CN114525368B - In-situ dyeing type bio-based tanning agent and preparation method and application thereof - Google Patents
In-situ dyeing type bio-based tanning agent and preparation method and application thereof Download PDFInfo
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- CN114525368B CN114525368B CN202210070911.6A CN202210070911A CN114525368B CN 114525368 B CN114525368 B CN 114525368B CN 202210070911 A CN202210070911 A CN 202210070911A CN 114525368 B CN114525368 B CN 114525368B
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- 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
- C14C3/10—Vegetable tanning
- C14C3/12—Vegetable tanning using purified or modified vegetable tanning agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
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Abstract
The invention belongs to the technical field of tanning materials, and discloses an in-situ dyeing type bio-based tanning agent, a preparation method and application thereof. The raw material of the in-situ dyeing type bio-based tanning agent comprises 100 parts of biomass raw material, 100-240 parts of activating agent and 0-50 parts of auxiliary color agent. The molecular structure of the in-situ dyeing type bio-based tanning agent provided by the invention contains abundant active groups, and when the in-situ dyeing type bio-based tanning agent is used for leather tanning, the in-situ dyeing type bio-based tanning agent can be subjected to a crosslinking reaction with amino groups on collagen fibers to form a multi-point covalent crosslinking structure, so that excellent tanning performance can be shown. The tanning agent can form a conjugate Schiff base structure in situ between the tanning agent molecules and the collagen fibers while the tanning agent is used for tanning, and endows tanning leather with a specific color by virtue of the conjugate structure and the auxiliary color effect of substituents, so that the leather is dyed in situ.
Description
Technical Field
The invention relates to the technical field of tanning materials, in particular to an in-situ dyeing type bio-based tanning agent, and a preparation method and application thereof.
Background
The leather industry is one of the pillar industries of the light industry in China. The leather raw material is green, natural, easy to obtain and continuous, and the product processed by the leather raw material is always required by people for pursuing good life. In recent years, however, the global leather industry has been faced with serious challenges due to environmental pollution problems in the leather industry, where chromium pollution is a key bottleneck that limits its ecological sustainability. From the perspective of thoroughly eliminating chromium pollution, the development and application of the organic tanning agent with the characteristic of Metal-free are important ways for breaking through the development bottleneck.
Among the existing organic tanning agents, aldehyde tanning agents such as modified glutaraldehyde, oxazolidine, organic phosphine salt tanning agents, TWT amphoteric organic tanning agents and the like show higher and stable tanning property and good leather forming performance, are mainstream organic tanning agents in the market at present, and can replace part of chrome tanning agents to use. In terms of application, the tanning performance of the tanning agent is good, but the problem that the tanning continuously releases formaldehyde to cause the exceeding of the formaldehyde content in leather products exists. In addition, the leather crust tanned by the aldehyde organic tanning agent generally has the problems of poor absorption and combination of common dyeing and finishing materials and the like due to low isoelectric points, and the problems of high chromaticity of dyeing waste liquid, increased difficulty of comprehensive wastewater treatment and the like due to low dye absorptivity. In particular, too low a dye binding fastness may cause colour migration of the leather product during use, thereby reducing its quality grade, which not only directly affects the consumer's expectations of the pleasant aesthetic experience of the product, but may also bring about a potential hazard to the consumer's physical health.
In view of this, the present invention has been made.
Disclosure of Invention
To solve the technical problems in the background art, a first object of the present invention is to provide an in-situ dyeing type bio-based tanning agent, which has excellent tanning performance and can realize in-situ dyeing.
The second aim of the invention is to provide a method for preparing the in-situ dyeing type bio-based tanning agent, which is simple, the tanning performance of the prepared tanning agent is good, and the application of the tanning agent can solve chromium pollution from the source.
The third object of the invention is to provide an application of an in-situ dyeing type bio-based tanning agent in leather tanning, wherein an in-situ chromophoric structure formed between the tanning agent and a leather collagen fiber ensures high color fastness of leather crust through covalent crosslinking with high stability.
In order to achieve the above purpose, the first technical scheme adopted by the invention is as follows: an in-situ dyeing type bio-based tanning agent comprises the following raw materials in parts by weight:
100 parts of biomass raw material, 100-240 parts of activating agent and 0-50 parts of auxiliary color former.
Preferably, the biomass raw material is a saccharide substance, and comprises any one or more of monosaccharide, disaccharide, oligosaccharide and derivatives thereof, polysaccharide and degradation products thereof;
preferably, the mono-, di-, oligosaccharides include, but are not limited to, glucose, fructose, sucrose, xylose;
preferably, the polysaccharide includes, but is not limited to, starch, sodium carboxymethyl cellulose, sodium alginate.
