Theoretical aspects of the reaction of zirconium compunds and vegetable tannins with the chromium-collagen complex
- Williams-Wynn, David Ernest Arthur
- Authors: Williams-Wynn, David Ernest Arthur
- Date: 1969
- Subjects: Zirconium compounds , Collagen , Chromium compounds , Tannins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4512 , http://hdl.handle.net/10962/d1013455
- Description: Studies have been made of the reactions which take place when zirconium compounds and vegetable tannins react with chromium tanned leather, in order to elucidate the mechanisms of the reactions which occur on retannage. Statistical procedures have been used in all investigations because of the variable nature of the substrate, and computer techniques have been applied to the repetitive statistical computations. Although chromium and vegetable tannages are well understood, further information on the reaction of zirconium with collagen was necessary before attempting to interpret the results of the studies of combination tannages with chromium, and this has been obtained by a comparative study of the reactions of chromium and zirconium with modified collagen. It is concluded that the mechanism of the reaction of basic zirconium sulphate with collagen is multipoint attachment of the tanning material by residual valency forces, although charge effects with basic groups may be supplementary. Zirconyl chloride reacts with carboxyl groups but does not form satisfactory, stable cross-links with collagen. Further evidence for this theory was obtained from the investigation of the reaction of zirconium compounds with chromium tanned collagen. Zirconyl sulphate does not interfere with effective chromium tannage and therefore can have little affinity for the carboxyl groups on the protein, but it displaces chromium complexes loosely held by auxiliary valencies without reducing the shrinkage temperature of the chromium leather Zirconyl chloride, although only fixed to a limited extent, apparently forms co-ordination compounds with the carboxyl groups, disrupting the chromium tannage because there is an over-all loss of hydrothermal stability. There is no evidence that zirconium co-ordinates with, or releases acid from chromium-collagen complexes, since combination chromium/zirconium tanned leathers are stable on storage. Retannage of chromium tanned leather with vegetable tanning materials generally results in loss of strength and a product which tends to deteriorate on ageing. Lower initial strength is probably due to the increased avidity of chromium tanned pelt for vegetable tannins, resulting from the liberation of internally neutralised reactive sites which are not normally available in vegetable tannage, and from the co- ordination of vegetable tannins and non-tannins to the chromium complex with the displacement of sulphate radicals. From a study of the retannage of chromium tanned modified collagen, it appears that basic groups probably play an important part in the rapid absorption of vegetable tannin. These reactions result in overloading of the fibre and an increased number of cross-links, both of which tend to produce weak leather. Deterioration with age is primarily a hydrolytic degradation of the protein which is catalysed by acid liberated from the chromium complexes by the entry of vegetable tannins, those factors which favour the formation of acid causing greater and more rapid deterioration.
- Full Text:
- Authors: Williams-Wynn, David Ernest Arthur
- Date: 1969
- Subjects: Zirconium compounds , Collagen , Chromium compounds , Tannins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4512 , http://hdl.handle.net/10962/d1013455
- Description: Studies have been made of the reactions which take place when zirconium compounds and vegetable tannins react with chromium tanned leather, in order to elucidate the mechanisms of the reactions which occur on retannage. Statistical procedures have been used in all investigations because of the variable nature of the substrate, and computer techniques have been applied to the repetitive statistical computations. Although chromium and vegetable tannages are well understood, further information on the reaction of zirconium with collagen was necessary before attempting to interpret the results of the studies of combination tannages with chromium, and this has been obtained by a comparative study of the reactions of chromium and zirconium with modified collagen. It is concluded that the mechanism of the reaction of basic zirconium sulphate with collagen is multipoint attachment of the tanning material by residual valency forces, although charge effects with basic groups may be supplementary. Zirconyl chloride reacts with carboxyl groups but does not form satisfactory, stable cross-links with collagen. Further evidence for this theory was obtained from the investigation of the reaction of zirconium compounds with chromium tanned collagen. Zirconyl sulphate does not interfere with effective chromium tannage and therefore can have little affinity for the carboxyl groups on the protein, but it displaces chromium complexes loosely held by auxiliary valencies without reducing the shrinkage temperature of the chromium leather Zirconyl chloride, although only fixed to a limited extent, apparently forms co-ordination compounds with the carboxyl groups, disrupting the chromium tannage because there is an over-all loss of hydrothermal stability. There is no evidence that zirconium co-ordinates with, or releases acid from chromium-collagen complexes, since combination chromium/zirconium tanned leathers are stable on storage. Retannage of chromium tanned leather with vegetable tanning materials generally results in loss of strength and a product which tends to deteriorate on ageing. Lower initial strength is probably due to the increased avidity of chromium tanned pelt for vegetable tannins, resulting from the liberation of internally neutralised reactive sites which are not normally available in vegetable tannage, and from the co- ordination of vegetable tannins and non-tannins to the chromium complex with the displacement of sulphate radicals. From a study of the retannage of chromium tanned modified collagen, it appears that basic groups probably play an important part in the rapid absorption of vegetable tannin. These reactions result in overloading of the fibre and an increased number of cross-links, both of which tend to produce weak leather. Deterioration with age is primarily a hydrolytic degradation of the protein which is catalysed by acid liberated from the chromium complexes by the entry of vegetable tannins, those factors which favour the formation of acid causing greater and more rapid deterioration.
