US3792976A - Aluminum-chrome acrylic acid complex tannage and leather aluminum or - Google Patents

Aluminum-chrome acrylic acid complex tannage and leather aluminum or Download PDF

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Publication number
US3792976A
US3792976A US00195871A US3792976DA US3792976A US 3792976 A US3792976 A US 3792976A US 00195871 A US00195871 A US 00195871A US 3792976D A US3792976D A US 3792976DA US 3792976 A US3792976 A US 3792976A
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United States
Prior art keywords
aluminum
leather
denotes
acrylic acid
parts
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Expired - Lifetime
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US00195871A
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English (en)
Inventor
H Erdmann
F Miller
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/04—Mineral tanning
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages

Definitions

  • the present invention relates to new salts which contain aluminum or aluminum and trivalent chrominum as central atoms in a trinuclear complex cation, and acrylic acid anions as acido groups with or without hydroxo groups.
  • the invention also relates to a tanning method using these complex trinuclear metal salts.
  • leather which is able to withstand the boiling test is obtained with these tanning salts.
  • a particularly good property is that unsaturated carboxylic acids contained in the complex can be polymerized in the leather for example by means of redox systems.
  • M denotes aluminum and M denotes trivalent chromium
  • R denotes the radical of acrylic acid combined twice between two metal atoms, denotes an integer from 1 to 3 and m denotes an integer from 2 to 6.
  • the new aluminum or aluminum/chromic complex salts may contain any monovalent anions provided they do not make the complex insoluble in water, for example chloride, bromide, iodide, perchlorate, nitrate, formate, acetate and propionate ions.
  • the complex salts according to the invention preferably contain chloride ions.
  • the aluminum complex salts have a structure in which, between the three central atoms, a total of six acido and hydroxyl groups, and at the two external metal atoms, three aquo groups in each case are coordinatively combined:
  • R denotes the acido radical of acrylic acid and A denotes a monovalent anion from the group given above.
  • the formula represents the ,u-hexacidohexaquotrialuminum salt (Al R H O) )A
  • Complex salts according to the invention may be prepared in various ways. For example aluminum salts of monobasic acids alone or together with appropriate chromic salts in the molar ratio of chromium to aluminum given by the formula may be dissolved in water, and monomeric acrylic acid with an equivalent amount of an alkaline reacting agent, or the alkali metal salt of this acid, added in such an amount that at least 0.67 carboxylic acid radical and not more than 1.33 hydroxyl groups are available for each metal atom. The sum of the number of acrylic acid radicals and that of the hydroxyl groups should amount to 2.0 per metal. After the reaction is over, the complex salts formed may be processed into powder in a spray-dryer.
  • the alkaline reacting agents may be not only oxides and hydroxides of alkali metals and alkaline earth metals but also their carbonates. Examples are sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium hydroxide, calcium carbonate, magnesium carbonate and dolomite.
  • the aluminum complex salts described herein are colorless. Mixed complexes of aluminum and trivalent chromium are pale green in powdered form, but greenish blue to ink blue in solution.
  • Salts according to the invention having the above formulae are outstandingly suitable for tanning. They have the advantage over prior art aluminum salts used for tanning that they are more resistant to hydrolysis. Therefore the material tanned therewith has a higher shrinkage temperature of 78 to 80C, a great fullness and high suppleness of handle. Complex salts prepared with trivalent chromium give pale, light blue leather which withstands the boiling test.
  • Aldehydes include especially formaldehyde, acetaldehyde, propionaldehyde, glyoxal and glutaraldehyde. Substances which split off aldehydes under the conditions of tanning may be used instead of the aldehydes or together with the same.
  • aldehydes include sodium hydroxylmethanesulfonate, hexamethylenetetramine, paraformaldehyde, paraldehyde, metaldehyde and particularly N-methylol compounds, for example those of urea, cyclic urea derivatives, melamine and dicyanodiamide. It has proved suitable to use the aldehydes in amounts of from 0.5 to 3 percent, preferably 1 to 1.5 percent, with reference to the weight of the material being tanned. Agents releasing aldehydes are advantageously used in amounts equivalent to the said amount of aldehyde or to the equivalent amount of aldehyde split off based in the equilibrium condition in solution.
  • the pretreatment of pelts with 3 percent formaldehyde not only improves the handle properties of the finished leather and prevents the aluminum in the tan being washed out but also increases the shrinkage temperature to 88 to 99C.
  • the salts according to this invention it has proved to be very convenient to use the salts according to this invention in amounts which are equivalent to 2.5 to 4 percent of A1 (or Al O and Cr O based on the weight of pelts being tanned.
