CN116397057B - Tanning method for in-situ growth of metal-organic framework nano tanning agent between collagen fibers - Google Patents
Tanning method for in-situ growth of metal-organic framework nano tanning agent between collagen fibers Download PDFInfo
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- CN116397057B CN116397057B CN202310536376.3A CN202310536376A CN116397057B CN 116397057 B CN116397057 B CN 116397057B CN 202310536376 A CN202310536376 A CN 202310536376A CN 116397057 B CN116397057 B CN 116397057B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 38
- 102000008186 Collagen Human genes 0.000 title claims abstract description 24
- 108010035532 Collagen Proteins 0.000 title claims abstract description 24
- 229920001436 collagen Polymers 0.000 title claims abstract description 24
- 239000000835 fiber Substances 0.000 title claims abstract description 24
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000013110 organic ligand Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 32
- 238000005554 pickling Methods 0.000 claims description 29
- 239000003513 alkali Substances 0.000 claims description 28
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 16
- 230000001105 regulatory effect Effects 0.000 claims description 15
- 239000001530 fumaric acid Substances 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 229910007926 ZrCl Inorganic materials 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims 1
- 239000010985 leather Substances 0.000 abstract description 13
- 239000003446 ligand Substances 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 230000000873 masking effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 12
- 238000002791 soaking Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a tanning method for in-situ growth of a metal-organic framework nano tanning agent between collagen fibers, and belongs to the technical field of clean tanning. The invention discloses a tanning method of a metal-organic framework nano tanning agent for in-situ growth among collagen fibers, which takes metal salt with tanning property and a small molecular organic ligand as raw materials, prepares MOFs nano tanning agent through in-situ method to obtain nano tanning agent with self-masking structure, utilizes the masking effect of the small molecular ligand on tanning metal ions, improves the stability of the tanning agent, improves the wet heat stability and physical and mechanical properties of tanned crust leather, and improves the problems of 'surface oversanning' and 'core' of tanned crust leather caused by poor stability of conventional metal tanning agents; the sources of the metal salt and the organic ligand used are wide, and the cost is low.
Description
Technical Field
The invention belongs to the technical field of clean tanning, and particularly relates to a tanning method for in-situ growth of a metal-organic framework nano tanning agent between collagen fibers.
Background
Tanning is the most critical process in tanning and is the process by which tanning agents penetrate into the hide and combine with collagen fibers to cause them to change quality. The chrome tanning agent can endow leather with excellent physical and chemical properties, and is the most widely used tanning agent. However, in the conventional chrome tanning, the chromium absorption rate is only 65-75%, the unabsorbed chromium is discharged in the form of waste water, leather scraps and the like, and the trivalent chromium used can be converted into hexavalent chromium with carcinogenicity under certain conditions, so that soil pollution is caused, and the human health is endangered. Therefore, development of chrome-free tanning agents is attracting attention.
The non-chrome metal tanning agent can endow tanned crust leather with excellent hydrothermal stability and physical and mechanical properties, and is the most hopeful to replace chrome tanning agent. However, the non-chrome metal tanning agent is unstable in structure and is not easy to form uniform and stable combination with collagen fibers. At present, a small molecular ligand is utilized to mask a non-chromium metal tanning agent, a stable metal-ligand structure is constructed, the combination rate of the tanning agent and collagen fibers can be slowed down, and the problems of 'surface oversanning' and 'core formation' of tanned crust leather are improved.
The metal-organic framework material is a nano material formed by self-assembly of a metal center and an organic ligand, and has the characteristics of multiple structures and functions, multiple unsaturated sites and the like. The organic ligand in the metal-organic frame material structure is self-masked by inorganic metal ions, so that the structure stability of the tanning agent can be realized, and the physicochemical properties of tanned crust leather are improved.
However, conventional metal-organic framework materials require high temperature and high pressure synthesis in organic solvents, increasing energy consumption and increasing the potential for environmental pollution.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a tanning method for in-situ growth of a metal-organic frame nano tanning agent between collagen fibers, which is used for solving the technical problems that the existing metal-organic frame material needs to be synthesized at high temperature and high pressure, the energy consumption is increased, and the possibility of environmental pollution is increased.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a tanning method for in-situ growth of a metal-organic framework nano tanning agent between collagen fibers, which comprises the following steps:
s1: determining the reference quality of pickling and tanning processes; adding water and sodium chloride into a rotary drum to fully dissolve to obtain a bath solution, placing the deashed pelt into the rotary drum, rotating in the bath solution, and then adjusting the pH value of the bath solution in the rotary drum to obtain an acid-immersed bath solution, and continuing to rotate;
s2: sequentially adding small molecular organic ligand and metal salt into the pickling bath liquid, rotating, then adjusting the pH value of the pickling bath liquid, heating, adding water, rotating again, then standing, rotating again, and washing out the drum by water.
