CN101781689A - Environment-friendly tanning agent for leather, preparation method and application thereof - Google Patents
Environment-friendly tanning agent for leather, preparation method and application thereof Download PDFInfo
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- CN101781689A CN101781689A CN200910005123A CN200910005123A CN101781689A CN 101781689 A CN101781689 A CN 101781689A CN 200910005123 A CN200910005123 A CN 200910005123A CN 200910005123 A CN200910005123 A CN 200910005123A CN 101781689 A CN101781689 A CN 101781689A
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Abstract
The invention discloses a tanning agent for furs and a preparation method thereof. The tanning agent for the furs comprises the following components in parts by weight: 50-100 parts of tetrakis (hydroxymethyl) phosphonium sulfate (THPS), 5-60 parts of additive, 6-50 parts of complexing agent, 1-10 parts of EDTA and 10-100 parts of water. The preparation method of the tanning agent of the invention has simple and convenient operating process; each component of the tanning agent causes no environmental pollution, thus the tanning agent for the furs is environment-friendly; the tanning agent product has good performance, high storage stability, colorless appearance and no peculiar smell; the tanning agent is used for tanning the furs; the shrink temperature for a leather board reaches to 83 DEG C; and the tanning agent has the advantages that the penetrability is strong, the filling capability is good, fleeces tanned by the tanning agent is spotlessly white and natural and the like. The tanning agent of the invention is suitable for tanning woolfells, and is a new technology in the field of fur coat preparation.
Description
Technical field
The present invention relates to make the new technology in fur coat field, concrete, the present invention relates to a kind of fur tanning agent, its preparation method and application, fur tanning agent of the present invention is a kind of high-effect tanning agent of fur cheaply.
Background technology
Along with the adjustment of world's industrial structure and the world's process hides transfer with system fur coat industry center of gravity, China has developed into the leather of World Focusing and fur manufacturing center and trade center of gravity (sees Zhang Zongcai.Pollutant analysis in the process hides discharge " leather science and engineering ", 2002 (15): P44-48).
Chromic tanning is since invention, and the application in process hides and fur industry is comparatively extensive and occupied dominant position, and chromic tanning still has irreplaceable advantage in leather industry up till now.But raising along with people's environmental consciousness, the pollution problem of chromic tanning is subjected to people's attention day by day, because sexavalent chrome has been proved and has had carinogenicity, one of index that the mass parts number average of sexavalent chrome in waste water classified as strict control by various countries environmental administration (is seen Tang Keyong.The source of pollution of chromium and harm thereof " leather science and engineering ", 1997 (7): P33-48), how to solve the key that the pollution of chromium problem becomes China's process hides system fur coat industrial sustainable development, wherein develop the focus that the chrome-free tanning chemical materials becomes current research.
Chemical name is the compound of four methylol phosphonium salts (tetrakishydroxymethylphosphonium), is called THP salt or THPS usually for short, and its chemical molecular formula is C
4H
12O
4P.THP salt mainly exists with tetrakis hydroxymethyl phosphonium chloride (THPC) and two kinds of forms of tetra methylol sulfuric acid phosphonium (THPS).In the prior art, THP salt is a kind of novel auxiliary chemicals, is commonly used for the fire retardant of textiles, and THP salt also is a kind of novel sterilant, is widely used in cooling water treatment system and oil-field water treatment system.
When THP salt is used for tan leather separately, stiff, the consolidation of the dermatotome that obtains; Extensibility is relatively poor in length and breadth in system fur coat process, and the following process of fur coat is caused disadvantageous effect.In early days, U.S. Pat P 3104151 once reported THP salt and phenols in conjunction with the method that is used for leather tanning; November 8 nineteen ninety-five, disclosed EP0681030A2 described THPS, as the application of casein linking agent in leather finish; The open CN1278304A of the Chinese patent of Britain Rhodia consumption special Co., Ltd (open day on December 27th, 2000) discloses and has proposed to tan or the crosslinking reaction realization leather tanning in retanning stage the master by collagen and three (methylol) phosphonium salt or with the condenses of four (methylol) phosphonium salts and acid amides or amine; Proposition THPS such as A.D.Convigton and aminoresin performed polymer are used, can make Ts reach more than 100 ℃ (see Zhang Tingyou, " tanning chemistry ", 2003, press of Sichuan University, P49-50).But these technology are not all effectively applied industrial.