Preferably, the activator is any one or more of an hydroformylation agent;
preferably, the hydroformylation agent is a periodate salt.
Preferably, the activator further comprises any one or more of an epoxy compound;
preferably, the epoxy compound is selected from the group consisting of 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl triethoxy silane and 3-glycidoxypropyl methyl diethoxy silane.
Preferably, the color agent comprises, but is not limited to, any one or more of melamine, cyanuric chloride, sodium p-aminobenzenesulfonate, sodium 2, 4-diaminobenzenesulfonate, sodium bromamine, and 1-amino-2-naphthol-4-sulfonic acid.
The second technical scheme adopted by the invention is as follows:
a method of preparing an in situ dyeing bio-based tanning agent comprising the steps of:
and mixing the biomass raw material with an activating agent, and reacting for 2-12 hours at the temperature of 5-15 ℃ to complete the first reaction.
Preferably, the first reaction further comprises a second reaction of adding a color assisting agent and reacting for 0.5-4 hours at the pH of 6.5-8.5 and the temperature of 30-60 ℃.
Preferably, the second reaction further comprises adding an epoxy compound, and reacting for 1-4 hours at 0.01~0.1 MPa,30~80 ℃.
The third technical scheme adopted by the invention is as follows:
the application of the in-situ dyeing type bio-based tanning agent in leather tanning.
Compared with the prior art, the invention has the following beneficial effects:
(1) the molecular structure of the in-situ dyeing type bio-based tanning agent provided by the invention contains abundant active groups, and can be subjected to crosslinking reaction with amino groups on collagen fibers to form a multi-point covalent crosslinking structure, so that the in-situ dyeing type bio-based tanning agent can show excellent tanning performance.
(2) The in-situ dyeing type bio-based tanning agent provided by the invention can form a conjugate Schiff base structure in-situ between the tanning agent molecules and the collagen fibers while tanning, and endows tanning leather with a specific color by virtue of the conjugate structure and the auxiliary color development effect of substituents, so that in-situ dyeing of leather is realized.
(3) The in-situ color development structure formed between the in-situ dyeing type bio-based tanning agent and the collagen fiber belongs to a covalent crosslinking structure, and has high stability, so that high color fastness of leather crust is ensured.
(4) The in-situ dyeing type bio-based tanning agent provided by the invention has the advantages that the main raw materials used in preparation are biomass, and the source is wide and renewable; in addition, the leather crust tanned by the tanning agent does not need special dyeing process in the wet finishing process, does not need to add extra dye, saves time and material cost, and realizes the reduction of leather making process and materials; therefore, the in-situ dyeing type bio-based tanning agent provided by the invention has good social and economic benefits.
(5) The in-situ dyeing type bio-based tanning agent provided by the invention can enable the prepared tanning agent to contain no free formaldehyde through carrying out cooperative regulation and modification on the molecular structure of biomass, can effectively solve the product quality problem caused by continuous release of free formaldehyde in tanning crust by the conventional organic tanning agent, and enables the tanning agent to meet the manufacturing requirement of ecological leather.
(6) The preparation method of the in-situ dyeing type bio-based tanning agent provided by the invention is friendly and simple to operate, mild in condition and convenient to popularize, so that the preparation method has good market competitiveness.
Drawings
Fig. 1 shows application examples 1 to 2, and examples 1 to 2 were used to obtain the appearance color and shrinkage temperature of tanned leather crust by the tanning method described in application example 1.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The first embodiment of the invention provides an in-situ dyeing type bio-based tanning agent, which comprises the following raw materials in parts by weight: 100 parts of biomass raw material, 100-240 parts of activating agent and 0-50 parts of auxiliary color former.
According to the invention, biomass is used as a raw material, a product with a dialdehyde main structural unit is obtained through structural modification, the dialdehyde substance can react with amino groups on leather collagen under an alkaline condition to form intramolecular and intermolecular crosslinking containing a Schiff base structure to show tannage, and meanwhile, a C=C double bond structure is formed through beta-elimination reaction, so that a conjugated Schiff base structure containing the C=C double bond characteristic is formed, the structure can absorb specific light waves, a substituent group on the conjugated Schiff base structure can generate a specific color assisting effect, and therefore, the tanning effect is generated and simultaneously, the specific color of the tannage is endowed, in-situ dyeing of leather is realized, and the problems of low absorption rate of organic tannage on traditional dyes, high pollution of dyeing waste liquid, low leather color fastness, easiness in color migration and the like are overcome.