Further, in S1, the reference mass of the pickling and tanning process is the mass of the delimed pelt.
Further, in S1, the mass of the water is 50-100% of the reference mass; the mass of the sodium chloride is 6 to 10 percent of the reference mass.
Further, in S1, the time of rotation in the bath is 5-15 min; after regulating the pH value of the bath liquid in the rotary drum, the rotation is continued for 50-180 min.
In S1, regulating the pH value of the bath liquid in the rotary drum to 1.5-3.5 by adopting an acid solution; the mass of the acid solution is 0.5-2.5% of the reference mass; the acid solution is formic acid solution or sulfuric acid solution; the mass ratio of the acid to the water in the acid solution is 1:10.
further, in S2, the mass of the small molecular organic ligand is 3-5% of the reference mass; the mass of the metal salt is 3-5% of the reference mass; after adding a micromolecular organic ligand into the pickling bath liquid, rotating for 10min, adding metal salt, rotating for 30-360 min, and regulating the pH value of the pickling bath liquid; the small molecule organic ligand is fumaric acid, 2-methylimidazole or terephthalic acid; the metal salt is ZrCl4, zn (NO 3) 2.6H2O or ZrOCl2.
Further, in S2, the pH value of the acid soaking bath liquid is regulated to be 4.0-6.0 by adopting alkali solution; the mass of the alkali solution is 0.5-2.5% of the reference mass; the alkali solution is sodium bicarbonate solution or sodium formate solution; the mass ratio of alkali to water in the alkali solution is 1:20.
further, in S2, heating to 38 ℃; the temperature of the added water is 38 ℃; the mass of the added water is 50-100% of the reference mass; and after the temperature is raised, the rotation is carried out again for 60 minutes.
Further, in S2, the standing time is 12-24 hours.
Further, in S2, the mixture is rotated for 30 to 90 minutes after standing.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a tanning method of a metal-organic framework nano tanning agent for in-situ growth among collagen fibers, which takes metal salt with tanning property and a small molecular organic ligand as raw materials, prepares MOFs nano tanning agent through an in-situ method to obtain the nano tanning agent with a self-masking structure, utilizes the masking effect of the small molecular ligand on tanning metal ions, improves the stability of the tanning agent, improves the wet heat stability and physical and mechanical properties of tanned crust leather, and improves the problems of 'surface oversanning' and 'core' of the tanned crust leather caused by poor stability of the conventional metal tanning agent; the sources of the metal salt and the organic ligand used are wide, and the cost is low. The tanning process provided by the invention has the same equipment as that required by conventional tanning, does not need to additionally increase tanning agent synthesis and tanning equipment during application, and has the advantages of simple operation and strong applicability; the invention can realize chrome-free tanning, avoid the use of organic solvent in tanning agent synthesis and chromium powder in tanning process, reduce the influence of tanning on environment and realize clean tanning.
Drawings
Figure 1 is an XRD spectrum of tanned crust leather in example 1 of the present invention.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features such as values, amounts, and concentrations that are defined herein in the numerical or percent ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise indicated, "comprising," "including," "having," or similar terms encompass the meanings of "consisting of … …" and "consisting essentially of … …," e.g., "a includes a" encompasses the meanings of "a includes a and the other and" a includes a only.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The invention discloses a tanning method for in-situ growth of metal-organic framework nano tanning agents among collagen fibers, which takes metal salt with tanning property and organic ligand as raw materials to prepare MOFs nano tanning agents among the collagen fibers in-situ, utilizes the masking effect of micromolecular ligand on tanning metal ions, improves the stability and permeability of the tanning agents, and improves the problems of 'surface oversanning' and 'core production' of tanned crust leather caused by poor stability of conventional metal tanning agents. The invention does not relate to the use of chromium powder and organic tanning agent, can effectively avoid chromium pollution, reduce the influence of tanning on environment and realize clean tanning. Mainly comprises the following steps:
(1) Pickling: weighing the quality of the deashed pelts as the reference quality of pickling and tanning processes; under the normal temperature condition, adding water and sodium chloride into a rotary drum for full dissolution, wherein the mass of the water is 50-100% of that of the rotary drum, and the mass of the sodium chloride is 6-10% of that of the rotary drum; placing the deashed pelts in a rotary drum, and rotating for 5-15 min; then dilute formic acid or sulfuric acid solution is used for regulating the pH value of bath liquid in the rotary drum to be 1.5-3.5, and the mass ratio of acid to water in the acid solution is 1:10, the mass of the acid solution is 0.5 to 2.5 percent of the standard; the deashing pelt is continuously rotated in the rotary drum for 50 to 180 minutes.