The inventor uses the peculiar property of various environmental protective type chemical materials on the basis of comprehensive prior art, overcome the various defectives of THPS, makes cheap, high-performance environmentally-friendly type tanning agent.
Summary of the invention
The present invention be directed to the prior art shortcoming and defect, the environment-friendly type tanning agent of a kind of THPS of containing be provided, wherein will with the ingenious collocation of the various chemical materials additives of THPS, be prepared into soft plentiful, tanning agent that color is pure white.This tanning agent product has that perviousness is strong, the tanning agent of stable storing, water white transparency and free from extraneous odour, and shrinkage temperature can reach 83 ℃.
Tanning agent of the present invention is made up of following component:
Tetra methylol sulfuric acid phosphonium salt (THPS): 50-100 part;
Additive: 5-60 part;
Complexing agent: 6-50 part;
Edta salt: 1-10 part; With
Water: 10-100 part;
The proportioning of wherein said component is represented with parts by weight.
Preferably, the composition of each component of tanning agent of the present invention is counted with parts by weight:
Tetra methylol sulfuric acid phosphonium (THPS): 60-90 part;
Additive: 10-50 part;
Complexing agent: 10-30 part;
EDTA:1-5 part; With
Water: 10-60 part.
In above-mentioned tanning agent of the present invention, described additive is selected from N-Methyl pyrrolidone, D-sorbyl alcohol, D-glucose and citric acid, preferred N-Methyl pyrrolidone or D-sorbyl alcohol.
In the above-mentioned tanning agent of the present invention, wherein said complexing agent is the conventional complexing agent that uses in this area, preferred ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS) or hexanediamine tetramethylene phosphonic acid sylvite (HDTMPA.K
6).
In above-mentioned tanning agent of the present invention, wherein said EDTA is ethylenediamine tetraacetic acid (EDTA) and derivative thereof, preferably uses the salt of ethylenediamine tetraacetic acid (EDTA), and particularly preferred edta salt is disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate.
Preferably, the additive described in the fur tanning agent of the present invention is N-Methyl pyrrolidone or D-sorbyl alcohol; Described complexing agent is ethylene diamine tetra methylene phosphonic acid sodium or hexanediamine tetramethylene phosphonic acid sylvite; Described EDTA is disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate.
Employed various auxiliary agents in the tanning agent of the present invention comprise the Chemicals that additive, complexing agent and EDTA etc. all can use on the market to be sold.
Tanning agent of the present invention is a colourless transparent liquid.Tanning agent of the present invention has that perviousness is strong, the advantage of stable storing, water white transparency and free from extraneous odour, and its shrinkage temperature can reach 83 ℃.
Another object of the present invention has provided the preparation method of above-mentioned tanning agent, and this method may further comprise the steps:
(1) with 40-50 ℃ water that EDTA dissolving back is stand-by;
(2) under agitation, slowly add the additive and the complexing agent liquid of required proportioning in the tetra methylol sulfuric acid phosphonium, under 25-35 ℃ temperature, stirred 10-30 minute, then the above-mentioned EDTA aqueous solution is added wherein, continue to keep temperature-resistant, stirred 40-60 minute, obtain the tanning agent of colourless transparent liquid shape;
Wherein in parts by weight, the composition of described each component is tetra methylol sulfuric acid phosphonium (THPS) 50-100 part, additive 5-60 part, complexing agent 6-50 part, EDTA1-10 part and water 10-100 part; The composition of preferred back tanning agent is tetra methylol sulfuric acid phosphonium (THPS) 60-90 part, additive 10-50 part, complexing agent 10-30 part, EDTA 1-5 part and water 10-60 part.
