CN101880334B - Preparation method of starch-based green leather tanning agent - Google Patents
Preparation method of starch-based green leather tanning agent Download PDFInfo
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- CN101880334B CN101880334B CN2010102278140A CN201010227814A CN101880334B CN 101880334 B CN101880334 B CN 101880334B CN 2010102278140 A CN2010102278140 A CN 2010102278140A CN 201010227814 A CN201010227814 A CN 201010227814A CN 101880334 B CN101880334 B CN 101880334B
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Abstract
The invention relates to a preparation method of starch-based green leather tanning agent, which comprises the following steps: first, putting corn starch into water, degrading to obtain degraded starch; carrying out reaction between the degraded starch and glutaraldehyde, and grafting glutaraldehyde onto the surface of the starch; and carrying reaction between the glutaraldehyde grafted starch and citric acid to obtain the starch-based green leather tanning agent. The preparation method takes the renewable and degradable starch with rich resources as the main raw material, introduces the glutaraldehyde into starch molecules through the acetalization reaction between the glutaraldehyde and the hydroxide radical in the starch molecules, carries out acetalization reaction between the aldehyde groups in glutaraldehyde molecules grafted on the starch molecules which do not react and the hydroxide radical of the citric acid to obtain the starch-based green leather tanning agent. The starch-based green leather tanning agent can serve as the main tanning agent, has the shrinkage temperature (Ts) when tanning leather up to 81DEG C, can replace chrome tanning agent and other metal tanning agent and reduce the pollution of the leather industry, and the finished leather has tight grain surface and soft feel, is pump and has good elasticity.
Description
Technical field
The present invention relates to a kind of preparation method of leather retanning agent, be specifically related to a kind of method for preparing the starch-based leather retanning agent with LUTARALDEHYDE, Hydrocerol A treated starch.
Background technology
The course of processing of leather is exactly the process of leather fiber being carried out the chemical physics modification with relevant chemical.Leather retanning agent is that one type of ability makes skin become the chemical substance of leather with rawhide fiber generation chemical action, and leather retanning agent can be divided into inorganic tanning agent, vegetable tanning agent, synthetic tanning agent and polymer tanning agent.Inorganic tanning agent comprises chrome tanning agent, aluminum tanning agent, iron tannage agent, zirconium tanning agent and titanium tannage agent etc. again.Up to the present; What consumption was maximum in leather production, the tanning effect is best is chrome tanning agent; The application of chrome tanning agent has nearly 150 years history, and other tanning agent outside the chrome tanning agent promptly plays auxiliary tanning owing to exist various performance deficiencies mainly as retanning agent behind chrome tanning.Chromium is a kind of scarce resource; A large amount of uses of chrome tanning agent can bring the serious environmental pollution problem; The pollution that chrome tanning agent causes not only shows as in the chrome tanning process chromate waste water, the chromium-bearing sludge that can produce a large amount of refractories reasons, contains chromium skin slag; Also show as chromium content overproof in the leatherware and produce chromic harm problem (Wei Deqing. the opportunities and challenges that accession to WTO back Chinese leather chemical faces. fine chemistry industry, 2005,22 (4): 247～248; But defend China, Liao Longli. the greenization of Green Chemistry and tanning chemistry. leather chemical industry, 2002,19 (6): 4-9; Kdusheva T., Vasilev D..Sepectrphometric method for dermination of AL
2O
3In vegetable-aluminum tanned leathers.JSLTC, 2007,91 (1): 25-29).Therefore, the use of chrome tanning agent makes becomes the potential source of pollution with the closely-related leatherware of people's daily life.
