CN1053448A - A kind of manufacture method of bleaching chromium-containing synthetic compound tanning agent - Google Patents
A kind of manufacture method of bleaching chromium-containing synthetic compound tanning agent Download PDFInfo
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- CN1053448A CN1053448A CN90105757A CN90105757A CN1053448A CN 1053448 A CN1053448 A CN 1053448A CN 90105757 A CN90105757 A CN 90105757A CN 90105757 A CN90105757 A CN 90105757A CN 1053448 A CN1053448 A CN 1053448A
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Abstract
The present invention is the manufacture method of bleaching chromium-containing synthetic compound tanning agent, it adopts phenol or cresols or mixed phenol and the directly synthetic mixture that contains dihydroxy diphenylsulphone and phenol sulfonic acid of the vitriol oil, pass through sulfomethylation again, regulating material pH value with said mixture again is that acid back and urea reaction generate a kind of new urea-formaldehyde condensation compound, and reacts through complexing under high temperature and acidic conditions as intermediate and alkali formula chromic salts with this and to make.The inventive method products made thereby has the chrome tanning characteristic, and its bleaching property, photostabilization are good, and the pollution of chromium of tanning waste water is little, and its waste water contains chromium (Cr
2O
3) be 0.4～0.5 grams per liter.
Description
The present invention is that a kind of bleaching type of processing light color, white soft ox upper leather (ox, buffalo, yak upper leather) and pig leather, glove leather that is applicable to contains the manufacture method of chromium synthetic compound tanning agent.
American documentation literature U.S.P2997364; U.S.P3254937; U.S.P3519379 and Japanese kokai publication sho 50-155601 disclose the manufacture method about the synthetic tanning agent that contains chromic salts.Wherein, U.S.P2997364 is with mixed phenol (phenol: be that raw material is handled with S-WAT and urea with formaldehyde condensation under alkaline medium cresols=1: 4) again, mix with chromium alum more thereafter.This type of synthetic tanning agent is not had a bleachability, and photostabilization is bad, and especially synthetic tanning agent and chromic salts only are mixture, exists so chromic salts still is the form of non-binding chromium, will be free in a large number during tanning in the waste liquid and causes obvious pollution of chromium.U.S.P3254937 proposed is sulfomethylation product and chromic salts blended manufacture method with the phenol formaldehyde (PF) condenses, and still there is the same shortcoming of aforementioned patent in this method.And these two kinds of disclosed methods of patent can only obtain to use as a kind of tanning agent that gives of planting quick tannage.The product that United States Patent (USP) U.S.P3519379 is made can only be made the quick tannage of planting of bottom leather (heavy leather) and process, and its problem is the same with the former.The modification basic chromic sulfate class of Japanese kokai publication sho 50-155601 patent manufacturing contains the synthetic tanning agent of chromium, and its bleaching property is relatively poor, and photostabilization is also bad, and the waste water pollution of chromium does not achieve a solution yet.The trade mark of Switzerland Ciba-Giege company is that the trade mark that contains chrome syntans and West Germany BASF AG of TannescoH is the chrome syntans that contains of Basytan CD, and the synthetic tanning agent that contains chromium of above-mentioned three kinds of patent disclosures, all have the common shortcoming: the one, bleaching property or bleaching property are not poor; The 2nd, when containing the synthetic tanning agent tan leather of chromium with such, the content (Cr of chromium in the waste water
2O
3) all greater than 1.5～2.0 grams per liters.The bleaching chromium-containing synthetic compound tanning agent of the inventive method manufacturing is with phenol or cresols or mixed phenol and the directly synthetic mixture (hereinafter to be referred as the A material) that contains dihydroxy diphenylsulphone and phenol sulfonic acid of the vitriol oil, again by sulfomethylation, and with A material adjusting material pH value serves as that acid back generates a kind of new urea-formaldehyde condensation compound with urea reaction.And with this as intermediate and alkali formula chromic salts, under high temperature and acidic conditions, react through complexing and to make.The bleaching chromium-containing synthetic compound tanning agent that the inventive method is made has bleaching property, photostabilization is good, has the chrome tanning characteristic again.Particularly be significantly less than aforementioned various product, waste water chrome content (Cr with the inventive method its tanning waste water pollution of chromium that manufactures a product
2O
3) only be 0.4～0.5 grams per liter.
