CN1053447A - A kind of manufacture method of mehtod for auxiliary bleaching synthetic tanning agent - Google Patents
A kind of manufacture method of mehtod for auxiliary bleaching synthetic tanning agent Download PDFInfo
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- CN1053447A CN1053447A CN90105756A CN90105756A CN1053447A CN 1053447 A CN1053447 A CN 1053447A CN 90105756 A CN90105756 A CN 90105756A CN 90105756 A CN90105756 A CN 90105756A CN 1053447 A CN1053447 A CN 1053447A
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Abstract
The present invention is the manufacture method that is applicable to the mehtod for auxiliary bleaching synthetic tanning agent of processing light color, white clothing leather, soft leather, it is a raw material through sulfonation-become sulfone-sulfomethylation-processing steps such as urine hydroformylation with phenols, the vitriol oil, formaldehyde, S-WAT (or sodium bisulfite or their mixture) and urea etc., can make a kind of mehtod for auxiliary bleaching synthetic tanning agent of anionic.Technology routine of the present invention is not polluted, and cost is low, and product can be dissolved in cold and hot water entirely, and pH value wide accommodation is used for tanning, blank leather white, and fast light good level-dyeing property, soft, plentiful, be the good chemical materials of producing high-grade clothes, soft white leather.
Description
The present invention is a kind of manufacture method that is used to process the mehtod for auxiliary bleaching synthetic tanning agent of light color or white clothes, soft leather, belongs to leather chemical tanning agent manufacturing technology field.
In recent years, market is to the natural style of leather goods, and light, thin, soft quality is had higher requirement, and especially for the dab leather, its leather base background color more needs the light good photostabilization of color harmony, thereby shows the color radiance of leather goods.In the leather chemical industry material, except that replacement type synthetic tanning agent, also having a class is the auxiliary type tanning agent, such tanning agent can further improve the white cold of chrome tanned leather base, be used as the impurity that the agent of stuffing post rinsing can reduce the skin surface attachment, thereby reduce variable color danger, it is the important subsidiary material of producing high-grade light color or colored leather goods.Czech patents CS215386(1984) once reported a kind of auxiliary type white synthetic tanning agent, it is with the phenol and the vitriol oil, only makes sulfomethylation, transfers PH to make the urine hydroformylation with dilute sulphuric acid, brightens a kind of synthetic tanning agent that composition is made with aluminium salt.The prepared product of this patented method, though bleaching action is arranged, photostabilization is undesirable, big with the consumption of dilute sulphuric acid accent PH, product contains low admittedly.And the Taesgan LD(trade mark of West Germany Bager company) light-colored leather retanning agent, its bleaching, photostabilization are all undesirable, and cost an arm and a leg.The present invention is a kind of mixture with phenols (referring to phenol, cresols, mixed phenol), the vitriol oil, formaldehyde, S-WAT or sodium bisulfite or S-WAT and sodium bisulfite with urea etc. is raw material through sulfonation-the become mehtod for auxiliary bleaching synthetic tanning agent of sulfone-sulfomethylation-a kind of anionic that the urine hydroformylation is made.Advantages such as the present invention is different from the manufacture method of above-mentioned Czech patents, and the inventive method technology routine is free from environmental pollution, and prepared product is bleached property, photostabilization is all good, and the solid content height, and the waste water pollution of chromium is little.
The objective of the invention is to develop a kind of technology routine, free from environmental pollution, its product have bleaching property and photostabilization good, be applicable to the manufacture method of the mehtod for auxiliary bleaching synthetic tanning agent of processing light color or white clothing leather, soft leather.
