslink density and the T g increased substantially.

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Oxidative crosslinking of alkyd resins studied with mass spectrometry and NMR using model compounds

Cited by 76 publications

References 31 publications

Derivatisation Technique for Infrared Spectroscopy – Characterisation of Oxidative Ageing Products in Modern Oil Paint

Derivatisation Technique for Infrared Spectroscopy – Characterisation of Oxidative Ageing Products in Modern Oil Paint

A study of new manganese complexes as potential driers for alkyd paints

Viscoelastic properties of alkyd ceramers

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