Employed water can be process water or softening water in the aforesaid method of the present invention, for improving the result of use of tanning agent of the present invention, preferably uses softening water, for example feedwater, distilled water or deionized water etc.
The operation of above-mentioned steps (2) can be carried out in the corrosion-resistant reaction vessel that chemical field is used always, for example, described operation can be carried out in the reaction vessel of material manufacturings such as stainless steel, glass reinforced plastic, also can carry out in the reaction vessel that has pottery or enamel lining; Preferred described operating in the reaction vessel that has pottery or enamel lining carried out; More preferably described reactor has temperature demonstration, temperature controlling system and whipping device; For example, described operating in the enamel stirring tank that has agitator, thermometer and cooling system carried out.
Preferably, the operation of above-mentioned steps (2) is at room temperature carried out, and described room temperature typically refers to the temperature about 25 ℃.
Another object of the present invention has provided the application of tanning agent of the present invention, and this tanning agent can be applicable to the tanning of various furs, is specially adapted to the tanning of woolfell.The fur of using tanning agent tanning of the present invention is soft and full, color is pure white, extension property is good in length and breadth, and shrinkage temperature can reach 83 ℃, and can give certain flame retardant resistance.
Tanning agent of the present invention not only has above-mentioned advantage, and because wherein employed raw material is the industrial chemicals of environment-friendly type, can not pollute environment, and cheap, and the preparation method is simple, has the tangible market advantage on environment protection and production cost.
Embodiment
Below by the present invention of specific examples more detailed description, the embodiment that provides only is used for example the present invention, but the protection domain that does not limit the present invention in any way.
The preparation of embodiment 1 tanning agent
1, with of the softening water dissolving of 1 part of disodium ethylene diamine tetraacetate with 25 parts 45 ℃;
2, tetra methylol sulfuric acid phosphonium (THPS) is placed the enamel stirring tank that has thermometer and cooling system for 60 parts, open and stir, slowly 30 parts of ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS) are added reactor, approximately after 10-15 minute 10 parts of N-Methyl pyrrolidone are slowly added reactor, controlled temperature 25-35 ℃, stirred 60 minutes, and obtained the tanning agent of colourless transparent liquid shape.
The preparation of embodiment 2 tanning agents
1, with of the softening water dissolving of 1 part of tetrasodium ethylenediamine tetraacetate with 40 parts 45 ℃;
2, tetra methylol sulfuric acid phosphonium (THPS) is placed the enamel stirring tank that has thermometer and cooling system for 75 parts, open and stir, slowly 15 parts of hexanediamine tetramethylene phosphonic acid sylvite (HDTMPA.K6) are added reactor, approximately after 10-15 minute 10 parts of D-sorbyl alcohols are slowly added reactor, controlled temperature 25-35 ℃, stirred 60 minutes, and obtained the tanning agent of colourless transparent liquid shape.
The preparation of embodiment 3 tanning agents
1, with of the softening water dissolving of 5 parts of disodium ethylene diamine tetraacetate with 10 parts 45 ℃;
2, tetra methylol sulfuric acid phosphonium (THPS) is placed the enamel stirring tank that has thermometer and cooling system for 60 parts, open and stir, slowly 20 parts of ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS) are added reactor, approximately after 10-15 minute 15 parts of N-Methyl pyrrolidone are slowly added reactor, controlled temperature 25-35 ℃, stirred 60 minutes, and obtained the tanning agent of colourless transparent liquid shape.
The preparation of embodiment 4 tanning agents
1, with of the softening water dissolving of 1 part of disodium ethylene diamine tetraacetate with 40 parts 45 ℃;
2, tetra methylol sulfuric acid phosphonium (THPS) is placed the enamel stirring tank that has thermometer and cooling system for 70 parts, open and stir, slowly 10 parts of hexanediamine tetramethylene phosphonic acid sylvite (HDTMPA.K6) are added reactor, approximately after 10-15 minute 20 parts of N-Methyl pyrrolidone are slowly added reactor, controlled temperature 25-35 ℃, stirred 60 minutes, and obtained the tanning agent of colourless transparent liquid shape.