(2) Tanning: adding small molecular organic ligand required by synthesizing metal-organic frame nano tanning agent into the acid soaking bath liquid, wherein the mass of the ligand is 3-5% of that of the basic material, and rotating for 10min; then adding metal salt into the rotary drum, wherein the mass of the metal salt is 3-5% of that of the reference, and rotating for 30-360 min; then dilute sodium bicarbonate or sodium formate solution is used for regulating the pH value of bath liquid in the rotary drum to 4.0-6.0, and the mass ratio of alkali to water in the alkali solution is 1:20, the mass of the alkali solution is 0.5 to 2.5 percent of the standard; heating to 38 ℃, adding 50-100% of hot water with the mass as a reference, turning to 60min, standing overnight, turning to 30-90 min the next day, and washing out the drum with water.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The following examples use instrumentation conventional in the art. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The following examples used various starting materials, unless otherwise indicated, were conventional commercial products, the specifications of which are conventional in the art. In the description of the present invention and the following examples, "%" means weight percent, and "parts" means parts by weight, and ratios means weight ratio, unless otherwise specified.
Example 1
The tanning method of the metal-organic framework nano tanning agent for in-situ growth between collagen fibers comprises the following steps:
s1: pickling: weighing the quality of the deashed pelts as the reference quality of pickling and tanning processes; under the normal temperature condition, adding water and sodium chloride into a rotary drum for full dissolution to obtain bath liquid, wherein the mass of the water is 60% of the reference mass, and the mass of the sodium chloride is 7% of the reference mass; placing the deashed pelts in a rotary drum, and rotating for 10min; then, the pH value of the bath liquid in the rotary drum is regulated to be 1.5 by diluted formic acid solution, so as to obtain an acid soaking bath liquid, wherein the mass ratio of acid to water in the acid solution is 1:10, the mass of the acid solution is 2.5% of the reference; the deashing pelt is continuously rotated in the rotary drum for 60min;
s2: adding fumaric acid into the pickling bath liquid, wherein the mass of the fumaric acid is 5% of the reference mass, and converting for 10min; next ZrCl is added into the rotary drum 4 ，ZrCl 4 The mass of (2) is 5% of the reference, and the process is carried out for 360min; then the pH value of the bath liquid in the rotary drum is regulated to 6.0 by diluted sodium bicarbonate solution, and the mass ratio of alkali to water in the alkali solution is 1:20, the mass of the alkali solution is 2.5% of the reference mass; lifting deviceHeating to 38deg.C, adding hot water of mass 100% and 38deg.C, standing for 12 hr, rotating for 60min the next day, and washing out the drum.
Example 2
The tanning method of the metal-organic framework nano tanning agent for in-situ growth between collagen fibers comprises the following steps:
s1: pickling: weighing the quality of the deashed pelts as the reference quality of pickling and tanning processes; under the normal temperature condition, adding water and sodium chloride into a rotary drum for full dissolution to obtain bath liquid, wherein the mass of the water is 50% of the reference mass, and the mass of the sodium chloride is 8% of the reference mass; placing the deashed pelts in a rotary drum, and rotating for 5min; then, the pH value of the bath liquid in the rotary drum is regulated to be 2.5 by diluted formic acid solution, so as to obtain an acid soaking bath liquid, wherein the mass ratio of acid to water in the acid solution is 1:10, the mass of the acid solution is 1.0% of the standard; the deashing pelt is continuously rotated in the rotary drum for 50min;
s2: adding fumaric acid into the pickling bath liquid, wherein the mass of the fumaric acid is 4% of the reference mass, and converting for 10min; next, zn (NO) is added into the drum 3 ) 2 ·6H 2 O，Zn(NO 3 ) 2 ·6H 2 The mass of O is 4% of the standard, and the process is carried out for 180min; then the pH value of the bath liquid in the rotary drum is adjusted to 5.0 by diluted sodium bicarbonate solution, and the mass ratio of alkali to water in the alkali solution is 1:20, the mass of the alkali solution is 1.5% of the reference mass; heating to 38deg.C, adding 38deg.C hot water 60% of the standard mass, standing for 15 hr, rotating for 30min the next day, and washing out the drum.