The biomass raw material contains any one or more of saccharides such as monosaccharides, disaccharides, oligosaccharides and polysaccharides, and specifically contains monosaccharides, disaccharides, oligosaccharides and derivatives thereof, polysaccharides and degradation products thereof. For example, the biomass feedstock may be monosaccharides and derivatives thereof, disaccharides and derivatives thereof, oligosaccharides and derivatives thereof, polysaccharides and degradation products thereof.
Wherein the mono-, di-, oligosaccharides include, but are not limited to, glucose, fructose, sucrose, xylose. The polysaccharide includes, but is not limited to, starch, sodium carboxymethyl cellulose, sodium alginate, and the like.
The activator is one or more of the hydroformylation agents, namely the hydroformylation agents are essential components; in some preferred embodiments, the hydroformylation agent is a periodate salt.
Since the introduction of the chromophoric groups consumes a certain amount of active aldehyde groups, the activator may also contain any one or more of the epoxy compounds in some cases in order to ensure good tanning properties of the tanning agent produced; in some preferred embodiments, the epoxy compound is selected from the group consisting of 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxy silane, 3-glycidoxypropyl triethoxy silane, and 3-glycidoxypropyl methyldiethoxy silane.
It should be noted that the auxiliary color agent has no dyeing function, and the molecular structure of the auxiliary color agent is introduced into the conjugated Schiff base structure formed in the tanning process of the tanning agent through Schiff base reaction, so that the regulation and control of the dyeing color system of the tanning agent can be realized, the color variety of the tanned leather blank is enriched, and the requirement of the market on the color diversity of leather products is better met; the color agent includes, but is not limited to, any one or more of melamine, cyanuric chloride, sodium p-aminobenzenesulfonate, sodium 2, 4-diaminobenzenesulfonate, sodium bromamine, and 1-amino-2-naphthol-4-sulfonic acid.
In a second embodiment, the present invention provides a method for preparing an in situ dyeing bio-based tanning agent, comprising the steps of: and mixing the biomass raw material with an activating agent, and reacting for 2-12 hours at the temperature of 5-15 ℃ to complete the first reaction. The method comprises the steps of fully dispersing or dissolving biomass raw materials in water, adding an activating agent under a stirring state, controlling the reaction temperature to be 5-15 ℃, reacting for 2-12 hours to finish a first reaction, and filtering and separating to obtain a mixed solution, namely the in-situ dyeing type bio-based tanning agent. It should be noted that the activator added in the process must contain an aldehyde agent, and the epoxy compound may be optionally added, for example, when the amount of the aldehyde agent is low or when it is desired to further improve the tanning performance of the tanning agent, a certain amount of the epoxy compound may be added; in the case of a tanning agent having a rich aldehyde group content and good tanning properties, no epoxy compound may be added.
In some preferred modes, in order to increase the color variety of the tanned leather crust, adding a color assisting agent after the first reaction, and reacting for 0.5-4 hours at the pH of 6.5-8.5 and the temperature of 30-60 ℃ to obtain the in-situ dyeing type bio-based tanning agent.
In other preferred modes, in order to ensure or improve the tanning performance of the tanning agent, an epoxy compound is added after the second reaction, and the reaction is carried out for 1-4 hours at the temperature of 30-80 ℃ under the pressure of 0.01-0.1 MPa, so as to obtain the in-situ dyeing type bio-based tanning agent. It should be noted that the addition of the epoxy compound in this step is not correlated with whether the epoxy compound is added in the first reaction, and whether it is added is mainly affected by the content of active tanning groups in the molecular structure of the tanning agent.
The invention takes biomass as a raw material, firstly adopts an activating agent to carry out structural modification on the biomass raw material, and obtains a product with a molecular structure rich in aldehyde groups. On the basis, on one hand, partial in-situ dyeing type bio-based tanning agent can be obtained through targeted screening of biomass raw material structures; on the other hand, the in-situ dyeing type bio-based tanning agent with more various upper dyeing systems and good tanning property can be prepared by further specifically introducing a coloring assisting group on the molecular structure of an aldehyde product and supplementing an active crosslinking group through modification of an epoxy compound based on the molecular structure characteristic of the aldehyde product.
The third embodiment of the invention provides the application of the in-situ dyeing type bio-based tanning agent in leather tanning. The molecular structure of the in-situ dyeing type bio-based tanning agent provided by the invention contains abundant active groups, and can be subjected to crosslinking reaction with amino groups on leather collagen fibers to form a multipoint covalent crosslinking structure, so that the in-situ dyeing type bio-based tanning agent can show excellent tanning performance. The tanning agent provided by the invention can form a conjugate Schiff base structure in situ between the tanning agent molecules and the collagen fibers while the tanning effect is generated, and endows the tanned leather with a specific color by virtue of the conjugate structure and the auxiliary color development effect of the substituent groups, so that the leather is dyed in situ. Meanwhile, an in-situ color development structure formed between the tanning agent and the leather collagen fiber belongs to a covalent crosslinking structure, and the stability is high, so that the high color fastness of the leather crust is ensured.