The present invention is achieved in that mehtod for auxiliary bleaching synthetic tanning agent is to be made by following steps:
(1) mixture of at first synthetic dihydroxy diphenylsulphone and phenol sulfonic acid, it is to be benchmark with phenols (referring to phenol, cresols, mixed phenol) and vitriol oil sum, by weight, each composition percentage composition sum counts 100%, phenols with 30～50% and 70～50% the vitriol oil mix being lower than under 70 ℃, reheat to 100～110 ℃ stirring insulation 1～2 hour, be warmed up to 148～150 ℃ subsequently, (200～300mmHg) insulated and stirred 1～4 hour under reduced pressure, be cooled to 60 ℃ again, can make the mixture (hereinafter to be referred as the A material) of dihydroxy diphenylsulphone and phenol sulfonic acid;
(2) second steps were to make the sulfomethylation product, it is to expect with A, sodium bisulfite (or mixture of 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 14～21% dilutes with 4～7% water, add the solution of preparing with the sodium bisulfite (or mixture of S-WAT or sodium bisulfite and S-WAT) of 13～22% water and 17～22% again, transferring pH value with 17～19% sodium hydroxide again is 8～9,40～50 ℃ and stir under add 18～23% formaldehyde and alcoholic acid mixture, stir insulation 1～2 hour down at 50～65 ℃, be warming up to 95～105 ℃ again, insulated and stirred 1～2 hour can make pH value and be 8～9 sulfomethylation product (hereinafter to be referred as the B material);
(3) the 3rd steps were to expect with A, the B material, urea, formaldehyde and alcoholic acid mixed solution, sodium hydroxide and water sum are benchmark, by weight, each composition percentage composition sum counts 100%, A material with 21～29% dilutes with 8～11% water, mix with 24～29% B material again, transfer pH value less than 1, adding 5～13% urea again mixes, be not higher than 50 ℃ of formaldehyde and alcoholic acid mixed solutions of adding 12～23% down subsequently, 40～50 ℃ of following insulated and stirred 1～2 hour, transferring pH value with 8～11% sodium hydroxide subsequently is 4.2, with micro-formic acid the pH value of material is adjusted back 4 again, promptly obtains containing the aqueous mehtod for auxiliary bleaching synthetic tanning agent of consolidating to 〉=50% of light brown viscous.
Phenols (phenol, cresols, mixed phenol) can generate dihydroxy diphenylsulphone and phenol azochlorosulfonate acid mixture with the vitriol oil by above-mentioned condition, so that sulfone bridge construction and urine hydroformylation neutralizing agent to be provided; Formaldehyde is sulfomethylation-urine hydroformylation condensation raw material; The mixture of S-WAT or sodium bisulfite or S-WAT and sodium bisulfite is a sulphonating agent; Urea is for forming the fast light structure of urine aldehyde type, and can improve the reactivity worth with skin protein.
The production technique routine of the inventive method, its production cost is far below imported product, and is free from environmental pollution.The product that makes with the present invention is a kind of mehtod for auxiliary bleaching synthetic tanning agent of anionic, this tanning agent can be dissolved in the hot water or cold water entirely, have the pH value wide accommodation, can be used for tanning white leather base, soft, plentiful, photostabilization is good, flat thin, the good level-dyeing property of grain.Waste water chromium content is low when in addition, being used as chrome-tanned retanning.
Below be the embodiment of the inventive method:
Example 1
(a) with in the 30kg phenol suction still, under agitation and be lower than 70 ℃ and add down the 70kg vitriol oils and be warming up to 100～110 ℃ again, stir insulation 2 hours, be warmed up to 148～150 ℃ subsequently, (200～300mmHg) insulations under reduced pressure, stirred 4 hours, and be cooled to 60 ℃, make dihydroxy diphenylsulphone and phenol azochlorosulfonate acid mixture (hereinafter to be referred as the A material);
(b) 40kg A material is mixed with the dilution of 13kg water, in the suction still, adds the solution that is made into 50kg water and 40kg sodium bisulfite again, using (40%) sodium hydroxide 40kg to transfer PH again is 8～9.Stir adding 50kg formaldehyde and 4kg alcohol mixeding liquid down at 50 ℃.Stir down insulation 1 hour at 60 ℃, being warming up to 100 ℃ of insulated and stirred, to make pH value in 1 hour be 8～9 sulfomethylation product (hereinafter to be referred as the B material).
(c) 100kg A is expected, add water 30kg dilution and add the 100kgB material, transferring PH is＜1, it is miscible in wherein to add 20kg urea again, stirring adding 50kg formaldehyde and 5kg alcohol mixeding liquid below 50 ℃ subsequently, 50 ℃ of following insulated and stirred 2 hours, using (40%) sodium hydroxide to transfer PH subsequently was 4.2, and transferring PH with formic acid again is 4 light brown viscous liquid mehtod for auxiliary bleaching synthetic tanning agent.Solid content 〉=50%.
