CN102747173B - Preparation method of aluminum-oxidized starch complex tanning agent - Google Patents
Preparation method of aluminum-oxidized starch complex tanning agent Download PDFInfo
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- CN102747173B CN102747173B CN201210224802.1A CN201210224802A CN102747173B CN 102747173 B CN102747173 B CN 102747173B CN 201210224802 A CN201210224802 A CN 201210224802A CN 102747173 B CN102747173 B CN 102747173B
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Abstract
A preparation method of an aluminum-oxidized starch complex tanning agent comprises steps of: first mixing starch and water, adding concentrated nitric acid and a catalyst, and stirring for reaction, washing reaction products with ethanol or acetone to obtain the oxidized starch; and evenly mixing the oxidized starch and aluminum ions, oscillating, steaming out excessive water by a rotary evaporimeter, and drying the obtained product. The method of the invention can effectively improve the tanning property of the aluminium tanning agent, maintain original advantages of the aluminum tanning agent and greatly mitigate the phenomenon of detanning. The method of the present invention employs nitrate as an oxidant to oxidize hydroxyl groups to generate oxidized starch with high degree of carboxylic substitution, and utilizes a principle of acid degradation to reduce the relative molecular mass of the oxidized starch, so as to obtain aluminum-containing macromolecular tanning agent with good permeability, high absorption rate and excellent tanning property. The obtained leather tanning agent has good tanning and filling performances, and is suitable for main tanning and retanning; after the main tanning, a pickled skin has a shrinkage temperature raised to 90 DEG C, gains pure white leather body and obvious thickness increase; and after retanning, a product has good elasticity, bright color, gloss, and soft and full handle.
Description
Technical field
The present invention relates to a kind of preparation method of natural polymer tanning agent, specially refer to a kind of preparation method of aluminium-Sumstar 190 complex compound tanning agent.
Background technology
Leather retanning agent is a kind of chemical generally using in leather industry production, light leather is produced and mainly be take chrome tanning agent as main at present, it can give the premium propertiess such as light leather softness, plentiful, hydrothermal stability is high, but trivalent chromium used can slowly be oxidized into sexavalent chrome and possess potential carinogenicity in the process of using, and its environmental pollution causing and water pollute and can not be ignored.Therefore, exploitation chrome-free tanning agent reduces or substitute chromium tanning agent is very important.The features such as starch tanning agent has reaction conditions gentleness in preparation process, it is low to consume energy, technique is unique, the leather products feel of application tanning is very soft and plentiful, but flexibility is not strong, and the leather shrinkage temperature that institute's tanning goes out is not high.And the leather that aluminum tanning agent tanning goes out is bright-colored, be easy to dyeing, on yield of leather and weight per unit area, show the character more excellent than chrome tanning agent, but the easy tempering of the independent tanned leather of aluminium becomes the major issue that yoke aluminum tanning agent develops.If the advantages of starch tanning agent and aluminum tanning agent is got up, and improve the shortcoming that its independent tanning produces, there is boundless application prospect.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of aluminium-Sumstar 190 complex compound tanning agent, aluminium-Sumstar 190 complex compound tanning agent of making by preparation method of the present invention, has solved the problems such as the easy tempering of the tanned leather of existing aluminum tanning agent, the tanned leather shrinkage temperature of starch tanning agent be not high.The present invention not only can realize shrinkage temperature high, be not easy the problems such as tempering, and the leather of producing is soft, plentiful, bright-colored, shrinkage temperature is more than 90 ℃, with low cost and can effectively reduce the pollution that chrome tanning agent brings.
For achieving the above object, the technical solution used in the present invention is:
Step 1, the mixed in molar ratio of starch and water being pressed to 1:5～15, then adds catalyzer and concentrated nitric acid successively wherein, and the mol ratio of catalyzer and starch is 0.01～0.1:1, the mol ratio of concentrated nitric acid and starch is at 0.5～5:1, stirring reaction 4～10h at 10～50 ℃;
Step 2, by the product of step 1 after ethanol or acetone extract, washing the Sumstar 190 of high carboxyl substituted degree;
Step 3, after Sumstar 190 is dried and Tai-Ace S 150 by the mass ratio of 0.5～5:1, be mixed to get mixture, now in mixture, add the water of 100 times of mixture total masses that it is fully dissolved, and to regulate pH value be 1～5,10～30h vibrates in the water-bath constant temperature oscillator of 20～60 ℃;
Step 4, is placed in Rotary Evaporators by the solution after oscillatory reaction and steams excessive moisture, takes out in the baking oven that is placed on 60～80 ℃ and dries and obtain aluminium-Sumstar 190 complex compound tanning agent.