The objective of the invention is defective at the existence of aforementioned patent method products made thereby, it is good to propose a kind of bleaching and photostabilization, the manufacture method applicable to the bleaching chromium-containing synthetic compound tanning agent of processing light color, white soft ox upper leather (ox, buffalo, yak upper leather) and pig clothes leather, glove leather that pollution of chromium is little.
The inventive method is achieved in that the present invention is finished by following steps: the first step prepares the mixture of dihydroxy diphenylsulphone and phenol sulfonic acid.With phenols (referring to phenol, cresols, mixed phenol), vitriol oil sum is benchmark, by weight, each composition percentage composition sum counts 100%, the phenols with 40～50% and 60～50% the vitriol oil mix, and are heated to 95～100 ℃, react 1～2 hour, under 200～300mmHg, above-mentioned material is warming up to 148～150 ℃, stirs insulation 1～4 hour, can make the mixture (being called for short the A material) of dihydroxy diphenylsulphone and phenol sulfonic acid.Second step preparation sulfomethylation condenses.Expect with A, the mixture of sodium bisulfite or S-WAT or sodium bisulfite and S-WAT, sodium hydroxide, formaldehyde and alcoholic acid mixed solution and water sum are benchmark, by weight, each composition percentage composition sum counts 100%, A material with 20～24% and 4～6% the sodium bisulfite or the mixture of S-WAT or sodium bisulfite and S-WAT, water with 33～40% is diluted mixture in addition, transferring pH value with sodium hydroxide is 8～9, under 40～45 ℃, add 12～27% formaldehyde and alcoholic acid mixed solution 55～65 ℃ of following insulated and stirred 1～2 hour, be warmed up to 99～100 ℃ again, stir insulation 1～2 hour, can make pH value and be 8～8.5 sulfomethylation condenses (hereinafter to be referred as the B material).The 3rd step was with above-mentioned A material, the B material, and urea, formaldehyde and alcoholic acid mixed solution, sodium hydroxide, alkali formula chromic salts, the water sum is a benchmark, by weight, each composition percentage composition sum counts 100%, A with 24～25% expects with after 2～3% the water dilution, mix with 19～31% B material, add 2.5～6% urea mixing again, at pH value less than 1 be not higher than and add 13～21% formaldehyde and alcoholic acid mixed solution under 45 ℃ the condition, under 55～65 ℃, protect and stirred 1～2 hour, transferring pH value with sodium hydroxide thereafter is 4.5, transferring pH value with micro-formic acid again is 4, must urinate the hydroformylation condenses, add at last 12～18% alkali formula chromic salts again, be reduced to 60 ℃ of dischargings in 95～100 ℃ of following stirring and refluxing 20～30 minutes, can make its pH value is 5～6, and containing is the slimy bleaching chromium-containing synthetic compound tanning agent of deep green thickness of 52 ± % admittedly.
The major advantage of the inventive method is: with the prepared product of the inventive method, can be dissolved in the hot water or cold water entirely, have use pH value wide ranges, the leather base of institute's tanning have pleasing white, good level-dyeing property, soft, plentiful, photostabilization is good, and becomes the flat characteristics such as thin of grain.When doing chrome-tanned retanning, waste water chromium (Cr
2O
3) content is low, only is 0.4～0.5 grams per liter.Present method products made thereby is the desirable supplementary material of producing high-grade sports shoes with white soft ox upper leather, as with the supporting use of auxiliary bleaching synthetic compound tanning agent, low-quality yak skin can be processed into white fancy leather with natural graining.
With the prepared product of the inventive method, supporting trying out in the pigskin garment leather of Chengdu tannery detected through Sichuan Province's leather and quality of item supervision and inspection station, and the tensile strength of the pigskin garment leather of this method products made thereby tanning is 10.4N/mm
2, elongation 26.5%, shrinkage temperature is greater than 98 ℃, and colour fastness test (level) is done/wet 4.0/4.5, and the height 11.1mm that bursts apart all meets national standard.