Example 2
(a) with in 50kg phenol and 0-cresols mixture (5: 1 ω t) the suction still.Under agitation with under being lower than 70 ℃ add the 50kg vitriol oils, be warming up to 100～110 ℃ again, stir insulation 2 hours.Be warmed up to 148～150 ℃ subsequently, (200～300mmHg) insulated and stirred 2.5 hours are cooled to 60 ℃ and make the dihydroxy diphenylsulphone that contains phenol sulfonic acid, i.e. the A material in decompression.
(b) 35kg A material is even with 12kg water diluted mixture, in the suction still, add the solution that 50kg water and 50kg S-WAT are made into again.Using (40%) sodium hydroxide to transfer PH again is 8～9.45 ℃ and stir under add 45kg formaldehyde and 5kg alcoholic acid mixed solution, stir insulation 1.5 hours down at 55 ℃, be warming up to 100 ℃ again, insulated and stirred can make B in 2 hours and expect.
(c) 80kg A material is added water 30kg dilution, add the 70kgB material again, transfer PH＜1, add 28kg urea again and mix.Stir down at 45 ℃ subsequently and add 50kg formaldehyde and 3kg alcoholic acid mixed solution.50 ℃ of following insulated and stirred 2.5 hours, using the sodium hydroxide of (40%) to transfer PH subsequently was 4.2, uses formic acid again, and the anti-PH of accent is light brown viscous liquid-mehtod for auxiliary bleaching synthetic tanning agent of 4.Solid content 〉=50%.
Example 3
(a) with 40kg mixed phenol (o-cresols: m-cresols: p-cresols=3.5: 4.0: 2.5 ω t) in the suction still, under agitation with under being lower than 70 ℃ add the 60kg vitriol oils, be warming up to 100～110 ℃ again and stir insulation 2 hours, be warmed up to 148～150 ℃ subsequently, in decompression (200～300mmHg) times insulated and stirred 3 hours.Be cooled to 60 ℃, make the A material.
(b) 50kg A material is diluted mixing with 10kg water, in the suction still, add the solution that 40kg water and 45kg sodium bisulfite and sodium sulfate (2: 1 ω t) are made into again.Using (40%) sodium hydroxide to transfer PH again is 8～9.50 ℃ and stir under add 40kg formaldehyde and 4kg alcoholic acid mixed solution, stir insulation 2 hours down at 60 ℃, be warming up to 100 ℃, insulated and stirred 1.5 hours can get B and expect.
(c) 60kg A material is added water 25kg dilution, add the 80kgB material, transfer PH＜1, add 30kg urea mixing again, stir down at 50 ℃ subsequently and add 60kg formaldehyde and 5kg alcoholic acid mixed solution, 55 ℃ of following insulated and stirred 2 hours, using (40%) sodium hydroxide to transfer PH subsequently was 4.2, is light brown viscous liquid-mehtod for auxiliary bleaching synthetic tanning agent of 4 again with the anti-PH of accent of formic acid.Solid content 〉=50%.
Example 4
(a) with in 35kg phenol and mixed phenol (1: 1 ω t) the suction still, under agitation and be lower than 70 ℃ and add down the 55kg vitriol oils and be warming up to 100～110 ℃ again, stir insulation 2 hours, be warmed up to 148～150 ℃ subsequently, under reduced pressure (200～300mmHg) insulations, stirring were cooled to 60 ℃ in 4 hours and make the A material.
(b) 40kg A material is diluted mixing with 15kg water, in the suction still, add the solution that is made into 40kg water and 42kg sodium bisulfite again, using (40%) sodium hydroxide 42kg to transfer PH again is 8～9.45 ℃ and stir under add 50kg formaldehyde and 5kg alcoholic acid mixed solution, stir insulation down at 60 ℃ and be warming up to 100 ℃ of insulated and stirred in 1 hour and can get B in 1.5 hours and expect.