Example 3
The tanning method of the metal-organic framework nano tanning agent for in-situ growth between collagen fibers comprises the following steps:
s1: pickling: weighing the quality of the deashed pelts as the reference quality of pickling and tanning processes; under the normal temperature condition, adding water and sodium chloride into a rotary drum for full dissolution to obtain bath liquid, wherein the mass of the water is 100% of the reference mass, and the mass of the sodium chloride is 10% of the reference mass; placing the deashed pelts in a rotary drum, and rotating for 15min; then, the pH value of the bath liquid in the rotary drum is regulated to be 1.5 by diluted formic acid solution, so as to obtain an acid soaking bath liquid, wherein the mass ratio of acid to water in the acid solution is 1:10, the mass of the acid solution is 2.5% of the reference; the deashing pelt is continuously rotated for 180min in a rotary drum;
s2: adding fumaric acid into the pickling bath liquid, wherein the mass of the fumaric acid is 5% of the reference mass, and converting for 10min; next ZrOCl is added into the rotary drum 2 ，ZrOCl 2 The mass of (2) is 5% of the reference, and the process is carried out for 360min; then the pH value of the bath liquid in the rotary drum is regulated to 6.0 by diluted sodium bicarbonate solution, and the mass ratio of alkali to water in the alkali solution is 1:20, the mass of the alkali solution is 2.5% of the reference mass; heating to 38deg.C, adding 38deg.C hot water 100% of the standard mass, standing for 18 hr, turning 90min the next day, and washing out the drum.
Example 4
The tanning method of the metal-organic framework nano tanning agent for in-situ growth between collagen fibers comprises the following steps:
s1: pickling: weighing the quality of the deashed pelts as the reference quality of pickling and tanning processes; under the normal temperature condition, adding water and sodium chloride into a rotary drum for full dissolution to obtain bath liquid, wherein the mass of the water is 70% of the reference mass, and the mass of the sodium chloride is 6% of the reference mass; placing the deashed pelts in a rotary drum, and rotating for 10min; then, the pH value of the bath liquid in the rotary drum is regulated to 2.0 by diluted formic acid solution, so as to obtain an acid soaking bath liquid, wherein the mass ratio of acid to water in the acid solution is 1:10, the mass of the acid solution is 2.0% of the standard; the deashing pelt is continuously rotated for 90min in a rotary drum;
s2: adding fumaric acid into the pickling bath liquid, wherein the mass of the fumaric acid is 5% of the reference mass, and converting for 10min; next ZrOCl is added into the rotary drum 2 ，ZrOCl 2 The mass of (2) is 3% of the reference mass, and the rotation is carried out for 30min; then the pH value of the bath liquid in the rotary drum is regulated to be 4.0 by diluted sodium bicarbonate solution, and the mass ratio of alkali to water in the alkali solution is 1:20, the mass of the alkali solution is 2.5% of the reference mass; heating to 38deg.C, adding 38deg.C hot water with mass of 100% of the standard mass, standing for 20 hr, turning 60min the next day, and washing out the drum.
Example 5
The tanning method of the metal-organic framework nano tanning agent for in-situ growth between collagen fibers comprises the following steps:
s1: pickling: weighing the quality of the deashed pelts as the reference quality of pickling and tanning processes; under the normal temperature condition, adding water and sodium chloride into a rotary drum for full dissolution to obtain bath liquid, wherein the mass of the water is 80% of the reference mass, and the mass of the sodium chloride is 9% of the reference mass; placing the deashed pelts in a rotary drum, and rotating for 15min; then, the pH value of the bath liquid in the rotary drum is regulated to be 1.5 by diluted formic acid solution, so as to obtain an acid soaking bath liquid, wherein the mass ratio of acid to water in the acid solution is 1:10, the mass of the acid solution is 2.5% of the reference; the deashing pelt continues to rotate in the rotary drum for 150min;
s2: adding terephthalic acid into the pickling bath liquid, wherein the mass of the terephthalic acid is 4% of the reference mass, and rotating for 10min; next, zn (NO) is added into the drum 3 ) 2 ·6H 2 O，Zn(NO 3 ) 2 ·6H 2 The mass of O is 4% of the standard, and the reaction time is 240min; then the pH value of the bath liquid in the rotary drum is adjusted to 5.0 by diluted sodium bicarbonate solution, and the mass ratio of alkali to water in the alkali solution is 1:20, the mass of the alkali solution is 2.0% of the reference mass; heating to 38deg.C, adding 38deg.C hot water with mass of 50% of the standard mass, standing for 25 hr, turning for 60min the next day, and washing out the drum.