Below be embodiments of the invention:
1. 40kg phenol is mixed with the 50kg vitriol oil, be heated to 95～100 ℃ of reactions 2 hours, material is warmed up to 148～150 ℃ being decompressed under the pressure of 200～300mmHg subsequently, and under agitation be incubated 2 hours and make the A material.With the A of 20kg material and 5kg sodium bisulfite with the water of 33kg in addition after the diluted mixture, transferring pH value with sodium hydroxide is 8～9, and at 40 ℃ of following 10kg formaldehyde and 1kg alcoholic acid mixed solutions of adding, subsequently 60 ℃ of following insulated and stirred 1 hour, be warmed up to 99～100 ℃ again, stir insulation 1 hour pH value is 8～8.5 B material.After A being expected the water dilution of 18kg usefulness 1.6kg, mixes the acquisition pH value with B material 20kg less than 1 acidic conditions, and interpolation 3kg urea mixes, be not higher than 45 ℃ of adding 12kg formaldehyde and alcoholic acid mixed solutions (blending ratio is 10: 1) down, and 60 ℃ of following insulated and stirred 1 hour, transferring pH value with sodium hydroxide subsequently is 4.5, with micro-formic acid the material pH value is adjusted to 4 again.Add 11kg alkali formula chromic salts again in 95 ℃ of following stirring and refluxing 30 minutes, last, be cooled to 60 ℃ of dischargings, can make deep green thickness slurry, its pH value is 5～6, solid content is the bleaching chromium-containing synthetic compound tanning agent of 52 ± %.
2. 45kg phenol and m-cresols (1: 2 ω t) are mixed with the 55kg vitriol oil, be heated to 95～100 ℃ of reactions 1.5 hours, material is warmed up to 148～150 ℃ being decompressed under the pressure of 200～300mmHg subsequently, and under agitation is incubated 2.5 hours and makes the A material.With the S-WAT of the A of 16kg material and 4kg with the water of 27kg in addition after the diluted mixture, transferring pH value with sodium hydroxide is 8～9, and under 45 ℃, the mixed solution that adds formaldehyde 8kg and ethanol 2kg, subsequently 55 ℃ of following insulated and stirred 1.5 hours, be warmed up to 99～100 ℃ again, stir insulation 2 hours pH value is 8～8.5 B material.After A being expected the water dilution of 20kg usefulness 1.8kg, 16kg mixes with the B material, obtain pH value less than 1 acidic conditions, and interpolation 2.5kg urea mixes, be lower than 45 ℃ of adding 18kg formaldehyde and alcoholic acid mixtures (ratio of mixture is 4: 1) down, and 60 ℃ of following insulated and stirred 1.5 hours, transferring pH value with sodium hydroxide subsequently was 4.5, with micro-formic acid the material pH value is adjusted to 4 again.Add 15kg alkali formula chromic salts again in 95～100 ℃ of following stirring and refluxing 25 minutes, be cooled to 60 ℃ of dischargings, making pH value is 5～6, and solid content is the slimy product of the made deep green of the inventive method of 52 ± %.
3. with 45kg mixture cresol (o-: m-: p-=5: 3: 1 ω t) mix, be heated to 95～100 ℃ of reactions 1 hour, under 200～300mmHk pressure, material is warmed up to 148～150 ℃ subsequently, and under agitation be incubated 3 hours and make the A material with the 45kg vitriol oil.With the sodium bisulfite of the A of 19kg material and 5.5kg with the water of 31kg in addition after the diluted mixture, transferring pH value with sodium hydroxide is 8～9, and at 42 ℃ of mixed solutions that add formaldehyde 19kg and ethanol 1.5kg down, subsequently 62 ℃ of following insulated and stirred 2 hours, be warmed up to 99～100 ℃ again, stir insulation 1 hour pH value is 8～8.5 B material.After A being expected the water dilution of 16kg usefulness 1.4kg, mixes the acquisition pH value with B material 18kg less than 1 acidic conditions, and the urea that adds 3.5kg mixes, be lower than 45 ℃ of adding 11kg formaldehyde and alcoholic acid mixed solutions (ratio of mixture is 12.7: 1) down, 65 ℃ of following insulated and stirred 2 hours, transferring pH value with sodium hydroxide subsequently is 4.5, with micro-formic acid the material pH value is adjusted to 4 again.Add 8kg alkali formula chromic salts again in 95～100 ℃ of following stirring and refluxing 20 minutes, be cooled to 60 ℃ of dischargings, can make product, solid content 52 ± % into the slimy the inventive method of deep green.