  • the same tanning conditions may be used with the salts according to the invention as are used with other aluminum tans. It has proved to be particularly advantageous to buffer the tanning liquor with alkaline reacting agents to a pH value of about 5 towards the end of the tanning.
  • the product obtained in this way is a colorless powder having very good solubility in water. It contains an amount of sodium chloride originating from the reaction of aluminum chloride, in addition to the salt according to the invention.
  • the complex salt thus obtained is used for tanning cowhides according to the following specification:
  • Completely delimed and bated pelts are treated in 100 percent of aqueous liquor containing 10 percent of sodium chloride and 3 percent of 30 percent aqueous formaldehyde solution. Thirty minutes later 15 percent of triacrylato-trihydroxotrialuminum chloride is added as a powder and after a period of 6 hours the whole is buffered to a pH value of 5.0 with about 5 percent of sodium bicarbonate in a number of portions. Total treatment time is about 8 to 10 hours. Then 1 percent of persulfuric acid/sulfite is added and the pH value of the liquor is corrected again to 5.0 after 1 hour.
  • the hides are fatliquored with 2 to 5 percent or pure fat in the form of a commercial cationic fatliquor in a l00 percent liquor at 50C. Drying, sawdusting and staking are carried out as usual.
  • a solution of 144 parts of acrylic acid and lO6 parts of sodium carbonate in 4,800 parts of water is added to a solution of 161 parts of aluminum chloride (AlCl '6- H 0) and 89 parts of chromic chloride (CrCl '6H O) in 200 parts of water while stirring.
  • the aged solution is spray-dried.
  • a white-green powder is obtained which dissolves well in water with a green color.
  • sodium chloride and sodium acrylate it contains a salt having the formula:
  • Example 1 may be used as in Example 1 for tanning, with or without pretreatment with formaldehyde.
  • Leather is obtained which withstands the boiling test, has a pale blue color and contains aluminum and acrylic acid radicals in a form incapable of being washed out.
  • a green powder which dissolves in water with a blue color.
  • sodium chloride it contains a salt having the formula:
  • Example II It may be used as in Example I for tanning with or without pretreatment with formaldehyde.
  • a gray leather is obtained which contains chromium and aluminum as well as the acrylic acid radicals present in a form incapable of being washed out.
  • a white powder is obtained which gives a colorless solution in water. It may be used for tanning as in Example 1.
  • a white powder is obtained which gives a colorless solution in water. It may be used as in Example 1 for tanning pelts or after-tanning chrome leather.
  • a mixture of 43.2 parts of monomeric acrylic acid and 33.6 parts of sodium bicarbonate in 500 parts of water is added to a solution of 90.4 parts of a commercial 66 percent basic aluminum chloride ([Al- (OH) ]Cl+2NaCl) having a content of 22 percent of A1 0 and 53.3 parts of chromic chloride (CrCl '6H O) in 300 parts of water and the whole is made up to 1,000 parts with water.
  • a blue violet solution is obtained.
  • a green salt is formed which dissolves in water with a green color. It contains sodium chloride as well as the salt according to the invention.
  • a mixture of 86.5 parts of monomeric acrylic acid and 101 parts of sodium bicarbonate in 500 parts of water is added to a solution of 48.2 parts of aluminum chloride (AlCl -6H O) and 106.6 parts of chromic chloride (CrCl '6l-l O) in 300 parts of water, and the whole is made up to 1,000 parts with water.
  • a red violet solution is obtained which changes to green in a few weeks.
  • a green salt is obtained which dissolves in water to give a green solution. It contains sodium chloride in addition to the salt according to the invention.
  • a mixture of 288 parts of monomeric acrylic acid and 67.0 parts of sodium bicarbonate in 500 parts of water is added to a solution of 45.2 parts of a commercial 66 percent basic aluminum chloride ([Al(Ol-l) ]Cl 2NaCl) having an A1 0 content of 22 percent and 106.6 parts of chromic chloride (CrCl '6H O) in 300 parts of water and the whole is made up to 1,000 parts with water.
  • An ink blue solution is obtained.
  • By spraydrying a blue green salt is obtained which gives a dark blue solution in water. It may be used for tanning as in Example 1.
  • M denotes aluminum and M denotes trivalent chromium as central atoms
  • R denotes the radical of acrylic acid twice combined between two metal atoms
  • a denotes an integer from 1 to 3
  • m denotes an integer from 2 to 6 and which contains monovalent anions which do not make the complex metal salt insoluble in water and are selected from the group consisting of chloride, bromide, iodide, perchlorate, nitrate, formate, acetate and propionate ions.
  • H2O R R OH H O OH OH OH should read Column 3, line #6, "99 C.” should read 90 C.
  • Column 6, line 32-33, "E I M R (0H (+)(+)(+)H should read --E I M R (OH) (H 0)E
  • should read EQ1M2(3 E)RE(OH)(6 IE)(H20)6 Signed and Scaled this Eighteenth Day of January 1977 [SEAL] Q AIIGSI.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
US00195871A 1969-09-05 1971-11-04 Aluminum-chrome acrylic acid complex tannage and leather aluminum or Expired - Lifetime US3792976A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691945006 DE1945006A1 (de) 1969-09-05 1969-09-05 Komplexe Aluminium- und Aluminium-Chrom-Salze