Leather industry is the mainstay industry of China's light industry; For very big contribution has been made in the raising of China's development of economic construction and living standards of the people; The subject matter of puzzlement leather industry maintenance Sustainable development at present is pollution problem, and wherein the pollution of chrome tanning agent is one of topmost pollution.To the pollution problem of chrome tanning agent, the way that mainly solves at present has: one is to use efficient chrome tanning adjuvant, improves infiltration and the absorption of chrome tanning agent in hide fiber, thereby reduces the quantity discharged that contains the chromium refuse in the production process.General chrome tanning agent is had only 60%～70% by what leather fiber absorbed, and remaining chrome tanning agent of 30%～40% becomes pollutent, uses the specific absorption behind the efficient chrome tanning adjuvant to bring up to more than 90%.The 2nd, replace chrome tanning agent with aluminium, iron, zirconium, titanium tannage agent and vegetable tanning agent, aldehyde tanning agent, synthetic tanning agent etc.The leather quality and the chrome tanning agent of these tanning agent tannings have a certain distance, also can produce many problems after using these tanning agents, like aluminium, zirconium, the titanium tannage agent is a large amount of also exists after using and pollute and the problem of shortage of resources; Vegetable tanning agent is that the root, stem, leaf from certain plants etc. extracts the result that can cause forest to be damaged after a large amount of the use; Synthetic tanning agent is the sulfonated bodies of phenol and formaldehyde condensation products, can produce in synthetic, use that formaldehyde pollutes and leather goods in the problem that exceeds standard of formaldehyde content, formaldehyde is considered to have carcinogenesis.The 3rd, adopt inorganic-organically combine tanning agent, as aldehyde-aluminium combine to tan, chrome tanning agent-Syntan Combination Tannage etc., problems such as pollution exist equally.These ways can only reduce limitedly or change kind and the fundamentally decontamination of pollution substance.The pollution problem of leather industry at present becomes the subject matter of its development of restriction; Produced pollution problems such as solution leather retanning agent become primary, critical problem (the Sveeram K.J. that keeps the leather industry Sustainable development; Raghava Rao J..High exhaust chrome-aluminum combination tanning part I:optimization of tanning.JSLTC; 2006,101 (3): 86-89; Nisgad Fathima N..Wet white leather processing:a new combination tanning system.JALCA, 2006,01 (2): 58-64; Madham B., Narasimman R., Gunasekaran S..Integrated chrome free upper leather processing part I:selection of tanning system.JALCA, 2005,100 (7): 282-290).
Summary of the invention
The object of the present invention is to provide a kind of preparation method of starch-based leather retanning agent; Metal tanning agents such as gained starch-based leather retanning agent instead chrome tanning agent; Reduce the pollution of leather industry; And use the finished product grain consolidation of starch-based leather retanning agent of the present invention institute tanning, soft, plentiful, good springiness.
For achieving the above object, the technical scheme that the present invention adopts is:
1) preparation of degraded starch:
Get 25～55 gram W-Gums and joined inherent 90～95 ℃ of insulation reaction of reaction vessel 1～2 hour, obtain degraded starch solution with the ydrogen peroxide 50 of 125～300 gram deionized waters, 0.25～0.55 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 45～95 gram LUTARALDEHYDEs and 0.5～1.0 gram tosic acid, control reaction temperature is 75～85 ℃, reacts 4～5 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 45～95 gram Hydrocerol As, control reaction temperature is 85～90 ℃, reacts 4～5 hours, has obtained the starch-based leather retanning agent.
The present invention is through starch and phenols and the monomeric controlled acetalation of Hydrocerol A; In natural green macromolecular material starch molecule, introduce a plurality of functional group-aldehyde radical, citric acid-based, carboxyls with tanning effect; Reach chemically modified and modification to starch molecule; The macromolecular chain that has the above-mentioned functions base can be infiltrated between the leather fiber, present synergistic effect as the time spent, significantly improve the flexibility of treated starch with collagen.
Embodiment
Embodiment 1:
1) preparation of degraded starch:
Get 25 gram W-Gums and joined the inherent 90 ℃ of insulation reaction of reaction vessel 1 hour, obtain degraded starch solution with the ydrogen peroxide 50 of 125 gram deionized waters, 0.25 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 45 gram LUTARALDEHYDEs and 0.5 gram tosic acid, control reaction temperature is 75 ℃, reacts 4 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 45 gram Hydrocerol As, control reaction temperature is 85 ℃, reacts 4 hours, has obtained the starch-based leather retanning agent.
Embodiment 2:
1) preparation of degraded starch:
Get 30 gram W-Gums and joined the inherent 91 ℃ of insulation reaction of reaction vessel 1.2 hours, obtain degraded starch solution with the ydrogen peroxide 50 of 150 gram deionized waters, 0.30 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 55 gram LUTARALDEHYDEs and 0.6 gram tosic acid, control reaction temperature is 77 ℃, reacts 4.2 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 55 gram Hydrocerol As, control reaction temperature is 86 ℃, reacts 4.2 hours, has obtained the starch-based leather retanning agent.