(c) 70kg A is expected, add water 30kg dilution, add the 75kgB material, transferring PH is＜1, it was miscible in wherein to add 35kg urea again, adds 30kg formaldehyde and 5kg alcoholic acid mixed solution stirring below 50 ℃ subsequently, 60 ℃ of following insulated and stirred 2 hours, using (40%) sodium hydroxide to transfer PH subsequently is 4.2, transfers PH 4 can make the aqueous mehtod for auxiliary bleaching synthetic tanning agent of light brown viscous with formic acid again.Solid content 〉=50%.
Example 5
(a) with in 45kg phenol and m-cresols (2: 1 ω t) the suction still, under agitation and not be higher than 70 ℃ and add the 55kg vitriol oil down, be warmed up to 100～110 ℃ again, stir insulation 1.5 hours, be warmed up to 148～150 ℃ subsequently, under 200～300mmHg decompression, stir insulation 1 hour, be cooled to 60 ℃, make the dihydroxy diphenylsulphone mixture (A material) that contains phenol sulfonic acid.
(b) 45kgA is expected in the suction still, add the aqueous solution that 30kg water and 50kg S-WAT and sodium bisulfite (3: 1 ω t) are made into after the dilution of 15kg water again, transferring material PH with sodium hydroxide again is 8～9.Stir adding 42kg formaldehyde and 3kg alcoholic acid mixed solution down at 40 ℃.Stir insulation 1 hour down at 60 ℃ subsequently, be warming up to 99～100 ℃ again, insulated and stirred got the B material in 2 hours.
(c) the 85kgA material is added water 28kg dilution, add the 75kgB material and transfer PH＜1, add again after 30kg urea is mixed, stir adding 40kg formaldehyde and 4kg alcoholic acid mixture down at 45 ℃, be incubated 1.5 hours down at 50 ℃, transferring material PH with sodium hydroxide subsequently is 4.2, is 4 with the anti-PH of accent of formic acid again, promptly makes the mehtod for auxiliary bleaching synthetic tanning agent of light brown viscous shape.Solid content 〉=50%.
The inventive method, the technology routine, pollution-free, product solid content 〉=50% of its manufacturing is applicable to light clothes of processing and soft leather, compares with Bayer company's T anigen LD, has outstanding advantage on bleaching, photostabilization.Especially supporting with the bleaching chromium-containing synthetic compound tanning agent of inventor's research, be particularly suitable for the export processing sports shoes with white soft ox upper leather, also low-quality yak skin can be processed into high-grade fancy leather, have important promotional value.
Claims (1)
1, a kind of manufacture method that is used to process the mehtod for auxiliary bleaching synthetic tanning agent of light color or white clothing leather, soft leather is characterized in that being finished by following steps:
(1) mixture of at first synthetic dihydroxy diphenylsulphone and phenol sulfonic acid, it is to be benchmark with phenols (referring to phenol, cresols, mixed phenol) and vitriol oil sum, by weight, each composition percentage composition sum counts 100%, phenols with 30～50% and 70～50% the vitriol oil mix being lower than under 70 ℃, reheat to 100～110 ℃ stirring insulation 1～2 hour, be warmed up to 148～150 ℃ subsequently, (200～300mmHg) insulated and stirred 1～4 hour under reduced pressure, be cooled to 60 ℃ again, can make the mixture (hereinafter to be referred as the A material) of dihydroxy diphenylsulphone and phenol sulfonic acid;
(2) second steps were to make the sulfomethylation product, it is to expect with A, sodium bisulfite (or mixture of 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 14～21% dilutes with 4～7% water, add the solution of preparing with the sodium bisulfite (or mixture of S-WAT or sodium bisulfite and S-WAT) of 13～22% water and 17～22% again, be 8～9 with 17～19% sodium hydroxide adjust pH again, 40～50 ℃ and stir under add 18～23% formaldehyde and alcoholic acid mixture, stir insulation 1～2 hour down at 50～65 ℃, be warming up to 95～105 ℃ again, insulated and stirred 1～2 hour can make the pH value and be 8～9 sulfomethylation product (hereinafter to be referred as the B material);