The tanning method of leather is a tanning method commonly used in the art. For example, it may be:
and (3) taking the pickling pelt or the gray leather as a tanning object, wherein the dosage of the tanning agent is 2% -8% of the leather weight during tanning, rotating for 0-4 h at normal temperature, then extracting alkali until the pH value of the bath liquid is 7.5-9.0, rotating for 20 min, heating to 40-45 ℃, continuing rotating for 120-360 min, stopping the drum overnight, rotating for 30 min the next day, discharging the drum, and carrying out bonding for 24-h to obtain the tanned leather crust.
In order to better understand the technical scheme provided by the invention, the in-situ dyeing type bio-based tanning agent, the preparation method and the performance test provided by the embodiment of the invention are respectively described in the following specific examples.
It is also worth to say that in the following application examples and application comparative examples:
1) The "parts" in the examples are all "parts by weight";
2) The shrinkage temperature (representing the wet heat stability of the leather crust) of the tanned leather crust is measured by adopting a shrinkage temperature meter;
3) The free formaldehyde content in crust leather is measured by adopting a high performance liquid chromatography method described in national standard GB/T19941-2005;
4) The color fastness of crust leather is measured by adopting a QBT 2537-2001 leather color fastness test reciprocating friction color fastness method.
Example 1
Taking 100 parts of alpha-methyl glucoside, fully dissolving in water, adding 5 parts of 3-glycidoxypropyl trimethoxy silane and 160 parts of sodium periodate under the stirring state, controlling the reaction temperature to be 5 ℃, reacting 12 and h, and filtering and separating to obtain the in-situ dyeing type bio-based tanning agent.
Example 2
Taking 100 parts of sucrose, fully dissolving in water, adding 180 parts of sodium periodate under stirring, controlling the reaction temperature to be 10 ℃, reacting 10 and h, and filtering and separating to obtain a first mixed solution;
and 5 parts of 1-amino-2-naphthol-4-sulfonic acid is added into the first mixed solution, the reaction temperature is controlled to be 30 ℃, the pH of a reaction system is 8.5, and the reaction is continued to be carried out for 0.5 h, so that the in-situ dyeing type bio-based tanning agent is obtained.
Example 3
100 parts of sucralose is fully dissolved in water, 10 parts of 3-glycidoxypropyl triethoxysilane and 150 parts of sodium periodate are added under stirring, the reaction temperature is controlled to be 15 ℃, the reaction is carried out at 8 and h, and the in-situ dyeing type bio-based tanning agent is obtained after filtration and separation.
Example 4
Taking 100 parts of sucrose, fully dissolving in water, adding 100 parts of sodium periodate under stirring, controlling the reaction temperature to be 10 ℃, reacting 6 and h, and filtering and separating to obtain a first mixed solution;
50 parts of 2, 4-diaminobenzene sodium sulfonate is added into the first mixed solution, the reaction temperature is controlled to be 60 ℃, the pH of a reaction system is 7.0, and the reaction is continued to be 4. 4 h, so that the in-situ dyeing type bio-based tanning agent is obtained.
Example 5
Taking 100 parts of starch, fully dispersing in water, adding 100 parts of sodium periodate under stirring, controlling the reaction temperature to be 10 ℃, reacting 12-h, and filtering and separating to obtain a first mixed solution;
adding 30 parts of sodium bromamine into the first mixed solution, controlling the reaction temperature to be 50 ℃, controlling the pH of a reaction system to be 8.0, and continuing to react for 2 h to obtain a second mixed solution;
and slowly adding 80 parts of 3-glycidoxypropyl methyl dimethoxy silane into the second mixed solution, regulating the reaction temperature to 30 ℃, and then reacting 4 h under 0.01 MPa to obtain the in-situ dyeing type bio-based tanning agent.
Example 6
Taking 100 parts of sodium carboxymethyl cellulose, fully dissolving in water, adding 100 parts of sodium periodate under stirring, controlling the reaction temperature to 15 ℃, reacting 8 and h, and filtering and separating to obtain a first mixed solution;
adding 20 parts of sodium sulfanilate into the first mixed solution, controlling the reaction temperature to be 40 ℃, controlling the pH of a reaction system to be 6.5, and continuing to react for 4 h to obtain an in-situ dyeing type bio-based tanning agent;
120 parts of 3-glycidoxypropyl methyl diethoxy silane is slowly added into the second mixed solution, the reaction temperature is regulated to 50 ℃, and then the reaction is carried out under 0.02 MPa for 1 h, thus obtaining the in-situ dyeing type bio-based tanning agent.