Described starch is industrial corn starch, yam starch or Starch rice.
The mole number of described starch is starch total mass and the ratio of glucose unit relative molecular mass.
Described catalyzer is ammonium meta-vanadate.
The concentration of described concentrated nitric acid is greater than 70%.
The relative molecular mass of aluminium-Sumstar 190 complex compound tanning agent prepared by the present invention is 1000～3000.
Use the crust leather obtaining after tanning agent tanning of the present invention, shrinkage temperature is higher, and is difficult for tempering, and it is bright-colored that the leather of producing has aluminum tanning agent, and yield of leather power consumption high and starch tanning agent is low, fullness ratio advantages of higher, reduces the pollution that leather industry produces.
Starch is a class polyalcohols material, contain a large amount of hydroxyls, oxygenant can be oxidized hydroxyl becomes carboxyl or aldehyde radical, other oxygenant also can carry out this type of reaction, but owing to being subject to the sterically hindered effect of other functional groups in carbochain, use general oxygenant to be difficult to obtain the Sumstar 190 that carboxyl substituted degree is higher, and concentrated nitric acid has strong oxidizing property, significantly the hydroxyl in Sumstar 190 generates carboxyl, under sour effect, starch can be degraded, and generates the structure of low polymerization degree, relative molecular mass can reduce, and is beneficial in tropocollagen molecule and permeates.The structural unit of starch is:
In formula can there is oxidizing reaction in the hydroxyl of 2,3,6 positions, and particularly 6 have stronger reactive behavior.
With the structure of glucose, replace the structural formula of above-mentioned starch below, chemical reaction is carried out to brief description.
This reaction is to take starch as raw material, under the effect of catalyzer, adds concentrated nitric acid and starch to be oxidized by the principle of above-mentioned oxidizing reaction, obtains Sumstar 190.Then Sumstar 190 and aluminum ion are carried out to complexing, generate stable complex compound, carry out tanning.
Compared with prior art, advantage of the present invention is:
1, nontoxic, environmental friendliness: adopt natural polymer starch, Tai-Ace S 150 as reaction raw materials, there are raw material sources extensive, advantages of nontoxic raw materials or hypotoxicity, the advantage such as price is cheaper, active group is many.Environmentally safe, has the characteristic of environmental protection.
2, cost is low: compare with general aluminum tanning agent, in aluminium-Sumstar 190 complex compound tanning agent that the method prepares, can give full play to the advantage of aluminum tanning, relative molecular mass is moderate, there is stronger penetrating quality, higher stability, it is wide that pH adds scope, the variation of organic content in owse is had compared with strong adaptability, also there is the feature pollution-free, consumption is less simultaneously.The raw material adopting is industrial conventional starch and conventional chemical product, and price is cheaper, so the cost of aluminium-Sumstar 190 complex compound tanning agent of preparation is lower.
3, performance is good: in conjunction with the advantage of aluminum tanning agent, starch tanning agent, improve flexibility, gained leather shrinking temperature can reach more than 90 ℃, be not easy tempering, good hand feeling, softness, have higher yield of leather and weight per unit area, and physical and mechanical properties reaches finished leather index completely.
Embodiment
Embodiment 1:
Step 1, the mixed in molar ratio that industrial corn starch and water are pressed to 1:10, then adding wherein successively catalyzer ammonium meta-vanadate and concentration is 75% concentrated nitric acid, the mol ratio of catalyzer and starch is 0.05:1, the mol ratio of concentrated nitric acid and starch is at 0.5:1, stirring reaction 10h at 10 ℃;
Step 2 obtains the product of step 1 the Sumstar 190 of high carboxyl substituted degree after alcohol extraction, washing;
Step 3, after Sumstar 190 is dried and Tai-Ace S 150 by the mass ratio of 0.5:1, be mixed to get mixture, now in mixture, add the water of 100 times of mixture total masses that it is fully dissolved, and to regulate pH value be 3,30h vibrates in the water-bath constant temperature oscillator of 20 ℃;
Step 4, is placed in Rotary Evaporators by the solution after oscillatory reaction and steams excessive moisture, takes out in the baking oven that is placed on 60 ℃ and dries and obtain aluminium-Sumstar 190 complex compound tanning agent.