(3) the 3rd steps were to expect with A, the B material, urea, formaldehyde and alcoholic acid mixed solution, sodium hydroxide and water sum are benchmark, by weight, each composition percentage composition sum counts 100%, A material with 21～29% dilutes with 8～11% water, mix with 24～29% B material again, adjust pH is less than 1, adding 5～13% urea again mixes, be not higher than 50 ℃ of formaldehyde and alcoholic acid mixed solutions of adding 12～23% down subsequently, 40～50 ℃ of following insulated and stirred 1～2 hour, be 4.2 with 8～11% sodium hydroxide adjust pH subsequently, with micro-formic acid the pH value of material adjusted back 4 again, promptly obtain containing solid 〉=50% the aqueous mehtod for auxiliary bleaching synthetic tanning agent of light brown viscous of being.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90105756A CN1019135B (en) | 1990-01-16 | 1990-01-16 | Mfg. mehtod for auxiliary bleaching synthetic tanning agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90105756A CN1019135B (en) | 1990-01-16 | 1990-01-16 | Mfg. mehtod for auxiliary bleaching synthetic tanning agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1053447A true CN1053447A (en) | 1991-07-31 |
| CN1019135B CN1019135B (en) | 1992-11-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90105756A Expired CN1019135B (en) | 1990-01-16 | 1990-01-16 | Mfg. mehtod for auxiliary bleaching synthetic tanning agent |
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| Country | Link |
|---|---|
| CN (1) | CN1019135B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063799C (en) * | 1998-01-19 | 2001-03-28 | 四川联合大学 | Tannin extract type amphoteric retanning agent and method for preparing same |
| CN101613769B (en) * | 2009-07-15 | 2013-11-20 | 天津市雄冠科技发展有限公司 | White synthetic tanning agent and preparation method thereof |
| CN103409567A (en) * | 2013-08-29 | 2013-11-27 | 宿迁市致富皮业有限公司 | Chrome-free leather tanning agent and application method thereof |
| CN107619890A (en) * | 2017-08-24 | 2018-01-23 | 南通双狮化工有限公司 | A kind of NEW TYPE OF COMPOSITE tanning agent |
| CN110785501A (en) * | 2017-05-17 | 2020-02-11 | 斯塔尔国际有限公司 | Tanning agent for leather production comprising a polycondensate of sulfonated phenol, urea and formaldehyde |
| CN112359153A (en) * | 2020-10-28 | 2021-02-12 | 宁夏成丰农业科技开发股份有限公司 | Processing method of imitated fox fur |
| CN113136462A (en) * | 2021-06-02 | 2021-07-20 | 南雄西顿化工有限公司 | Preparation method of modified synthetic tanning agent |
-
1990
- 1990-01-16 CN CN90105756A patent/CN1019135B/en not_active Expired
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063799C (en) * | 1998-01-19 | 2001-03-28 | 四川联合大学 | Tannin extract type amphoteric retanning agent and method for preparing same |
| CN101613769B (en) * | 2009-07-15 | 2013-11-20 | 天津市雄冠科技发展有限公司 | White synthetic tanning agent and preparation method thereof |
| CN103409567A (en) * | 2013-08-29 | 2013-11-27 | 宿迁市致富皮业有限公司 | Chrome-free leather tanning agent and application method thereof |
| CN110785501A (en) * | 2017-05-17 | 2020-02-11 | 斯塔尔国际有限公司 | Tanning agent for leather production comprising a polycondensate of sulfonated phenol, urea and formaldehyde |
| CN110785501B (en) * | 2017-05-17 | 2022-03-22 | 斯塔尔国际有限公司 | Tanning agent for leather production comprising a polycondensate of sulfonated phenol, urea and formaldehyde |
| CN107619890A (en) * | 2017-08-24 | 2018-01-23 | 南通双狮化工有限公司 | A kind of NEW TYPE OF COMPOSITE tanning agent |
| CN112359153A (en) * | 2020-10-28 | 2021-02-12 | 宁夏成丰农业科技开发股份有限公司 | Processing method of imitated fox fur |
| CN113136462A (en) * | 2021-06-02 | 2021-07-20 | 南雄西顿化工有限公司 | Preparation method of modified synthetic tanning agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1019135B (en) | 1992-11-18 |
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