4. the phenol with 40kg mixes with the 60kg vitriol oil with mixture cresol (3: 1 ω t), is heated to 95～100 ℃ of reactions 1 hour, under 200～300mmHg, material is warmed up to 148～150 ℃ subsequently, and under agitation is incubated 4 hours and makes the A material.After 18.5kgA material, 4.2kg sodium bisulfite and S-WAT mixture (2: 1 ω t) the usefulness water diluted mixture of 30.7kg, transferring pH value with sodium hydroxide is 8～9, and at 45 ℃ of mixed solutions that add formaldehyde 22kg and ethanol 2kg down, subsequently 65 ℃ of following insulated and stirred 1.5 hours, be warmed up to 99～100 ℃ again, stirring insulation, to make its pH value in 1.5 hours be 8～8.5 B material.After A being expected the water dilution of 17.5kg usefulness 1.6kg, mixes the acquisition pH value with B material 22kg less than 1 acidic conditions, and the urea that adds 2.2kg mixes, be lower than 45 ℃ of formaldehyde and alcoholic acid mixed solutions (ratio of mixture is 10: 1) that add 10kg down, and 55 ℃ of following insulated and stirred 1.5 hours, transferring pH value with sodium hydroxide subsequently is 4.5, with micro-formic acid the material pH value is adjusted to 4 again.Add 10kg alkali formula chromic salts again in 98 ℃ of following stirring and refluxing 20～30 minutes, be cooled to 60 ℃ of dischargings, can make the product of the inventive method.Its solid content 52 ± %.
5. the 42kg crude phenols are mixed with the 50kg vitriol oil, be heated to 100～110 ℃ of reactions 2 hours, under 200～300mmHg decompression, material is warmed to 148～150 ℃ subsequently, and under agitation be incubated 1 hour and make the A material.After 18kgA material and the 4kg S-WAT usefulness water diluted mixture of 30kg, transferring PH with NaOH is 8～9, and at 45 ℃ of following 21kg formaldehyde and alcoholic acid mixed solutions (ratio of mixture 10: 1) of adding, subsequently 60 ℃ of following insulated and stirred 1 hour, be warmed up to 100 ℃ again, stir insulation and made the B material in 2 hours, pH value is 8～8.5.18kgA material is mixed acquisition PH less than 1 acidic conditions with the water dilution back of 1.6kg with the 20kgB material, and interpolation 1.8kg urea mixes.Add down 15kg formaldehyde and alcoholic acid mixed solutions (10: 1) not being higher than 45 ℃, and 60 ℃ of following insulated and stirred 1.5 hours, be 4.5 with sodium hydroxide accent PH subsequently, transferring its pH value with micro-formic acid again is 4.Add 10kg alkali formula chromic salts again, and 100 ℃ of following stirring and refluxing 40 minutes, be cooled to 60 ℃ of dischargings, the product that can make the inventive method is a deep green mud.Contain solid 52 ± %.