Embodiment 2:
Step 1, the mixed in molar ratio that industrial yam starch and water are pressed to 1:5, then adding wherein successively catalyzer ammonium meta-vanadate and concentration is 75% concentrated nitric acid, the mol ratio of catalyzer and starch is 0.01:1, the mol ratio of concentrated nitric acid and starch is at 1:1, stirring reaction 6h at 30 ℃;
Step 2 obtains the product of step 1 the Sumstar 190 of high carboxyl substituted degree after acetone extract, washing;
Step 3, is mixed to get mixture with Tai-Ace S 150 by the mass ratio of 1:1 after Sumstar 190 is dried, and show and add the water of 100 times of mixture total masses that it is fully dissolved in mixture, and to regulate pH value is 1, and 20h vibrates in the water-bath constant temperature oscillator of 40 ℃;
Step 4, is placed in Rotary Evaporators by the solution after oscillatory reaction and steams excessive moisture, takes out in the baking oven that is placed on 70 ℃ and dries and obtain aluminium-Sumstar 190 complex compound tanning agent.
Embodiment 3:
Step 1, the mixed in molar ratio that industrial Starch rice and water are pressed to 1:8, then adding wherein successively catalyzer ammonium meta-vanadate and concentration is 75% concentrated nitric acid, the mol ratio of catalyzer and starch is 0.08:1, the mol ratio of concentrated nitric acid and starch is at 2:1, stirring reaction 4h at 50 ℃;
Step 2 obtains the product of step 1 the Sumstar 190 of high carboxyl substituted degree after alcohol extraction, washing;
Step 3, is mixed to get mixture with Tai-Ace S 150 by the mass ratio of 3:1 after Sumstar 190 is dried, and show and add the water of 100 times of mixture total masses that it is fully dissolved in mixture, and to regulate pH value is 4, and 10h vibrates in the water-bath constant temperature oscillator of 60 ℃;
Step 4, is placed in Rotary Evaporators by the solution after oscillatory reaction and steams excessive moisture, takes out in the baking oven that is placed on 65 ℃ and dries and obtain aluminium-Sumstar 190 complex compound tanning agent.
Embodiment 4:
Step 1, the mixed in molar ratio that industrial corn starch and water are pressed to 1:12, then adding wherein successively catalyzer ammonium meta-vanadate and concentration is 75% concentrated nitric acid, the mol ratio of catalyzer and starch is 0.03:1, the mol ratio of concentrated nitric acid and starch is at 4:1, stirring reaction 8h at 20 ℃;
Step 2 obtains the product of step 1 the Sumstar 190 of high carboxyl substituted degree after acetone extract, washing;
Step 3, is mixed to get mixture with Tai-Ace S 150 by the mass ratio of 4:1 after Sumstar 190 is dried, and show and add the water of 100 times of mixture total masses that it is fully dissolved in mixture, and to regulate pH value is 2, and 25h vibrates in the water-bath constant temperature oscillator of 30 ℃;
Step 4, is placed in Rotary Evaporators by the solution after oscillatory reaction and steams excessive moisture, takes out in the baking oven that is placed on 80 ℃ and dries and obtain aluminium-Sumstar 190 complex compound tanning agent.
Embodiment 5:
Step 1, the mixed in molar ratio that industrial Starch rice and water are pressed to 1:15, then adding wherein successively catalyzer ammonium meta-vanadate and concentration is 75% concentrated nitric acid, the mol ratio of catalyzer and starch is 0.1:1, the mol ratio of concentrated nitric acid and starch is at 5:1, stirring reaction 5h at 40 ℃;
Step 2 obtains the product of step 1 the Sumstar 190 of high carboxyl substituted degree after alcohol extraction, washing;
Step 3, is mixed to get mixture with Tai-Ace S 150 by the mass ratio of 5:1 after Sumstar 190 is dried, and show and add the water of 100 times of mixture total masses that it is fully dissolved in mixture, and to regulate pH value is 5, and 15h vibrates in the water-bath constant temperature oscillator of 50 ℃;
Step 4, is placed in Rotary Evaporators by the solution after oscillatory reaction and steams excessive moisture, takes out in the baking oven that is placed on 75 ℃ and dries and obtain aluminium-Sumstar 190 complex compound tanning agent.