Example 7
Taking 100 parts of sodium alginate, fully dissolving in water, adding 120 parts of sodium periodate under stirring, controlling the reaction temperature to be 5 ℃, reacting 6 and h, and filtering and separating to obtain a first mixed solution;
and adding 10 parts of sodium bromamine into the first mixed solution, controlling the reaction temperature to be 50 ℃, controlling the pH of a reaction system to be 8.0, and continuing to react for 3 h to obtain the in-situ dyeing type bio-based tanning agent.
Example 8
Taking 100 parts of glucose, fully dissolving in water, adding 50 parts of 3-glycidoxypropyl triethoxysilane and 100 parts of sodium periodate under the stirring state, controlling the reaction temperature to be 10 ℃, reacting 2 and h, and filtering and separating to obtain a first mixed solution;
adding 30 parts of cyanuric chloride into the first mixed solution, controlling the reaction temperature to be 60 ℃, controlling the pH of a reaction system to be 7.5, and continuing to react for 2 h to obtain a second mixed solution;
and slowly adding 50 parts of 3-glycidoxypropyl trimethoxy silane into the second mixed solution, regulating the reaction temperature to 80 ℃, and then reacting 2 h under 0.1 MPa to obtain the in-situ dyeing type bio-based tanning agent.
Example 9
Taking 100 parts of D-xylose, fully dissolving in water, adding 20 parts of 3-glycidoxypropyl dimethoxy silane and 100 parts of sodium periodate under the stirring state, controlling the reaction temperature to be 5 ℃, reacting 4 and h, and filtering and separating to obtain a first mixed solution;
adding 30 parts of melamine into the first mixed solution, controlling the reaction temperature to be 50 ℃, controlling the pH of a reaction system to be 8.0, and continuing to react for 3 h to obtain a second mixed solution;
and slowly adding 60 parts of 3-glycidoxypropyl dimethoxy silane into the second mixed solution, regulating the reaction temperature to 60 ℃, and then reacting 3 h under 0.08 MPa to obtain the in-situ dyeing type bio-based tanning agent.
Example 10
Taking 100 parts of dextrin, fully dissolving in water, adding 10 parts of 3-glycidoxypropyl triethoxysilane and 120 parts of sodium periodate under the stirring state, controlling the reaction temperature to be 10 ℃, reacting 10 and h, and filtering and separating to obtain a first mixed solution;
adding 20 parts of 1-amino-2-naphthol-4-sulfonic acid into the first mixed solution, controlling the reaction temperature to be 40 ℃, controlling the pH of a reaction system to be 8.5, and continuously reacting to 0.5 h to obtain a second mixed solution;
and slowly adding 80 parts of 3-glycidoxypropyl triethoxysilane into the second mixed solution, regulating the reaction temperature to 80 ℃, and then reacting 2 h under 0.08 MPa to obtain the in-situ dyeing type bio-based tanning agent.
Example 11
Taking 60 parts of starch and 40 parts of dextrin, fully dispersing in water, adding 20 parts of 3-glycidoxypropyl diethoxysilane and 120 parts of sodium periodate in a stirring state, controlling the reaction temperature to be 5 ℃, reacting 12 and h, and filtering and separating to obtain a first mixed solution;
adding 50 parts of sodium bromamine into the first mixed solution, controlling the reaction temperature to be 60 ℃, controlling the pH of a reaction system to be 6.5, and continuing to react for 4. 4 h to obtain a second mixed solution;
and slowly adding 60 parts of 3-glycidoxypropyl diethoxy silane into the second mixed solution, regulating the reaction temperature to 50 ℃, and then reacting 2 h under 0.02 MPa to obtain the in-situ dyeing type bio-based tanning agent.
Example 12
Taking 60 parts of sucrose and 40 parts of alpha-methyl glucoside, fully dissolving in water, adding 180 parts of sodium periodate under stirring, controlling the reaction temperature to be 5 ℃, reacting 12 and h, and filtering and separating to obtain a first mixed solution;
50 parts of 2, 4-diaminobenzene sodium sulfonate is added into the first mixed solution, the reaction temperature is controlled to be 40 ℃, the pH of a reaction system is 8.5, and the reaction is continued to be 0.5 h, so that the in-situ dyeing type bio-based tanning agent is obtained.