The preparation of embodiment 5 tanning agents
1, with of the softening water dissolving of 1 part of disodium ethylene diamine tetraacetate with 40 parts 45 ℃;
2, tetra methylol sulfuric acid phosphonium (THPS) is placed the enamel stirring tank that has thermometer and cooling system for 80 parts, open and stir, slowly 10 parts of hexanediamine tetramethylene phosphonic acid sylvite (HDTMPA.K6) are added reactor, approximately after 10-15 minute 10 parts of N-Methyl pyrrolidone are slowly added reactor, controlled temperature 25-35 ℃, stirred 60 minutes, and obtained the tanning agent of colourless transparent liquid shape.
The preparation of embodiment 6 tanning agents
1, with of the softening water dissolving of 2 parts of disodium ethylene diamine tetraacetate with 50 parts 45 ℃;
2, tetra methylol sulfuric acid phosphonium (THPS) is placed the enamel stirring tank that has thermometer and cooling system for 50 parts, open and stir, slowly 15 parts of ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS) are added reactor, approximately after 10-15 minute 8 parts of N-Methyl pyrrolidone are slowly added reactor, controlled temperature 25-35 ℃, stirred 60 minutes, and obtained the tanning agent of colourless transparent liquid shape.
The preparation of embodiment 7 tanning agents
1, with of the softening water dissolving of 1 part of tetrasodium ethylenediamine tetraacetate with 10 parts 45 ℃;
2, tetra methylol sulfuric acid phosphonium (THPS) is placed the enamel stirring tank that has thermometer and cooling system for 70 parts, open and stir, slowly 20 parts of ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS) are added reactor, approximately after 10-15 minute 20 parts of D-sorbyl alcohols are slowly added reactor, controlled temperature 25-35 ℃, stirred 60 minutes, and obtained the tanning agent of colourless transparent liquid shape.
The preparation of embodiment 8 tanning agents
1, with of the softening water dissolving of 1 part of disodium ethylene diamine tetraacetate with 25 parts 45 ℃;
2, tetra methylol sulfuric acid phosphonium (THPS) is placed the enamel stirring tank that has thermometer and cooling system for 80 parts, open and stir, slowly 10 parts of ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS) are added reactor, approximately after 10-15 minute 20 parts of D-sorbyl alcohols are slowly added reactor, controlled temperature 25-35 ℃, stirred 60 minutes, and obtained the tanning agent of colourless transparent liquid shape.
The preparation of embodiment 9 tanning agents
1, with of the softening water dissolving of 1 part of disodium ethylene diamine tetraacetate with 20 parts 45 ℃;
2, tetra methylol sulfuric acid phosphonium (THPS) is placed the enamel stirring tank that has thermometer and cooling system for 50 parts, open and stir, slowly 15 parts of ethylene diamine tetra methylene phosphonic acid sodium (EDTMPS) are added reactor, approximately after 10-15 minute 8 parts of N-Methyl pyrrolidone are slowly added reactor, controlled temperature 25-35 ℃, stirred 60 minutes, and obtained the tanning agent of colourless transparent liquid shape.
The application example of embodiment 10 tanning agents
A, tanning (is example with wet sour sheepskin)
In rotary drum, add the water (liquor ratio 1: 10) that is equivalent to 10 times of sour sheepskin (wet pelt) weight, add NaCl 50g/L with respect to the water yield in the system, controlled temperature 35-38 ℃, rotate after 5-10 minute, add the environment-friendly type woolfell tanning agent 5-6ml/L (with respect to the water yield in the system) of embodiment 5.Drop in the rotary drum after then sour woolfell being beaten the limit, rotate after 4-6 hour, begin to regulate owse pH value (dividing 0.5 hour at interval four times), after the pH value reaches 6.7, stop drum and spend the night with 5% sodium carbonate solution.After intermittently stirring 20-30 minute next day, surveying the pH value is 6.7, begins skin, takes horse and leaves standstill.