Claims (5)
1. a preparation method for aluminium-Sumstar 190 complex compound tanning agent, is characterized in that, comprises the following steps:
Step 1, the mixed in molar ratio of starch and water being pressed to 1:5～15, then adds catalyzer and concentrated nitric acid successively wherein, and the mol ratio of catalyzer and starch is 0.01～0.1:1, the mol ratio of concentrated nitric acid and starch is at 0.5～5:1, stirring reaction 4～10h at 10～50 ℃;
Step 2, by the product of step 1 after ethanol or acetone extract, washing the Sumstar 190 of high carboxyl substituted degree;
Step 3, after Sumstar 190 is dried and Tai-Ace S 150 by the mass ratio of 0.5～5:1, be mixed to get mixture, now in mixture, add the water of 100 times of mixture total masses that it is fully dissolved, and to regulate pH value be 1～5,10～30h vibrates in the water-bath constant temperature oscillator of 20～60 ℃;
Step 4, is placed in Rotary Evaporators by the solution after oscillatory reaction and steams excessive moisture, takes out in the baking oven that is placed on 60～80 ℃ and dries and obtain aluminium-Sumstar 190 complex compound tanning agent.
2. the preparation method of aluminium-Sumstar 190 complex compound tanning agent according to claim 1, is characterized in that: described starch is industrial corn starch, yam starch or Starch rice.
3. the preparation method of aluminium-Sumstar 190 complex compound tanning agent according to claim 1, is characterized in that: the mole number of described starch is starch total mass and the ratio of glucose unit relative molecular mass.
4. the preparation method of aluminium-Sumstar 190 complex compound tanning agent according to claim 1, is characterized in that: described catalyzer is ammonium meta-vanadate.
5. the preparation method of aluminium-Sumstar 190 complex compound tanning agent according to claim 1, is characterized in that: the concentration of described concentrated nitric acid is greater than 70%.
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| CN103242562B (en) * | 2013-04-28 | 2015-03-18 | 四川大学 | Degradable starch-degradable chromium-containing leather pulp composite as well as preparation method and application thereof |
| CN104651543A (en) * | 2013-11-21 | 2015-05-27 | 谈丽娜 | Preparation method of filling-foaming-type leather re-tanning agent |
| CN106011328A (en) * | 2016-06-16 | 2016-10-12 | 温州大学 | Zirconium-diethanol amine complex tanning agent and preparation method thereof |
| CN107119154B (en) * | 2017-07-06 | 2019-04-26 | 四川大学 | The preparation method of the polyfunctional group polysaccharide-based ligand-metal complex tanning agent of width distribution |
| CN111333741B (en) * | 2020-03-03 | 2022-03-22 | 广东省石油与精细化工研究院 | High molecular compound dechlorinating agent and preparation method thereof |
| CN112831617B (en) * | 2021-02-08 | 2021-11-09 | 四川大学 | Light-colored polycarboxyl oxidized polysaccharide tanning agent and preparation method and application thereof |
| US11834724B2 (en) * | 2021-02-08 | 2023-12-05 | Sichuan University | Light-colored polycarboxylated polysaccharide tanning agent, and preparation method and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870464A (en) * | 1970-07-24 | 1975-03-11 | Nat Res Dev | Process for tanning with a multivalent metal and an organic compound |
| CN1037329A (en) * | 1989-05-18 | 1989-11-22 | 胡宪金 | Method with diluted nitric acid as oxidant to produce oxalic acid |
| CN1038082A (en) * | 1988-05-25 | 1989-12-20 | 罗桂云 | Artificial cement marble and manufacture method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870464A (en) * | 1970-07-24 | 1975-03-11 | Nat Res Dev | Process for tanning with a multivalent metal and an organic compound |
| CN1038082A (en) * | 1988-05-25 | 1989-12-20 | 罗桂云 | Artificial cement marble and manufacture method thereof |
| CN1037329A (en) * | 1989-05-18 | 1989-11-22 | 胡宪金 | Method with diluted nitric acid as oxidant to produce oxalic acid |
Non-Patent Citations (2)
| Title |
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| 不同刚性模块的协同效应;陈慧等;《中国皮革》;20060630;第35卷(第11期);第7页第1段、第8页第1.3.1节、表1、图e * |
| 陈慧等.不同刚性模块的协同效应.《中国皮革》.2006,第35卷(第11期), |
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