US2732278A - Tanning with tetrakis- - Google Patents
Tanning with tetrakis- Download PDFInfo
- Publication number
- US2732278A US2732278A US2732278DA US2732278A US 2732278 A US2732278 A US 2732278A US 2732278D A US2732278D A US 2732278DA US 2732278 A US2732278 A US 2732278A
- Authority
- US
- United States
- Prior art keywords
- tanning
- thpc
- tannage
- tetrakis
- cowhide
- 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
- AKXUUJCMWZFYMV-UHFFFAOYSA-M tetrakis(hydroxymethyl)phosphanium;chloride Chemical compound [Cl-].OC[P+](CO)(CO)CO AKXUUJCMWZFYMV-UHFFFAOYSA-M 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 12
- 239000010985 leather Substances 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 235000013311 vegetables Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- SXXLKZCNJHJYFL-UHFFFAOYSA-N 4,5,6,7-tetrahydro-[1,2]oxazolo[4,5-c]pyridin-5-ium-3-olate Chemical compound C1CNCC2=C1ONC2=O SXXLKZCNJHJYFL-UHFFFAOYSA-N 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 6
- 210000003491 Skin Anatomy 0.000 description 6
- 102100016214 THPO Human genes 0.000 description 6
- 101710040065 THPO Proteins 0.000 description 6
- VXMKYRQZQXVKGB-CWWHNZPOSA-N Tannin Chemical compound O([C@H]1[C@H]([C@@H]2OC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)O[C@H]([C@H]2O)O1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 VXMKYRQZQXVKGB-CWWHNZPOSA-N 0.000 description 6
- 235000015450 Tilia cordata Nutrition 0.000 description 6
- 235000011941 Tilia x europaea Nutrition 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000004571 lime Substances 0.000 description 6
- 229920001864 tannin Polymers 0.000 description 6
- 239000001648 tannin Substances 0.000 description 6
- 235000018553 tannin Nutrition 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- RXKJFZQQPQGTFL-UHFFFAOYSA-N Dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 235000017343 Quebracho blanco Nutrition 0.000 description 2
- 241000065615 Schinopsis balansae Species 0.000 description 2
- ASCUXPQGEXGEMJ-GPLGTHOPSA-N [(2R,3S,4S,5R,6S)-3,4,5-triacetyloxy-6-[[(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-(4-methylanilino)oxan-2-yl]methoxy]oxan-2-yl]methyl acetate Chemical compound CC(=O)O[C@@H]1[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H](COC(=O)C)O[C@@H]1OC[C@@H]1[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](NC=2C=CC(C)=CC=2)O1 ASCUXPQGEXGEMJ-GPLGTHOPSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000008366 buffered solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 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
Definitions
- This invention relates to the tanning of hides and the manufacture of leather.
- An object of this invention is to provide novel and improved processes for tanning hides. Another object is to provide leather having new and desirable properties.
- hides includes all animal skins that are tanned commercially, such as cowhide, horsehide, calfskin, pigskin, sheepskin and fur skins.
- the bulk of commercial tannage is by use of vegetable tannins and chrome tannage.
- Vegetable tanning is slow and tedious, requiring many steps and several weeks of time.
- Chrome tannage is quicker but more expensive. Both produce leathers having pronounced discoloration; hence, neither is suitable for the production of white or lightcolored leathers. Both require a low pH (acidic condition); hence the lime commonly used in preparing skins for tanning must be completely removed or neutralized.
- a quick and thorough tannage at high or low pH, yielding leather having substantially no discoloration is achieved by treating hides with tetrakis-(hydroxymethyl) phosphonium chloride (hereinafter abbreviated as THPC).
- THPC tetrakis-(hydroxymethyl) phosphonium chloride
- Only a small percentage of THPC is required for satisfactory tannage and it may be applied as an aqueous solution or dissolved in an organic solvent, such as a lower aliphatic alcohol or ketone.
- the hide is prepared as for conventional tannage.
- THPC readily tans hides that have not been pickled and that contain residual lime from the liming step.
