US2129553A - Tanning material - Google Patents
Tanning material Download PDFInfo
- Publication number
- US2129553A US2129553A US2129553DA US2129553A US 2129553 A US2129553 A US 2129553A US 2129553D A US2129553D A US 2129553DA US 2129553 A US2129553 A US 2129553A
- Authority
- US
- United States
- Prior art keywords
- formaldehyde
- urea
- tanning
- sulfonate
- sulfone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000463 material Substances 0.000 title description 40
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 100
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 88
- 239000004202 carbamide Substances 0.000 description 44
- -1 sulfone sulfonate Chemical class 0.000 description 30
- 239000010985 leather Substances 0.000 description 26
- KZTYYGOKRVBIMI-UHFFFAOYSA-N Diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 20
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000007859 condensation product Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating Effects 0.000 description 8
- 238000004061 bleaching Methods 0.000 description 6
- 150000003457 sulfones Chemical class 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000005282 brightening Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 210000003491 Skin Anatomy 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 125000004432 carbon atoms Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
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
- C14C3/08—Chemical tanning by organic agents
- C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
- C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated
-
- 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
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
Definitions
- This invention relates to the manufacture of tanning materials suitable for tanning pickled stock, for retanning leather already made by other means, and for bleaching or brightening chrome leather.
- the dihydroxy diaryl sulfone sulfonate prepared by any suitable method, as for instance those disclosed in the above mentioned copending application, 'is dis- .solvedor diluted with water and to the solution urea is added and dissolved with the aid of heat if desired.
- The-temperature of the solution is then raised to a point at which the urea and sulfone will react with formaldehyde and the formaldehyde added slowly. When all the formaldehydehas been added the temperature is maintained at or near the boiling point of the solution until reaction is complete. It may then be cooled,
- the relative proportion of urea, sulfone sulfonate and formaldehyde that may be used varies 40 overs. wide range.
- the best ratio we have found is two molecular equivalents each of formaldehyde and sulfone sulfonate to one molecularequivalent of urea. These ratios we believe give on condensation a molecule having the formula wherein the R's represent similar or dissimilar dihydroxy diaryl sulfone sulfonates attached to v 9 the methylene groups by nuclear carbon atoms.
- the formaldehyde may be reduced to a lower limit of one mol. of formaldehyde for each two mols of sulfone sulfonate particularly when less than the best ratio i of urea to suifonate is used. An excess over this lower limit equivalent to the quantity of urea used is desirable.
- a convenient rule to follow is to use at least one mol. of formaldehyde for each two mols of sulfone sulfonate plus one mol. of 5') formaldehyde for each mol. of urea.
- the conditions of reaction such as temperature, 20 dilution, acidity, etc., are largely a matter of choice and affect the speed of the reaction more than the quality of the reaction product.
- Lower temperatures and high dilution slow the reaction and if the acidity becomes too high difficulty may be met in maintaining a suitably controlled rate of reaction.
- conditions of 30 reaction we have found convenient are illustrated but by a few simple tests other conditions equally suitable can be readily determined. In these examples the parts given are by weight.
- Example 1.50 parts of 4:4 dihydroxy di- 35 phenyl sulfone is added to 70 parts of 98% sulfuric acid and the mixture heated-at 1i0-l20 C.
- Example 2 parts of 4:4 dihydroxy di-- 50 phenyl sulfone is sulfonated as in Example 1 using parts of 98% sulfuric acid. .6 parts of urea is dissolved in the sulfonation mixture and 51 parts of water added. The mixture is then heated to 98-100 C. and 20 parts of 30% aqueous formaldehyde added slowly over 10 minutes. The mixture is maintained at 98-100 C. and stirred continuously for three hours, then cooled, partly neutralized with 34 parts of caustic soda and diluted with water to a final mass of 520 parts.
- the tanning materials'p'roduced' as in these examples may be used alone or in combination with other tanning materials in tanning skins or in retanning leather made byother tanning materials but their greatest value is found in their ability to bleach and brighten .chrome tanned leather. a white leather that has a resistance to sunlight even greater than that produced from tanning materials made from the sulfone'sulfonate and formaldehyde alone.
- dihydroxy diaryl sul fone sulfonates such as those in which one or both the phenyl groups of the diphenyl compound are substituted by one or more methyl or other alkyl groups may be substituted for the dihydroxy diphenyl sulfone sulfonate used in these examples.
- Example 3 100 pounds of fully tanned chrome calfskin is drummed for an hour at F. with pounds of water and ten pounds, or other suitable quantity, of the tanning material prepared as described in Example 1; The stock is now washed with water till it shows a pH of 4-4 when it may be oiled arid finished in any recognized manner.
- the leather so produced has a white surface of remarkable resistance to the action of strong sunlight.
- a synthetic tanning material which in the acidic form consists of the joint condensation product of a dihydroxy diaryl sulf one sulfonate and urea with formaldehyde.
- a synthetic tanning material which in the acidic form consists of the joint condensation product of a dihydroxy diphenyl sulfone sulfonate and urea with formaldehyde.