Example 13
Taking 60 parts of xylose and 40 parts of dextrin, fully dissolving in water, adding 10 parts of 3-glycidoxypropyl diethoxysilane, 10 parts of 3-glycidoxypropyl trimethoxysilane and 120 parts of sodium periodate in a stirring state, controlling the reaction temperature to be 10 ℃, reacting 10 h, and filtering and separating to obtain a first mixed solution;
adding 20 parts of sodium bromamine acid and 20 parts of sodium sulfanilate into the first mixed solution, controlling the reaction temperature to be 50 ℃, controlling the pH of a reaction system to be 7.5, and continuing to react for 3 h to obtain a second mixed solution;
and slowly adding 20 parts of 3-glycidoxypropyl trimethoxy silane into the second mixed solution, regulating the reaction temperature to 70 ℃, and then reacting 2 h under 0.05 MPa to obtain the in-situ dyeing type bio-based tanning agent.
Example 14
Taking 80 parts of sucrose and 20 parts of sucralose, fully dissolving in water, adding 180 parts of sodium periodate under stirring, controlling the reaction temperature to be 5 ℃, reacting 10 and h, and filtering and separating to obtain a first mixed solution;
and adding 40 parts of sodium bromamine into the first mixed solution, controlling the reaction temperature to be 40 ℃, controlling the pH of a reaction system to be 8.0, and continuing to react for 2 h to obtain the in-situ dyeing type bio-based tanning agent.
Example 15
Taking 80 parts of sucralose and 20 parts of alpha-methyl glucoside, fully dissolving in water, adding 180 parts of sodium periodate under stirring, controlling the reaction temperature to be 5 ℃, reacting 12 and h, and filtering and separating to obtain the in-situ dyeing type bio-based tanning agent.
Example 16
Taking 60 parts of alpha-methyl glucoside and 40 parts of dextrin, fully dispersing in water, adding 20 parts of 3-glycidoxypropyl trimethoxy silane and 140 parts of sodium periodate in a stirring state, controlling the reaction temperature to be 10 ℃, reacting 10 h, and filtering and separating to obtain a first mixed solution;
adding 20 parts of sodium 2, 4-diaminobenzene sulfonate and 30 parts of sodium sulfanilate into the first mixed solution, controlling the reaction temperature to be 60 ℃, controlling the pH of a reaction system to be 7.5, and continuing to react for 4 h to obtain a second mixed solution;
and slowly adding 80 parts of 3-glycidoxypropyl trimethoxy silane 3-glycidoxypropyl dimethoxy silane into the second mixed solution, regulating the reaction temperature to 60 ℃, and then reacting for 4 h under 0.02 MPa to obtain the in-situ dyeing type bio-based tanning agent.
Comparative example 1
Taking 100 parts of sucrose, fully dissolving in water, adding 100 parts of sodium periodate under stirring, controlling the reaction temperature to be 10 ℃, reacting 6 and h, and filtering and separating to obtain the glycosylaldehyde tanning agent.
Application example 1
Taking the pickled sheep pelt, weighing, weighting by one time, taking the weight as a material standard, firstly adding 100% of water, 6% of sodium chloride and 4% of the bio-based organic tanning agent prepared in the embodiment 3 into a rotary drum, uniformly stirring, putting the pickled sheep pelt into the rotary drum, rotating at normal temperature for 4 h, extracting alkali until the pH value of bath solution is 8.5, rotating for 20 min, heating to 40 ℃, continuing rotating for 240 min, stopping the drum overnight, rotating for 30 min the next day, discharging the drum, and carrying out the bonding for 24 h to obtain tanned leather crust.
Taking the tanned leather crust after wringing and shaving, weighing and taking the tanned leather crust as a material standard, putting the tanned leather crust into a rotary drum, sequentially carrying out softening, neutralization, water washing, filling and fatliquoring according to the conventional process, and drying to obtain the crust leather.
Application example 2
Taking the pickled sheep pelt, weighing, weighting by one time, taking the weight as a material standard, firstly adding 100% of water, 6% of sodium chloride and 4% of the bio-based organic tanning agent prepared in the example 4 into a rotary drum, uniformly stirring, putting the pickled sheep pelt into the rotary drum, rotating at normal temperature for 4 h, extracting alkali until the pH value of bath solution is 8.5, rotating for 20 min, heating to 40 ℃, continuing rotating for 240 min, stopping the drum overnight, rotating for 30 min the next day, discharging the drum, and carrying out the bonding for 24 h to obtain tanned leather crust.