- the pH at which THPC tans best is near the isoelectric point of the hide. This will vary somewhat with different kinds of hide and with the type of pretanning treatment given the hide. In general it is in the range of pH 4-6 and the optimum pH for THPC tannage is usually in the range 3-9. At lower pH values tannage is considerably slower while at higher values some of the THPC may be lost through reaction with the alkaline reagent. Usually, however, satisfactory results may be obtained throughout the pH range of about 2-12.
- the temperature of the tanning bath may be varied widely up to the shrinkage temperature of the hide being treated. Faster tannage is obtained at elevated temperatures. Even at ordinary room temperature, however, very rapid tannage isobtained so that usually there is little advantage in applying heat to the tanning bath. Even at 15-20 C. tannage is usually complete in 1-2 hours.
- THPC tannage
- absorption of THPC substantially ceases. of time or high concentrations of THPC do not result in significantly higher degrees of tannage or greater absorption of the reagent.
- untanned or partially tanned hide, as well as leathers tanned by conventional processes have a powerful afiinity for THPC and will absorb it from even very dilute solutions. This is a great advantage since it enables the tanner to use an initially strong tanning bath and yet, after it is progressively depleted through use, to exhaust the bath to substantially zero concentration of THPC before discarding it.
- Ts stands for the shrinkage temperature of the hide or leather as determined in a hot water bath.
- cowhide used in these examples was the commercial white hide obtained after the usual liming and unhairing stages of beamhouse processing.
- the hide was stored in a cold room after pickling with salt and hydrochloric acid.
- Prior to use the pickled cowhide was depickled by immersion in sodium bicarbonate, then thoroughly rinsed in water.
- 15 grams (on a dry weight basis) of the cowhide was treated with ml. of an aqueous buffered solution of tetrakis-(hydroxymethyl) phosphonium chloride.
- gentle agitation of the cowhide under treatment was accomplished by carrying out the re action in a bottle which was rolled on a jar mill.
- the bottle cap contained a vent, above the liquid level, to prevent build up of pressure which was particularly noted in Examples 6, 8, 9, 14, and 15.
- the calfskin used was pickled calfskin obtained from a commercial tannery. After the materials had been treated with THPC they were rinsed thoroughly in water and air dried. All the treatments, except the treatment of Example 10, gave white, firm, flexible leather products.
- a process for tanning hides comprising treating the hides with tetrakis-(hydroxymethyl) phosphonium chloride at a pH of about 2 to 12.
- a process for tanning hides comprising treating the hides with tetrakis-(hydroxymethyl) phosphonium chloride at a pH of about 2 to 12, and then retanning with vegetable tannin.
- a process for retanning leather comprising treating the leather with tetrakis-(hydroxymethyl) phosphonium chloride at a pH of about 2 to 12.
Description
United States Patent TANNING WITH TETRAKIS-(HYDROXYMETHYL) PHOSPHONIUM CHLORIDE Edward M. Filachione, Philadelphia, Pa., assignor to the United States of America as represented by the Secretary of Agriculture No Drawing. Application March 22, 1955, Serial No. 496,086
A non-exclusive, irrevocable, royalty-free license in the invention herein described for all governmental purposes, throughout the world, with power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.
This invention relates to the tanning of hides and the manufacture of leather.
An object of this invention is to provide novel and improved processes for tanning hides. Another object is to provide leather having new and desirable properties.
The term hides," as used herein, includes all animal skins that are tanned commercially, such as cowhide, horsehide, calfskin, pigskin, sheepskin and fur skins.
The bulk of commercial tannage is by use of vegetable tannins and chrome tannage.
Vegetable tanning is slow and tedious, requiring many steps and several weeks of time.
Chrome tannage is quicker but more expensive. Both produce leathers having pronounced discoloration; hence, neither is suitable for the production of white or lightcolored leathers. Both require a low pH (acidic condition); hence the lime commonly used in preparing skins for tanning must be completely removed or neutralized.