Embodiment 3:
1) preparation of degraded starch:
Get 35 gram W-Gums and joined the inherent 92 ℃ of insulation reaction of reaction vessel 1.4 hours, obtain degraded starch solution with the ydrogen peroxide 50 of 180 gram deionized waters, 0.35 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 65 gram LUTARALDEHYDEs and 0.65 gram tosic acid, control reaction temperature is 80 ℃, reacts 4.4 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 65 gram Hydrocerol As, control reaction temperature is 87 ℃, reacts 4.4 hours, has obtained the starch-based leather retanning agent.
Embodiment 4:
1) preparation of degraded starch:
Get 40 gram W-Gums and joined the inherent 93 ℃ of insulation reaction of reaction vessel 1.6 hours, obtain degraded starch solution with the ydrogen peroxide 50 of 210 gram deionized waters, 0.40 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 75 gram LUTARALDEHYDEs and 0.8 gram tosic acid, control reaction temperature is 82 ℃, reacts 4.6 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 75 gram Hydrocerol As, control reaction temperature is 88 ℃, reacts 4.6 hours, has obtained the starch-based leather retanning agent.
Embodiment 5:
1) preparation of degraded starch:
Get 50 gram W-Gums and joined the inherent 94 ℃ of insulation reaction of reaction vessel 1.8 hours, obtain degraded starch solution with the ydrogen peroxide 50 of 250 gram deionized waters, 0.50 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 85 gram LUTARALDEHYDEs and 0.85 gram tosic acid, control reaction temperature is 84 ℃, reacts 4.8 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 85 gram Hydrocerol As, control reaction temperature is 89 ℃, reacts 4.8 hours, has obtained the starch-based leather retanning agent.
Embodiment 6:
1) preparation of degraded starch:
Get 55 gram W-Gums and joined the inherent 95 ℃ of insulation reaction of reaction vessel 2 hours, obtain degraded starch solution with the ydrogen peroxide 50 of 300 gram deionized waters, 0.55 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 95 gram LUTARALDEHYDEs and 1.0 gram tosic acid, control reaction temperature is 85 ℃, reacts 5 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 95 gram Hydrocerol As, control reaction temperature is 90 ℃, reacts 5 hours, has obtained the starch-based leather retanning agent.
Claims (7)
1. the preparation method of a starch-based leather retanning agent is characterized in that:
1) preparation of degraded starch:
Get 25～55 gram W-Gums and joined inherent 90～95 ℃ of insulation reaction of reaction vessel 1～2 hour, obtain degraded starch solution with the ydrogen peroxide 50 of 125～300 gram deionized waters, 0.25～0.55 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 45～95 gram LUTARALDEHYDEs and 0.5～1.0 gram tosic acid, control reaction temperature is 75～85 ℃, reacts 4～5 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 45～95 gram Hydrocerol As, control reaction temperature is 85～90 ℃, reacts 4～5 hours, has obtained the starch-based leather retanning agent.
2. the preparation method of starch-based leather retanning agent according to claim 1 is characterized in that:
1) preparation of degraded starch:
Get 25 gram W-Gums and joined the inherent 90 ℃ of insulation reaction of reaction vessel 1 hour, obtain degraded starch solution with the ydrogen peroxide 50 of 125 gram deionized waters, 0.25 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 45 gram LUTARALDEHYDEs and 0.5 gram tosic acid, control reaction temperature is 75 ℃, reacts 4 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 45 gram Hydrocerol As, control reaction temperature is 85 ℃, reacts 4 hours, has obtained the starch-based leather retanning agent.
3. the preparation method of starch-based leather retanning agent according to claim 1 is characterized in that:
1) preparation of degraded starch:
Get 30 gram W-Gums and joined the inherent 91 ℃ of insulation reaction of reaction vessel 1.2 hours, obtain degraded starch solution with the ydrogen peroxide 50 of 150 gram deionized waters, 0.30 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 55 gram LUTARALDEHYDEs and 0.6 gram tosic acid, control reaction temperature is 77 ℃, reacts 4.2 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 55 gram Hydrocerol As, control reaction temperature is 86 ℃, reacts 4.2 hours, has obtained the starch-based leather retanning agent.