- a synthetic tanning material which in the acidic form consists of the joint condensation product of 4:4 dihydroxy diphenyl sulfone sulfonate and urea with formaldehyde.
- a synthetic tanning material which in the acidic form consists of the joint condensation products of substantially two molecular equivalents of a dihydroxy diphenyl sulfone sulfonate and substantially one molecular equivalent of urea and substantially two molecular equivalents of formaldehyde.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Description
Patent ed Sept. 6 1938 UNITED STATES TANNING MATERIAE Alfred Russell and 'John w. Copenhaver, Philadelphia, Pa., assignors to Rohm & Haas Company,
Philadelphia, Pa.
No Drawing. Application October so, 1937, Serial No. 172,042
10 Claims.
This invention relates to the manufacture of tanning materials suitable for tanning pickled stock, for retanning leather already made by other means, and for bleaching or brightening chrome leather.
In our 'copending application, Serial No. 161,- 066, filed August 26, 1937, it is shown that excellent tanning materials especially suitable for the bleaching of chrome leather can be made by sulfonating a dihydroxy diaryl sulfone and condensing the resulting sulfone sulfonate with formaldehyde, We have now found that by co-condensing urea with the sulfone sulfonate and formaldehyde, a joint urea-sulfone sulfonate-formaldel5 hyde condensate is obtained that has certain advantages over the material obtained from the sulfone sulfonate and formaldehyde only. These advantages are particularly noticeable when the new tanning materials are used to bleach chrome stock. A better bleaching and brightening is obtained and the leather has a greater resistance to the action of sunlight.
In practicing the invention the dihydroxy diaryl sulfone sulfonate prepared by any suitable method, as for instance those disclosed in the above mentioned copending application, 'is dis- .solvedor diluted with water and to the solution urea is added and dissolved with the aid of heat if desired. The-temperature of the solution is then raised to a point at which the urea and sulfone will react with formaldehyde and the formaldehyde added slowly. When all the formaldehydehas been added the temperature is maintained at or near the boiling point of the solution until reaction is complete. It may then be cooled,
neutralized to the proper pH and diluted with water to the desired concentration.
The relative proportion of urea, sulfone sulfonate and formaldehyde that may be used varies 40 overs. wide range. The best ratio we have found is two molecular equivalents each of formaldehyde and sulfone sulfonate to one molecularequivalent of urea. These ratios we believe give on condensation a molecule having the formula wherein the R's represent similar or dissimilar dihydroxy diaryl sulfone sulfonates attached to v 9 the methylene groups by nuclear carbon atoms.
Reducing the quantity of urea decreases the quantity of this material in the final condensate but and only the maximum advantage of the invention lost by the reduction. The formaldehyde may be reduced to a lower limit of one mol. of formaldehyde for each two mols of sulfone sulfonate particularly when less than the best ratio i of urea to suifonate is used. An excess over this lower limit equivalent to the quantity of urea used is desirable. .A convenient rule to follow is to use at least one mol. of formaldehyde for each two mols of sulfone sulfonate plus one mol. of 5') formaldehyde for each mol. of urea.
Increasing the quantity of urea and/or formaldehyde above the best ratios above mentioned leads to the formation of more complicated molecules that also have tanning properties but no if further improvement is thereby obtained. How ever, if desired, up to four mols of formaldehyde and up to two mols of urea can be used with two mols of sulfone sulfonate.
The conditions of reaction such as temperature, 20 dilution, acidity, etc., are largely a matter of choice and affect the speed of the reaction more than the quality of the reaction product. We prefer to carry out the reaction at or about the boiling point of water and at the natural pH 25 of the sulfone sulfonate solution. Lower temperatures and high dilution slow the reaction and if the acidity becomes too high difficulty may be met in maintaining a suitably controlled rate of reaction. In the following examples, conditions of 30 reaction we have found convenient are illustrated but by a few simple tests other conditions equally suitable can be readily determined. In these examples the parts given are by weight.
Example 1.50 parts of 4:4 dihydroxy di- 35 phenyl sulfone is added to 70 parts of 98% sulfuric acid and the mixture heated-at 1i0-l20 C.
' for from 15 to 20 minutes or until a product enten minutes and the reaction mixture maintained v at 98-100 C. for four hours. It is then cooled somewhat, partly neutralized with 34 parts of caustic soda and diluted with water to a final.
mass of 520 parts.
Example 2. parts of 4:4 dihydroxy di-- 50 phenyl sulfone is sulfonated as in Example 1 using parts of 98% sulfuric acid. .6 parts of urea is dissolved in the sulfonation mixture and 51 parts of water added. The mixture is then heated to 98-100 C. and 20 parts of 30% aqueous formaldehyde added slowly over 10 minutes. The mixture is maintained at 98-100 C. and stirred continuously for three hours, then cooled, partly neutralized with 34 parts of caustic soda and diluted with water to a final mass of 520 parts.