Taking the tanned leather crust after wringing and shaving, weighing and taking the tanned leather crust as a material standard, putting the tanned leather crust into a rotary drum, sequentially carrying out softening, neutralization, water washing, filling and fatliquoring according to the conventional process, and drying to obtain the crust leather.
Comparative example 1 was used
Taking the pickled sheep pelt, weighing, weighting by one time, taking the weight as a material standard, firstly adding 100% of water, 6% of sodium chloride and 4% of commercial TWT organic tanning agent into a rotary drum, uniformly rotating, putting the pickled sheep pelt into the rotary drum, rotating at normal temperature by 4 h, then extracting alkali until the pH value of bath liquid is 8.5, rotating for 20 min, heating to 40 ℃, continuing to rotate for 240 min, stopping the drum overnight, rotating for 30 min the next day, discharging the drum, and carrying out the bridge 24 h to obtain tanned leather crust with the color of off-white.
Taking a tanned leather crust after wringing and shaving, weighing and taking the tanned leather crust as a material standard, putting the tanned leather crust into a rotary drum, sequentially carrying out softening, neutralization, water washing, filling, dyeing and fatliquoring according to a conventional process, and drying to obtain crust leather; the dye used in dyeing is commercial acid leather brown dye.
Comparative example 2 was used
Taking the pickled sheep pelt, weighing, weighting by one time, taking the weight as a material standard, firstly adding 100% of water, 6% of sodium chloride and 4% of commercial organic phosphine salt tanning agent into a rotary drum, uniformly rotating, putting the pickled sheep pelt into the rotary drum, rotating at normal temperature for 4 h, then extracting alkali until the pH of bath liquid is 6.5, rotating for 20 min, heating to 40 ℃, continuing to rotate for 120 min, stopping the drum overnight, adding 0.6% of sodium perborate the next day, rotating for 60 min at normal temperature, controlling water, washing with running water for 10 min, discharging the drum, and carrying out bonding for 24 h, thereby obtaining tanned leather crust with white color.
Taking a tanned leather crust after wringing and shaving, weighing and taking the tanned leather crust as a material standard, putting the tanned leather crust into a rotary drum, sequentially carrying out softening, neutralization, water washing, filling, dyeing and fatliquoring according to a conventional process, and drying to obtain crust leather; the dye used in dyeing is commercial small molecule reactive orange dye.
Comparative example 3 was used
Taking the pickled sheep pelt, weighing, weighting by one time, taking the weight as a material standard, firstly adding 100% of water, 6% of sodium chloride and 4% of glycosyl aldehyde tanning agent prepared in comparative example 1 into a rotary drum, uniformly rotating, putting the pickled sheep pelt into the rotary drum, rotating at normal temperature for 4 h, then extracting alkali until the pH of bath solution is 6.5, rotating for 20 min, heating to 40 ℃, continuing rotating for 120 min, stopping the drum for the next day, adding 0.6% of sodium perborate and rotating for 60 min at normal temperature, controlling water, washing with running water for 10 min, discharging the drum, and carrying out bridge 24 h to obtain tanned leather crust with the color of off-white.
Taking a tanned leather crust after wringing and shaving, weighing and taking the tanned leather crust as a material standard, putting the tanned leather crust into a rotary drum, sequentially carrying out softening, neutralization, water washing, filling, dyeing and fatliquoring according to a conventional process, and drying to obtain crust leather; the dye used in dyeing is commercial acid leather brown dye.
Experimental example
Shrinkage temperature detection and color evaluation were performed on the tanned leather crust completed in application examples 1 to 2 and application comparative examples 1 to 3, and after wet finishing and dry finishing, free formaldehyde content and color fastness were detected for all tanned leather crust, and the results are shown in table 1.
TABLE 1
。
As can be seen from table 1, the in-situ dyeing type bio-based tanning agent provided in examples 1 to 2 was used to tan the leather crust having both high wet heat stability and high color fastness, compared to the tanning leather crust provided in comparative examples 1 to 3; compared with the leather crust provided by the application comparative examples 1-2, the leather crust provided by the application examples 1-2 does not contain free formaldehyde, which shows that the bio-based organic tanning agent provided by the embodiment of the invention has good tanning performance, dyeing performance and ecological environmental protection.
For application of comparative example 1, the tanning agent used is a commercial organic tanning agent, and the synthetic raw material contains formaldehyde, so that a certain amount of free formaldehyde remains in the tanning agent product and in the tanning crust, and the health and environmental protection performance of the leather product are affected. In addition, the tanning agent tanned leather is off-white, and dyeing is needed when color leather is produced. However, the binding force between tanning crust and dye molecules is mainly Van der Waals force and physical deposition, so that the tanning crust and dye molecules have poor dry and wet rubbing resistance and other properties.