B, oxygen are washed
In rotary drum, add the water (liquor ratio is 1: 10) of 10 times of the weight of the wet woolfell be equivalent to above-mentioned tanning, about 35 ℃ of controlled temperature with respect to the water yield in the system, add salt (NaCl) 30g/L, Wei Jia
Protect a mao agent M-60 (general rich company product) 2ml/L and Wei Jia
Float toner H-21 (general rich company product) 4g/L, the wet woolfell that adds above-mentioned tanning then carries out oxygen and washes in rotary drum, rotated about about 15 minutes, add hydrogen peroxide (30%) 6-8ml/L (with respect to the water yield in the system), intermittently rotated 6-8 hour, control pH value 7.5-8.0, go out skin, control water, dries after 20 minutes naturally with Warm Wash.
By above-mentioned application as can be known, this tanning agent is easy to use, simple to operate, after the tanning dermatotome soft plentiful, color is pure white.
Below described embodiment of the present invention in detail, can do a lot of improvement and variation obviously for a person skilled in the art and can not deviate from essence spirit of the present invention.All these changes and improvements are all within protection scope of the present invention.
Claims (10)
1. fur tanning agent is characterized in that this tanning agent is made up of following component:
Tetra methylol sulfuric acid squama (THPS): 50-100 part;
Additive: 5-60 part;
Complexing agent: 6-50 part;
EDTA: 1-10 part;
Water: 10-100 part;
Wherein said each component is in parts by weight.
2. according to the described fur tanning agent of claim 1, it is characterized in that the composition of this each component of tanning agent is counted with parts by weight:
Tetra methylol sulfuric acid squama (THPS): 60-90 part;
Additive: 10-50 part;
Complexing agent: 10-30 part;
EDTA: 1-5 part;
Water: 10-60 part.
3. according to claim 1 or 2 described fur tanning agents, it is characterized in that described additive is selected from N-Methyl pyrrolidone, D-sorbyl alcohol, D-glucose and citric acid.
4. according to the described fur tanning agent of claim 3, it is characterized in that described additive is preferably N-Methyl pyrrolidone or D-sorbyl alcohol.
5. according to claim 1 or 2 described fur tanning agents, it is characterized in that described complexing agent is ethylene diamine tetra methylene phosphonic acid sodium or hexanediamine tetramethylene phosphonic acid sylvite.
6. according to the described fur tanning agent of claim 4, it is characterized in that described complexing agent is ethylene diamine tetra methylene phosphonic acid sodium or hexanediamine tetramethylene phosphonic acid sylvite.
7. according to claim 1 or 2 described fur tanning agents, it is characterized in that described EDTA is disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate.
8. according to the described fur tanning agent of claim 6, it is characterized in that described EDTA is disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate.
9. the preparation method of any described fur tanning agent of claim 1-8, this method may further comprise the steps:
(1) EDTA is dissolved stand-by with 40-50 ℃ water;
(2) under agitation, according to required proportioning additive and complexing agent liquid are slowly added in the tetra methylol sulfuric acid squama, under 25-35 ℃ of temperature, stirred 10-30 minute, then to wherein adding the above-mentioned EDTA aqueous solution, continue to keep temperature-resistant, stirred 40-60 minute, and obtained the tanning agent of colourless transparent liquid shape;
Wherein in parts by weight, the composition of described each component of tanning agent is tetra methylol sulfuric acid squama (THPS) 50-100 part, additive 5-60 part, complexing agent 6-50 part, EDTA1-10 part and water 10-100 part; The composition of preferred wherein said tanning agent is in parts by weight, tetra methylol sulfuric acid squama (THPS) 60-90 part, additive 10-50 part, complexing agent 10-30 part, EDTA 1-5 part and water 10-60 part; With
Preferred described step (2) is carried out in enamel still.