According to the invention, a quick and thorough tannage at high or low pH, yielding leather having substantially no discoloration, is achieved by treating hides with tetrakis-(hydroxymethyl) phosphonium chloride (hereinafter abbreviated as THPC). Only a small percentage of THPC is required for satisfactory tannage and it may be applied as an aqueous solution or dissolved in an organic solvent, such as a lower aliphatic alcohol or ketone.
In general, the hide is prepared as for conventional tannage. THPC readily tans hides that have not been pickled and that contain residual lime from the liming step. The pH at which THPC tans best is near the isoelectric point of the hide. This will vary somewhat with different kinds of hide and with the type of pretanning treatment given the hide. In general it is in the range of pH 4-6 and the optimum pH for THPC tannage is usually in the range 3-9. At lower pH values tannage is considerably slower while at higher values some of the THPC may be lost through reaction with the alkaline reagent. Usually, however, satisfactory results may be obtained throughout the pH range of about 2-12.
The temperature of the tanning bath may be varied widely up to the shrinkage temperature of the hide being treated. Faster tannage is obtained at elevated temperatures. Even at ordinary room temperature, however, very rapid tannage isobtained so that usually there is little advantage in applying heat to the tanning bath. Even at 15-20 C. tannage is usually complete in 1-2 hours.
Only a small amount of THPC is required for tannage, usually about 15% based on the dry weight of the hide. When the tannage is complete, absorption of THPC substantially ceases. of time or high concentrations of THPC do not result in significantly higher degrees of tannage or greater absorption of the reagent. On the other hand, untanned or partially tanned hide, as well as leathers tanned by conventional processes, have a powerful afiinity for THPC and will absorb it from even very dilute solutions. This is a great advantage since it enables the tanner to use an initially strong tanning bath and yet, after it is progressively depleted through use, to exhaust the bath to substantially zero concentration of THPC before discarding it.
The following examples illustrate several embodiments of the invention. 1
The abbreviation Ts stands for the shrinkage temperature of the hide or leather as determined in a hot water bath.
EXAMPLES l-lS The cowhide used in these examples was the commercial white hide obtained after the usual liming and unhairing stages of beamhouse processing. The hide was stored in a cold room after pickling with salt and hydrochloric acid. Prior to use the pickled cowhide was depickled by immersion in sodium bicarbonate, then thoroughly rinsed in water. Generally 15 grams (on a dry weight basis) of the cowhide was treated with ml. of an aqueous buffered solution of tetrakis-(hydroxymethyl) phosphonium chloride. Gentle agitation of the cowhide under treatment was accomplished by carrying out the re action in a bottle which was rolled on a jar mill. The bottle cap contained a vent, above the liquid level, to prevent build up of pressure which was particularly noted in Examples 6, 8, 9, 14, and 15. The calfskin used was pickled calfskin obtained from a commercial tannery. After the materials had been treated with THPC they were rinsed thoroughly in water and air dried. All the treatments, except the treatment of Example 10, gave white, firm, flexible leather products.
Pertinent data are shown in the following table.
Treatments involving extended periods Table-Tanning with THPC Initial Ooncn. of
05 Hour 1 Hour 2 Hours 4 Hours 24 Hours THPC, Percent pH pH None Phosphate tate Phosphate. Bicarbonate".
. o Phosphate. Lime Phosphate do do Bicarbonate... Phosphate.
mcngomcnumorgecnmpsmmm Analysis, percent phosphorus, of treated cowhide: after 1 hr. 0.23% (0.26% M. F. B.); after 2 hrs., 0.31% (0.34% M. F. B.); alterhrs. 0.37%
(0.41% M. F. B)
b Analysis, (0.74% M. F. B.
a The weight gain of the treated calfskin was approximately 36%.
EXAMPLE 16 A sample of cowhide which had been tanned with tetrakis-(hydroxymethyl) phosphonium chloride as in Example 3 above (Ts=79 C.) was treated with a concentrated solution (30% solids or 105 Barkorneter) of sulfited quebracho extract. After two days the vegetable tannin had completely penetrated the cowhide, and the shrinkage temperature of the cowhide under treatment was elevated to 90 C. After rinsing in water the treated cowhide dried to a leather resembling sole leather.