For application of comparative example 2, the tanning agent used is an organic phosphine salt tanning agent, one of the synthetic raw materials is formaldehyde, and the molecular structure of the tanning agent contains four active hydroxymethyl groups, so that the tanning agent can be well combined with collagen fibers. Although the bond between the organophosphonium salt and the collagen fibers is stable, when the pH of the tanning bath is higher than 4.0, the organophosphonium salt tanning agent is decomposed to generate free formaldehyde, resulting in overproof free formaldehyde content of the tannage and continuous release of free formaldehyde during storage. When the small molecular dye is used for dyeing, the obtained leather product has low color fastness and is easy to migrate. For application of comparative example 3, the tanning agent used is glycosyl aldehyde tanning agent which can be well combined with collagen fibers, but the isoelectric point of tanned leather is lower than 5.0, and when commercial acid dye is used for dyeing, the obtained leather product has low color fastness and color is easy to migrate.
Compared with the in-situ dyeing type bio-based tanning agent, the molecular structure of the in-situ dyeing type bio-based tanning agent provided by the invention contains abundant active groups, and the in-situ dyeing type bio-based tanning agent can be subjected to crosslinking reaction with amino groups on collagen fibers to form a multi-point covalent crosslinking structure, so that the in-situ dyeing type bio-based tanning agent can show excellent tanning performance; meanwhile, the tanning agent does not contain an active hydroxymethyl structure capable of releasing free formaldehyde, so that the tanned leather product does not contain free formaldehyde. When the tanning agent and the collagen fiber are used for tanning, a conjugate Schiff base structure is formed in situ between the tanning agent molecule and the collagen fiber, and the specific color of the tanned leather is endowed by means of the auxiliary color development effect of the conjugate structure and the substituent group, so that the leather is dyed in situ, and the in situ color development structure belongs to a covalent crosslinking structure, so that the stability is high, and the high color fastness of the leather is ensured.
Therefore, compared with the traditional organic tanning agent, the in-situ dyeing type bio-based tanning agent obtained by adopting the raw materials and the preparation method of the embodiment of the invention not only can endow tanning blanks with high wet and heat stability and high color fastness, but also can endow the tanning blanks with good health and environmental protection, and can effectively and cooperatively solve the problems of chromium pollution, formaldehyde release, poor dye absorption combination and the like existing in the tanning industry at present. Meanwhile, the tanning agent can realize the reduction of tanning procedures and materials, and has remarkable social and economic benefits.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. An in-situ dyeing type bio-based tanning agent is characterized by comprising the following raw materials in parts by weight:
100 parts of biomass raw material, 100-240 parts of activating agent, and more than 0 and less than or equal to 50 parts of auxiliary color agent;
the activator comprises any one or more of an hydroformylation agent, and any one or more of an epoxy compound;
the epoxy compound is selected from 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl triethoxy silane and 3-glycidoxypropyl methyl diethoxy silane;
the color-assisting agent comprises any one or more of cyanuric chloride, sodium sulfanilate, sodium 2, 4-diaminobenzenesulfonate, sodium bromamine acid and 1-amino-2-naphthol-4-sulfonic acid;
the biomass raw material is a saccharide substance and comprises any one or more of monosaccharide, disaccharide, oligosaccharide and derivatives thereof, polysaccharide and degradation products thereof;
the hydroformylation agent is periodate.
2. The in situ dyeing bio-based tanning agent of claim 1, wherein said monosaccharides, disaccharides, oligosaccharides comprise glucose, fructose, sucrose, xylose.
3. The in situ dyeing bio-based tanning agent of claim 1, wherein said polysaccharide comprises starch, sodium carboxymethyl cellulose, sodium alginate.
4. A process for preparing an in situ dyeing biobased tanning agent according to any of claims 1 to 3, comprising the steps of:
and mixing the biomass raw material with an activating agent, and reacting for 2-12 hours at the temperature of 5-15 ℃ to complete the first reaction.
5. The method of in situ dyeing bio-based tanning agent of claim 4, further comprising adding a color assisting agent after said first reaction, and reacting at a pH of 6.5-8.5 and a temperature of 30-60 ℃ for 0.5-4 hours.
6. The method of in situ dyeing bio-based tanning agent of claim 5, further comprising adding an epoxy compound after said second reaction, and reacting at 30-80 ℃ for 1-4 hours under 0.01-0.1 MPa.
7. An in situ dyeing bio-based tanning agent prepared by the method of any one of claims 4 to 6.
8. Use of an in situ dyeing bio-based tanning agent according to any one of claims 1 to 3, 7 in the tanning of leather.
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