Claims (1)
1, a kind of manufacture method that is applicable to the bleaching chromium-containing synthetic compound tanning agent of processing light color, white soft ox upper leather (ox, buffalo, yak upper leather) and pig leather, glove leather is characterized in that being finished by following reactions steps:
(1) the first step prepares the mixture (hereinafter to be referred as the A material) of dihydroxy diphenylsulphone and phenol sulfonic acid, it is to be benchmark with phenols (referring to phenol, cresols, mixed phenol), vitriol oil sum, by weight, each composition percentage composition sum counts 100%, and the phenols with 40～50% and 60～50% the vitriol oil mix, be heated to 95～100 ℃, reacted 1～2 hour, and under 200～300mmHg pressure, above-mentioned material was warming up to 148～150 ℃, stir insulation 1～4 hour, can make the A material;
(2) second steps preparation sulfomethylation condenses (hereinafter to be referred as the B material), it is to expect with A, the mixture of sodium bisulfite or S-WAT or sodium bisulfite and S-WAT, sodium hydroxide, formaldehyde and alcoholic acid mixed solution, the water sum is a benchmark, by weight, each composition percentage composition sum counts 100%, with the mixture of the sodium bisulfite of 20～24% A material and 4～6% or S-WAT or sodium bisulfite and S-WAT with 33～40% water diluted mixture in addition, transferring its pH value with sodium hydroxide is 8～9, under 40～45 ℃, the formaldehyde and the alcoholic acid mixed solution of adding 12～27%, trembled 1～2 hour 55～65 ℃ of following insulated and stirred, be warmed up to 99～100 ℃ again, stir insulation 1～2 hour, can make pH value and be 8～8.5 B and expect.
(3) the 3rd steps were to expect with A, the B material, urea, formaldehyde and alcoholic acid mixed solution, sodium hydroxide, alkali formula chromic salts, the water sum is a benchmark, by weight, each composition percentage composition sum counts 100%, A with 24～25% expects with after 2～3% the water dilution, mix with 19～31% B material, add 2.5～6% urea mixing again, in the pH value less than 1 be not higher than under 45 ℃ the condition, the formaldehyde and the alcoholic acid mixed solution of adding 13～21%, under 55～65 ℃, insulated and stirred 1～2 hour is 4.5 with the sodium hydroxide adjust pH thereafter, is 4 with micro-formic acid adjust pH again, must urinate the hydroformylation condenses, last 12～18% the alkali formula chromic salts of adding again is reduced to 60 ℃ of dischargings again in 95～100 ℃ of following stirring and refluxing 20～30 minutes, and can make its pH value is 5～6, containing is the slimy bleaching chromium-containing synthetic compound tanning agent of deep green thickness of 52 ± % admittedly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90105757A CN1019134B (en) | 1990-01-16 | 1990-01-16 | Method for mfg. bleaching chromium-containing synthetic compound tanning agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90105757A CN1019134B (en) | 1990-01-16 | 1990-01-16 | Method for mfg. bleaching chromium-containing synthetic compound tanning agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1053448A true CN1053448A (en) | 1991-07-31 |
| CN1019134B CN1019134B (en) | 1992-11-18 |
Family
ID=4879560
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90105757A Expired CN1019134B (en) | 1990-01-16 | 1990-01-16 | Method for mfg. bleaching chromium-containing synthetic compound tanning agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1019134B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103255242A (en) * | 2013-05-23 | 2013-08-21 | 青岛联康油脂制品有限公司 | Preparation method of sulfone bridge type synthetic tanning agent |
| CN111826482A (en) * | 2020-07-21 | 2020-10-27 | 徐州鸿丰高分子材料有限公司 | Preparation method of water-soluble synthetic tanning agent containing chromium sulfomethylated bisphenol S |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044819C (en) * | 1997-04-29 | 1999-08-25 | 中国科学院成都有机化学研究所 | Process for preparing resin retaning agent |
-
1990
- 1990-01-16 CN CN90105757A patent/CN1019134B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103255242A (en) * | 2013-05-23 | 2013-08-21 | 青岛联康油脂制品有限公司 | Preparation method of sulfone bridge type synthetic tanning agent |
| CN103255242B (en) * | 2013-05-23 | 2015-11-18 | 青岛联康油脂制品有限公司 | A kind of preparation method of sulfone bridge type synthetic tanning agent |
| CN111826482A (en) * | 2020-07-21 | 2020-10-27 | 徐州鸿丰高分子材料有限公司 | Preparation method of water-soluble synthetic tanning agent containing chromium sulfomethylated bisphenol S |
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| Publication number | Publication date |
|---|---|
| CN1019134B (en) | 1992-11-18 |
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