- Full Text:
The chemistry of the wattle tannins
- Authors: Roux, David Gerhardus
- Date: 1953
- Subjects: Tannin plants , Tannins , Wattles (Plants)
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: vital:4492 , http://hdl.handle.net/10962/d1013098
- Description: Four species of acacia of Auatralian origin are associated with the wattle industry in South Africa. Black wattle, Acacia mollissima willd., is the most important of these and is today almost exclusively cultivated. The tree grows successfully only in a limited area of rich soil and high rainfall and is easily affected by adverse conditions caused by insect pests, frost damage and drought. Expansion of the area under cultivation is therefore, not feasible, although the world demand for vegetable extracts far exceeds the available supply. The remaining species such as green (Acacia decurrrens willd.) and silver wattles (Acacia dealbata Link.) possess many desirable characteristics which resist such adverse factors. Their barks, however, give reddish extracts, which are considered unsuitable for tannery usage because of the red colour they impart to the leather. Hybridisation studies, involving the crossing of green and silver wattle with the black, and aimed at produc1ng progenies containing many of the desirable characterlstics of the parent plants, are thus a natural result and have been in progress for a considerable period. Summary, p. i.
- Full Text:
- Authors: Roux, David Gerhardus
- Date: 1953
- Subjects: Tannin plants , Tannins , Wattles (Plants)
- Language: English
- Type: text , Thesis , Doctoral , PhD
- Identifier: vital:4492 , http://hdl.handle.net/10962/d1013098
- Description: Four species of acacia of Auatralian origin are associated with the wattle industry in South Africa. Black wattle, Acacia mollissima willd., is the most important of these and is today almost exclusively cultivated. The tree grows successfully only in a limited area of rich soil and high rainfall and is easily affected by adverse conditions caused by insect pests, frost damage and drought. Expansion of the area under cultivation is therefore, not feasible, although the world demand for vegetable extracts far exceeds the available supply. The remaining species such as green (Acacia decurrrens willd.) and silver wattles (Acacia dealbata Link.) possess many desirable characteristics which resist such adverse factors. Their barks, however, give reddish extracts, which are considered unsuitable for tannery usage because of the red colour they impart to the leather. Hybridisation studies, involving the crossing of green and silver wattle with the black, and aimed at produc1ng progenies containing many of the desirable characterlstics of the parent plants, are thus a natural result and have been in progress for a considerable period. Summary, p. i.
- Full Text:
A preliminary investigation of the structure of green wattle tannin (acacia decurrens willd)
- Authors: Glueck, Leonard David
- Date: 1952
- Subjects: Tannins , Tannin plants
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4475 , http://hdl.handle.net/10962/d1011988 , Tannins , Tannin plants
- Description: Green wattle tannin extracts were separated by lead salt precipitation into a phenolic tannin fraction and a nontannin fraction. The combustion analysis of the tannin fraction corresponded to an empirical formula C₁₅H₁₄O₆. Methoxy and acetyl values showed four oxygens were hydroxy groups while the residual oxygens could either be ether linked or carbonyl groups. Diazomethane methylation produced a white product of high methoxyl value which indicated that the four hydroxyl groups were phenolic. Chromatography of the lead salt purified tannin showed an indistinct non-fluorescent trail. Ether extraction of the tannin removed the associated Phenolic bodies. The ethereal extract unlike black wattle extracts contained no fisetin and evaporation of the ethereal solutions yielded a gummy non-crystalline residue. Alkaline fusion of the purified tannin produced for the first tlme a variety of acidic and phenolic compounds i.e. resorcinol, pyrogaloll, phloroglucinol β-resorcylic acid, gallic acid and protocatechuic acid. From the high yields of resorcinol (6%) and gallic acid (3%), these units appear to predominate. These degradation productions, coupled with the analytical figures, indicate a possible C₁₅ unit with resorcinol and pyrogallol nuclei as a basis. The non-tannin fraction failed to reveal any compound which might cause the excessive redness in green wattle extracts. Chromatography of this non-tannin fraction showed the presence of sucrose.
- Full Text:
- Authors: Glueck, Leonard David
- Date: 1952
- Subjects: Tannins , Tannin plants
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4475 , http://hdl.handle.net/10962/d1011988 , Tannins , Tannin plants
- Description: Green wattle tannin extracts were separated by lead salt precipitation into a phenolic tannin fraction and a nontannin fraction. The combustion analysis of the tannin fraction corresponded to an empirical formula C₁₅H₁₄O₆. Methoxy and acetyl values showed four oxygens were hydroxy groups while the residual oxygens could either be ether linked or carbonyl groups. Diazomethane methylation produced a white product of high methoxyl value which indicated that the four hydroxyl groups were phenolic. Chromatography of the lead salt purified tannin showed an indistinct non-fluorescent trail. Ether extraction of the tannin removed the associated Phenolic bodies. The ethereal extract unlike black wattle extracts contained no fisetin and evaporation of the ethereal solutions yielded a gummy non-crystalline residue. Alkaline fusion of the purified tannin produced for the first tlme a variety of acidic and phenolic compounds i.e. resorcinol, pyrogaloll, phloroglucinol β-resorcylic acid, gallic acid and protocatechuic acid. From the high yields of resorcinol (6%) and gallic acid (3%), these units appear to predominate. These degradation productions, coupled with the analytical figures, indicate a possible C₁₅ unit with resorcinol and pyrogallol nuclei as a basis. The non-tannin fraction failed to reveal any compound which might cause the excessive redness in green wattle extracts. Chromatography of this non-tannin fraction showed the presence of sucrose.
- Full Text:
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