EXAMPLE 17 I ercent phosphorus, of treated cowhide: after 1 hr. 0.34% P (0.38% M. F. B.); after 2 hrs, 0.43% P (0.48% M. F. B.); after 4 hrs. 0.67% I (THPO). Hence, it appears probable that when THPC is used as a tanning agent in an alkaline solution, the active agent is THPO. In any case, I have found that THPO is a tanning agent and, in alkaline solutions, is equivalent to THPC. In acid solutions it appears to be less reactive than THPC, though still effective.
I claim:
1. A process for tanning hides comprising treating the hides with tetrakis-(hydroxymethyl) phosphonium chloride at a pH of about 2 to 12.
2. A process for tanning hides comprising treating the hides with tetrakis-(hydroxymethyl) phosphonium chloride at a pH of about 2 to 12, and then retanning with vegetable tannin.
3. A process for retanning leather comprising treating the leather with tetrakis-(hydroxymethyl) phosphonium chloride at a pH of about 2 to 12.
References Cited in the file of this patent UNITED STATES PATENTS 2,668,096 Reeves et a1. Feb. 2, 1954
Claims (1)
1. A PROCESS FOR TANNING HIDES COMPRISING TREATING THE HIDES WITH TETRAKIS-(HYDROXYMETHYL) PHOSPHONIUM CHLORIDE AT A PH OF ABOUT 2 TO 12.
Publications (1)
Publication Number | Publication Date |
---|---|
US2732278A true US2732278A (en) | 1956-01-24 |
Family
ID=3442002
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US2732278D Expired - Lifetime US2732278A (en) | Tanning with tetrakis- |
Country Status (1)
Country | Link |
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US (1) | US2732278A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2992879A (en) * | 1959-09-25 | 1961-07-18 | Windus Wallace | Tanning with tetrakis (hydroxymethyl) phosphonium chloride and phenol |
US2993744A (en) * | 1959-02-18 | 1961-07-25 | Lewellyn G Picklesimer | Thpo tanned leather |
US3256154A (en) * | 1963-10-18 | 1966-06-14 | Gillette Co | Hair waving composition and method |
US3419344A (en) * | 1966-04-20 | 1968-12-31 | Swift & Co | Fatliquoring with tetrakis (hydroxy-alkylene) phosphonium halide and an organic phosphate ester and leather flameproofed thereby |
WO2002038813A1 (en) * | 2000-11-13 | 2002-05-16 | Rhodia Consumer Specialties Limited | Tannages |
US6540790B2 (en) | 1997-10-30 | 2003-04-01 | Rhodia Consumer Specialties Limited | Tanning leather |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2668096A (en) * | 1952-04-22 | 1954-02-02 | Wilson A Reeves | Flameproof fibrous aminoethylated cellulose derivatives |
-
0
- US US2732278D patent/US2732278A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2668096A (en) * | 1952-04-22 | 1954-02-02 | Wilson A Reeves | Flameproof fibrous aminoethylated cellulose derivatives |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2993744A (en) * | 1959-02-18 | 1961-07-25 | Lewellyn G Picklesimer | Thpo tanned leather |
US2992879A (en) * | 1959-09-25 | 1961-07-18 | Windus Wallace | Tanning with tetrakis (hydroxymethyl) phosphonium chloride and phenol |
US3256154A (en) * | 1963-10-18 | 1966-06-14 | Gillette Co | Hair waving composition and method |
US3419344A (en) * | 1966-04-20 | 1968-12-31 | Swift & Co | Fatliquoring with tetrakis (hydroxy-alkylene) phosphonium halide and an organic phosphate ester and leather flameproofed thereby |
US6540790B2 (en) | 1997-10-30 | 2003-04-01 | Rhodia Consumer Specialties Limited | Tanning leather |
WO2002038813A1 (en) * | 2000-11-13 | 2002-05-16 | Rhodia Consumer Specialties Limited | Tannages |
GB2383049A (en) * | 2000-11-13 | 2003-06-18 | Rhodia Cons Spec Ltd | Tannages |
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