The tanning materials'p'roduced' as in these examples may be used alone or in combination with other tanning materials in tanning skins or in retanning leather made byother tanning materials but their greatest value is found in their ability to bleach and brighten .chrome tanned leather. a white leather that has a resistance to sunlight even greater than that produced from tanning materials made from the sulfone'sulfonate and formaldehyde alone. Other dihydroxy diaryl sul fone sulfonates such as those in which one or both the phenyl groups of the diphenyl compound are substituted by one or more methyl or other alkyl groups may be substituted for the dihydroxy diphenyl sulfone sulfonate used in these examples.
In order to illustratethe use of these tanning materials to brighten chrome tanned leather the following example is given.
Example 3.-100 pounds of fully tanned chrome calfskin is drummed for an hour at F. with pounds of water and ten pounds, or other suitable quantity, of the tanning material prepared as described in Example 1; The stock is now washed with water till it shows a pH of 4-4 when it may be oiled arid finished in any recognized manner. The leather so produced has a white surface of remarkable resistance to the action of strong sunlight.
We claim:
1. The process of preparing a synthetic tanning material which comprises co-condensing a dihydroxy diaryl sulfone sulfonate and urea with formaldehyde.
2. The process of preparing a synthetic tanning material which comprises co-condensing a dihydroxy diphenyl sulfone sulfonate and urea with formaldehyde.
3. The process of preparing a synthetic tan- When used for this purpose they give ning material which comprises co-condensing 4:4 dihydroxy diphenyl sulfone sulfonate and urea with formaldehyde.
4. The process of preparing a synthetic tanning material which comprises co-condensin substantially two molecular equivalents of a dihydroxy diphenyl sul'fone sulfonate and substantially one molecular equivalent of urea and substantially two molecular equivalents of formaldehyde.
5. A synthetic tanning material which in the acidic form consists of the joint condensation product of a dihydroxy diaryl sulf one sulfonate and urea with formaldehyde.
6. A synthetic tanning material which in the acidic form consists of the joint condensation product of a dihydroxy diphenyl sulfone sulfonate and urea with formaldehyde.
7. A synthetic tanning material which in the acidic form consists of the joint condensation product of 4:4 dihydroxy diphenyl sulfone sulfonate and urea with formaldehyde.
8. A synthetic tanning material which in the acidic form consists of the joint condensation products of substantially two molecular equivalents of a dihydroxy diphenyl sulfone sulfonate and substantially one molecular equivalent of urea and substantially two molecular equivalents of formaldehyde.
9. In the process of making leather the improvement which comprises treating a. chrome tanned leather with a joint condensation product of a. dihydroxy diphenyl sulfone sulfonate, urea and formaldehyde.
10. In the process of making leather the improvement which comprises treating a chrome tanned leather with a joint condensation product of substantially two molecular equivalents of a dihydroxy diphenyl sulfone sulfonate, substantially one molecular equivalent of urea, and substantially two molecular equivalents of formaldehyde.
ALFRED RUSSELL. JOHN W; COPENHAVER.
Publications (1)
Publication Number | Publication Date |
---|---|
US2129553A true US2129553A (en) | 1938-09-06 |
Family
ID=3429649
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US2129553D Expired - Lifetime US2129553A (en) | Tanning material |
Country Status (1)
Country | Link |
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US (1) | US2129553A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2733977A (en) * | 1956-02-07 | Process of tanning with salt of ampho- | ||
US2809088A (en) * | 1952-07-12 | 1957-10-08 | Bayer Ag | Process of retanning leather with a condensation product of sulfones of monohydric phenols, non-aromatic amines and formaldehyde |
US3029212A (en) * | 1957-09-09 | 1962-04-10 | Nopco Chem Co | Synthetic tanning agent and process for preparing same |
US3533724A (en) * | 1965-02-10 | 1970-10-13 | Bayer Ag | Substantially dry syntan or waste sulfite liquor pretannage of vegetable tanned or syntanned leather |
US4009996A (en) * | 1973-11-08 | 1977-03-01 | Ciba-Geigy Corporation | Reaction products of phenolsulphonic acid-urea-formaldehyde as tanning agents and process for their manufacture |
-
0
- US US2129553D patent/US2129553A/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2733977A (en) * | 1956-02-07 | Process of tanning with salt of ampho- | ||
US2809088A (en) * | 1952-07-12 | 1957-10-08 | Bayer Ag | Process of retanning leather with a condensation product of sulfones of monohydric phenols, non-aromatic amines and formaldehyde |
US3029212A (en) * | 1957-09-09 | 1962-04-10 | Nopco Chem Co | Synthetic tanning agent and process for preparing same |
US3533724A (en) * | 1965-02-10 | 1970-10-13 | Bayer Ag | Substantially dry syntan or waste sulfite liquor pretannage of vegetable tanned or syntanned leather |
US4009996A (en) * | 1973-11-08 | 1977-03-01 | Ciba-Geigy Corporation | Reaction products of phenolsulphonic acid-urea-formaldehyde as tanning agents and process for their manufacture |
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