4. the preparation method of starch-based leather retanning agent according to claim 1 is characterized in that:
1) preparation of degraded starch:
Get 35 gram W-Gums and joined the inherent 92 ℃ of insulation reaction of reaction vessel 1.4 hours, obtain degraded starch solution with the ydrogen peroxide 50 of 180 gram deionized waters, 0.35 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 65 gram LUTARALDEHYDEs and 0.65 gram tosic acid, control reaction temperature is 80 ℃, reacts 4.4 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 65 gram Hydrocerol As, control reaction temperature is 87 ℃, reacts 4.4 hours, has obtained the starch-based leather retanning agent.
5. the preparation method of starch-based leather retanning agent according to claim 1 is characterized in that:
1) preparation of degraded starch:
Get 40 gram W-Gums and joined the inherent 93 ℃ of insulation reaction of reaction vessel 1.6 hours, obtain degraded starch solution with the ydrogen peroxide 50 of 210 gram deionized waters, 0.40 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 75 gram LUTARALDEHYDEs and 0.8 gram tosic acid, control reaction temperature is 82 ℃, reacts 4.6 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 75 gram Hydrocerol As, control reaction temperature is 88 ℃, reacts 4.6 hours, has obtained the starch-based leather retanning agent.
6. the preparation method of starch-based leather retanning agent according to claim 1 is characterized in that:
1) preparation of degraded starch:
Get 50 gram W-Gums and joined the inherent 94 ℃ of insulation reaction of reaction vessel 1.8 hours, obtain degraded starch solution with the ydrogen peroxide 50 of 250 gram deionized waters, 0.50 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 85 gram LUTARALDEHYDEs and 0.85 gram tosic acid, control reaction temperature is 84 ℃, reacts 4.8 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 85 gram Hydrocerol As, control reaction temperature is 89 ℃, reacts 4.8 hours, has obtained the starch-based leather retanning agent.
7. the preparation method of starch-based leather retanning agent according to claim 1 is characterized in that:
1) preparation of degraded starch:
Get 55 gram W-Gums and joined the inherent 95 ℃ of insulation reaction of reaction vessel 2 hours, obtain degraded starch solution with the ydrogen peroxide 50 of 300 gram deionized waters, 0.55 gram;
2) LUTARALDEHYDE treated starch preparation:
In above-mentioned degraded starch solution, add 95 gram LUTARALDEHYDEs and 1.0 gram tosic acid, control reaction temperature is 85 ℃, reacts 5 hours, obtains the LUTARALDEHYDE modified starch solution;
3) starch-based leather retanning agent preparation:
In above-mentioned LUTARALDEHYDE modified starch solution, add 95 gram Hydrocerol As, control reaction temperature is 90 ℃, reacts 5 hours, has obtained the starch-based leather retanning agent.
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| CN101880334B true CN101880334B (en) | 2012-05-09 |
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| CN104651544A (en) * | 2013-11-21 | 2015-05-27 | 谈丽娜 | Preparation method of green leather tanning agent in the type of copolymer of starch and phenols |
| CN110395016A (en) * | 2019-07-20 | 2019-11-01 | 漳州香洲皮革有限公司 | Sweat proof leather and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2182602C1 (en) * | 2001-10-16 | 2002-05-20 | Федеральное государственное унитарное предприятие Центральный научно-исследовательский институт кожевенно-обувной промышленности | Method of leather production |
| JP2007222704A (en) * | 2006-02-21 | 2007-09-06 | Mitsubishi Rayon Co Ltd | Manufacturing method for starch based water absorbent material |
| CN101851310A (en) * | 2010-06-09 | 2010-10-06 | 齐河力厚化工有限公司 | Preparation method of acrylic acid retanning agents |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2182602C1 (en) * | 2001-10-16 | 2002-05-20 | Федеральное государственное унитарное предприятие Центральный научно-исследовательский институт кожевенно-обувной промышленности | Method of leather production |
| JP2007222704A (en) * | 2006-02-21 | 2007-09-06 | Mitsubishi Rayon Co Ltd | Manufacturing method for starch based water absorbent material |
| CN101851310A (en) * | 2010-06-09 | 2010-10-06 | 齐河力厚化工有限公司 | Preparation method of acrylic acid retanning agents |
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