10. the application of any described fur tanning agent of claim 1-8, wherein said tanning agent is used for the tanning of various furs; Preferably described tanning agent is applied to the tanning of woolfell.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910005123A CN101781689B (en) | 2009-01-19 | 2009-01-19 | Environment-friendly tanning agent for leather, preparation method and application thereof |
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| CN200910005123A CN101781689B (en) | 2009-01-19 | 2009-01-19 | Environment-friendly tanning agent for leather, preparation method and application thereof |
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| CN101781689B CN101781689B (en) | 2012-09-05 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260761A (en) * | 2011-06-30 | 2011-11-30 | 北京泛博化学股份有限公司 | Fur tanning agent and preparation method thereof |
| CN102453776A (en) * | 2010-10-26 | 2012-05-16 | 北京泛博科技有限责任公司 | Tanning agent and preparation method thereof |
| CN102534058A (en) * | 2010-12-24 | 2012-07-04 | 焦作隆丰皮草企业有限公司 | Tanning method for double-face leather |
| CN103243185A (en) * | 2013-05-21 | 2013-08-14 | 宁夏成丰工贸有限公司 | Tibet lamb skin tanning technology |
| CN103243186A (en) * | 2013-05-23 | 2013-08-14 | 宁夏成丰工贸有限公司 | Clean production technology of Tibet lamb skin |
| CN103243183A (en) * | 2013-05-28 | 2013-08-14 | 宁夏成丰工贸有限公司 | Process for quickly producing domestic goat skins |
| CN109055630A (en) * | 2018-08-31 | 2018-12-21 | 陕西科技大学 | The combination tannage of cage modle octa-aminopropyl silsesquioxane and THPS |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1192284B1 (en) * | 1999-06-18 | 2004-02-18 | Rhodia Consumer Specialties Limited | Leather tanning |
| CN100500870C (en) * | 2006-11-09 | 2009-06-17 | 宁波工程学院 | Preparation method of tetra hydroxy methyl phosphonium salt chromium-less tanning agent |
| CN101182589A (en) * | 2007-11-16 | 2008-05-21 | 陕西科技大学 | Method of THP and multi-amino-compounds combining tanning leather |
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2009
- 2009-01-19 CN CN200910005123A patent/CN101781689B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102453776A (en) * | 2010-10-26 | 2012-05-16 | 北京泛博科技有限责任公司 | Tanning agent and preparation method thereof |
| CN102453776B (en) * | 2010-10-26 | 2014-04-30 | 北京泛博科技有限责任公司 | Tanning agent and preparation method thereof |
| CN102534058A (en) * | 2010-12-24 | 2012-07-04 | 焦作隆丰皮草企业有限公司 | Tanning method for double-face leather |
| CN102260761A (en) * | 2011-06-30 | 2011-11-30 | 北京泛博化学股份有限公司 | Fur tanning agent and preparation method thereof |
| CN103243185A (en) * | 2013-05-21 | 2013-08-14 | 宁夏成丰工贸有限公司 | Tibet lamb skin tanning technology |
| CN103243186A (en) * | 2013-05-23 | 2013-08-14 | 宁夏成丰工贸有限公司 | Clean production technology of Tibet lamb skin |
| CN103243183A (en) * | 2013-05-28 | 2013-08-14 | 宁夏成丰工贸有限公司 | Process for quickly producing domestic goat skins |
| CN103243183B (en) * | 2013-05-28 | 2015-09-09 | 宁夏成丰农业科技开发股份有限公司 | A kind of tibet lamp rapid production process |
| CN109055630A (en) * | 2018-08-31 | 2018-12-21 | 陕西科技大学 | The combination tannage of cage modle octa-aminopropyl silsesquioxane and THPS |
| CN109055630B (en) * | 2018-08-31 | 2021-02-12 | 陕西科技大学 | Combined tanning method of cage type octa-aminopropyl silsesquioxane and THPS |
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| CN101781689B (en) | 2012-09-05 |
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