Publications (1)

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US3792976A true US3792976A (en) 1974-02-19

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US00195871A Expired - Lifetime US3792976A (en) 1969-09-05 1971-11-04 Aluminum-chrome acrylic acid complex tannage and leather aluminum or

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US (1) US3792976A (de)
BE (1) BE755742A (de)
CH (1) CH552014A (de)
DE (1) DE1945006A1 (de)
FR (1) FR2060948A5 (de)
GB (1) GB1298975A (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049379A (en) * 1974-05-30 1977-09-20 Basf Aktiengesellschaft Complex basic zirconium salts and aluminum salts
US4264319A (en) * 1978-07-20 1981-04-28 Henkel Kommanditgesellschaft Auf Aktien Water-insoluble aluminosilicates in the manufacture of leather
US4622156A (en) * 1984-04-10 1986-11-11 Alcan International Limited Tanning of leather
KR101572973B1 (ko) 2014-07-17 2015-11-30 경북대학교 산학협력단 신규 이작용기 가교제 화합물, 이의 제조 방법 및 이를 포함하는 약물 방출용 하이드로젤 소프트 콘택트렌즈

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220867A (en) * 1940-04-30 1940-11-05 Du Pont Tanning
US2327815A (en) * 1941-01-31 1943-08-24 American Cyanamid Co Aluminium salt of hydroxy carboxylic acids
US2942930A (en) * 1958-11-07 1960-06-28 Fred P Luvisi Alum tannage
US3714211A (en) * 1970-09-03 1973-01-30 Basf Ag Complex trinuclear metal salts

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220867A (en) * 1940-04-30 1940-11-05 Du Pont Tanning
US2327815A (en) * 1941-01-31 1943-08-24 American Cyanamid Co Aluminium salt of hydroxy carboxylic acids
US2942930A (en) * 1958-11-07 1960-06-28 Fred P Luvisi Alum tannage
US3714211A (en) * 1970-09-03 1973-01-30 Basf Ag Complex trinuclear metal salts

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049379A (en) * 1974-05-30 1977-09-20 Basf Aktiengesellschaft Complex basic zirconium salts and aluminum salts
US4264319A (en) * 1978-07-20 1981-04-28 Henkel Kommanditgesellschaft Auf Aktien Water-insoluble aluminosilicates in the manufacture of leather
US4622156A (en) * 1984-04-10 1986-11-11 Alcan International Limited Tanning of leather
KR101572973B1 (ko) 2014-07-17 2015-11-30 경북대학교 산학협력단 신규 이작용기 가교제 화합물, 이의 제조 방법 및 이를 포함하는 약물 방출용 하이드로젤 소프트 콘택트렌즈

Also Published As

Publication number Publication date
DE1945006A1 (de) 1971-03-11
BE755742A (fr) 1971-03-03
CH552014A (de) 1974-07-31
GB1298975A (en) 1972-12-06
FR2060948A5 (de) 1971-06-18

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