Referring to fig. 1, an XRD spectrum of the tanned crust leather in example 1 is shown. From the figure, it can be seen that a characteristic diffraction peak of UiO-66 (Zr-terephthalic acid) appears in the tanned crust leather, which indicates successful in situ growth between collagen fibers to give a metal-organic framework nano-tanning agent.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (5)
1. The tanning method of the metal-organic framework nano tanning agent for in-situ growth between collagen fibers is characterized by comprising the following steps of:
s1: determining the reference quality of pickling and tanning processes; adding water and sodium chloride into a rotary drum to fully dissolve to obtain a bath solution, placing the deashed pelt into the rotary drum, rotating in the bath solution, and then adjusting the pH value of the bath solution in the rotary drum to obtain an acid-immersed bath solution, and continuing to rotate;
s2: sequentially adding a micromolecular organic ligand and metal salt into the pickling bath liquid, rotating, then adjusting the pH value of the pickling bath liquid, heating, adding water, rotating again, then standing, rotating again, and washing out the drum by water;
in the S1, an acid solution is adopted to adjust the pH value of the bath liquid in the rotary drum to 1.5-3.5; the mass of the acid solution is 0.5-2.5% of the reference mass; the acid solution is formic acid solution or sulfuric acid solution; the mass ratio of the acid to the water in the acid solution is 1:10;
s1, the reference quality of the pickling and tanning process is the quality of the deashed pelts;
in S2, the mass of the small molecular organic ligand is 3% -5% of the reference mass; the mass of the metal salt is 3% -5% of the reference mass; after adding a small molecular organic ligand into the pickling bath liquid, rotating for 10min, adding metal salt, rotating for 30-360 min, and adjusting the pH value of the pickling bath liquid; the small molecule organic ligand is fumaric acid, 2-methylimidazole or terephthalic acid; the metal salt is ZrCl 4 、Zn(NO 3 ) 2 ·6H 2 O or ZrOCl 2 ；
S2, adjusting the pH value of the acid leaching bath solution to 4.0-6.0 by adopting an alkali solution; the mass of the alkali solution is 0.5-2.5% of the reference mass; the alkali solution is sodium bicarbonate solution or sodium formate solution; the mass ratio of alkali to water in the alkali solution is 1:20, a step of;
s2, heating to 38 ℃; the temperature of the added water is 38 ℃; the mass of the added water is 50% -100% of the reference mass; and after the temperature is raised, the rotation is carried out again for 60 minutes.
2. The tanning method of an in-situ growth metal-organic framework nano tanning agent among collagen fibers according to claim 1, wherein in S1, the mass of water is 50-100% of the reference mass; the mass of the sodium chloride is 6-10% of the reference mass.
3. The tanning method of an in-situ growth metal-organic framework nano tanning agent among collagen fibers according to claim 1, wherein in S1, the time of rotation in bath liquid is 5-15 min; and after regulating the pH value of the bath liquid in the rotary drum, continuing to rotate for 50-180 min.
4. The tanning method of an in-situ growth metal-organic framework nano tanning agent among collagen fibers according to claim 1, wherein in S2, the standing time is 12-24 h.
5. The tanning method of an in-situ growth metal-organic framework nano tanning agent among collagen fibers according to claim 1, wherein in S2, the tanning agent is rotated for 30-90 min after standing.
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| CN112341631A (en) * | 2020-10-30 | 2021-02-09 | 陕西科技大学 | Method for synthesizing ZnAl-MOF-LDH nano material based on template-oriented method |
| CN113073160A (en) * | 2021-04-29 | 2021-07-06 | 陕西科技大学 | Carboxylic acid ligand MOFs nano tanning agent with stable framework structure and preparation method and application thereof |
| CN114164308A (en) * | 2021-11-18 | 2022-03-11 | 陕西科技大学 | Multi-carboxyl metal complex tanning agent with self-masking effect and preparation method thereof |
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| CN112341631A (en) * | 2020-10-30 | 2021-02-09 | 陕西科技大学 | Method for synthesizing ZnAl-MOF-LDH nano material based on template-oriented method |
| CN113073160A (en) * | 2021-04-29 | 2021-07-06 | 陕西科技大学 | Carboxylic acid ligand MOFs nano tanning agent with stable framework structure and preparation method and application thereof |
| CN114164308A (en) * | 2021-11-18 | 2022-03-11 | 陕西科技大学 | Multi-carboxyl metal complex tanning agent with self-masking effect and preparation method thereof |
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