CN115197476B - Bio-based aerogel and preparation method and application thereof - Google Patents
Bio-based aerogel and preparation method and application thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
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- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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- C08J2401/04—Oxycellulose; Hydrocellulose
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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Abstract
The invention belongs to the technical field of leather making materials, and discloses a preparation method of bio-based aerogel and an application method of the bio-based aerogel in leather processing. The bio-based aerogel raw material comprises 100 parts of biomass raw material, 20-100 parts of epoxy compound, 20-100 parts of amino polymer and 0-50 parts of functional auxiliary agent; the bio-based aerogel provided by the invention can be used for coating leather, and endows the leather coating with excellent heat insulation performance, waterproof performance and flame retardant performance.
Description
Technical Field
The invention relates to the technical field of tanning materials, in particular to a biological base aerogel and a preparation method and application thereof.
Background
The leather industry plays a very important role in the light industry manufacturing industry in China, and the production scale is the first global, is the pillar industry of the light industry, makes great contribution to foreign exchange, employment and economic development in China, and is an important industry related to national folk life. Along with the improvement of the living standard of people in China, the demand of people for meat is continuously increased, but animal skins as byproducts are seriously damaged to the ecological environment in China if the animal skins are not reasonably utilized. In recent years, people have reduced consumption enthusiasm of traditional leather products, and have brought great impact to the whole leather industry, and the traditional leather products need functionality to improve the consumption value, so as to promote transformation and upgrading of the traditional leather industry and sustainable development of the traditional leather industry.
The processing of functional leather materials using animal skins is an ideal approach to solving the above problems. The functional leather mainly refers to products with other special functions beyond the functions of warm keeping, covering and beautifying of the conventional leather, such as common antibacterial, mildew-proof, deodorant, waterproof, oil-proof, antifouling, flame-retardant and the like. The variety of functional leather products is continuously increased, the quality is steadily improved, and the application field is expanded to various fields such as civil use, military use and the like. At present, leather is developing to functional high-end markets at home and abroad, especially in the aspects of shoes, clothing, furniture and automobiles. However, the functional characteristics of the functional leather are mostly single, and if multiple functions are required, multiple functional materials are required. Therefore, the development of novel multifunctional leather materials and application technology thereof is one of the important directions in the current and future leather fields.
In view of this, the present invention has been made.
Disclosure of Invention
In order to solve the problems that the functional characteristics of the current functional leather are single and the multifunctional leather is complex to manufacture, the invention provides the bio-based aerogel, and the preparation method and the application thereof.
In order to achieve the above purpose, the first technical scheme provided by the invention is as follows:
a bio-based aerogel comprises the following raw materials in parts by weight:
100 parts of biomass raw material, 20-100 parts of epoxy compound, 20-100 parts of amino polymer and 0-50 parts of functional auxiliary agent.
Further, the biomass raw material is polysaccharide substances including, but not limited to, cellulose, sodium alginate, xanthan gum, starch, chitosan and derivatives thereof.
Further, the epoxy compound is selected from any one or more of 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl triethoxy silane, 3-glycidoxypropyl methyl diethoxy silane and gamma-aminopropyl triethoxy silane.
Further, the amino polymers include, but are not limited to, collagen and its degradation products, chitosan, and polyethyleneimine.
Further, the functional auxiliary agents are bio-based aldehydes and polyhydroxy phosphates.
Further, the bio-based aldehydes include dialdehyde polysaccharides, dialdehyde oligosaccharides and dialdehyde small molecule sugars.
The second technical scheme adopted by the invention is as follows:
a method for preparing bio-based aerogel, namely the preparation method of the first technical scheme, carries out grafting reaction on hydroxyl, amino and methoxy or ethoxy or epoxy of epoxy compound of biomass raw material, simultaneously introduces amino polymer and functional auxiliary agent, adjusts the type and the dosage of the functional auxiliary agent according to the type and molecular structure characteristics of the biomass raw material, epoxy compound and amino polymer, and utilizes covalent crosslinking reaction between methoxy or ethoxy and hydroxyl, epoxy and amino as well as aldehyde and amino to realize effective chemical bonding among the biomass raw material, epoxy compound and functional auxiliary agent, thereby constructing a stable three-dimensional crosslinked network, and endowing the final bio-based aerogel with stable micro-nano pore channel structure, so that the final bio-based aerogel has good heat insulation, hydrophobicity and flame retardance.
Further, the specific method for preparing the bio-based aerogel comprises the following steps:
uniformly mixing a biomass raw material, an epoxy compound, an amino polymer and a functional auxiliary agent, adding water at normal temperature to 60 ℃, then adjusting the pH of a system to 6.5 to 8.0, and reacting for 1-4 hours to obtain sol;
rapidly freezing at-80 ℃ to-20 ℃ for 48-72 h to obtain a freeze-dried product; and
and aging and crosslinking the freeze-dried product at 80-120 ℃ for 30-60 min to obtain the bio-based aerogel.
The third technical scheme adopted by the invention is as follows:
use of a biobased aerogel in leather processing.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention can endow the bio-based aerogel with a firm micro-nano pore canal structure by controlling the molecular structure and the molecular weight of the biomass raw material and introducing the functional auxiliary agent, and provides a guarantee for simultaneously playing good heat insulation and flame retardance.
(2) When the bio-based aerogel provided by the invention is used for leather finishing, not only can excellent heat insulation and flame retardance be given to leather, but also a layer of micro-nano composite structure can be formed on the surface of the leather, and meanwhile, excellent hydrophobicity is given to the leather by utilizing the characteristic of low surface energy of the aerogel particles subjected to hydrophobization treatment.
(3) The bio-based aerogel provided by the invention has good social and economic benefits due to the wide source and renewable biomass raw materials used in preparation.
Drawings
The thermal conductivity, limiting oxygen index and surface water drop penetration (1 min) of the unfinished crust leather, the thermal conductivity, limiting oxygen index and surface water drop penetration (1 min) of the three-proofing finishing agent coated crust leather and the thermal conductivity, limiting oxygen index and surface water drop penetration (1 min) of the bio-based aerogel coated crust leather are shown in the figure 1 from left to right.
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 a bio-based aerogel, which comprises the following raw materials in parts by weight:
100 parts of biomass raw material, 20-100 parts of epoxy compound, 20-100 parts of amino polymer and 0-50 parts of functional auxiliary agent.
As described in the background art, most of the existing functional leathers have a problem of relatively single functionality. In view of this, based on many years of intensive researches on structural characteristics of biomass by the applicant, a first embodiment of the present invention is proposed, namely, biomass is used as a raw material, and abundant characteristic groups of hydroxyl groups and amino groups, and active methoxy groups or ethoxy groups of epoxy compounds are utilized, and the regulation and control of types and amounts of functional auxiliary agents are assisted, so that the preparation of bio-based aerogel with various functional characteristics is realized based on covalent crosslinking reaction between methoxy groups or ethoxy groups and hydroxyl groups, epoxy groups and amino groups, and aldehyde groups and amino groups, and the bio-based aerogel is further applied to leather processing, and meanwhile, excellent heat insulation, hydrophobicity and flame retardance are endowed to leather.
It should be noted that the biomass raw material is polysaccharide substances, including but not limited to cellulose, sodium alginate, xanthan gum, starch, chitosan and derivatives thereof.
In some preferred embodiments, the epoxy compound is selected from any one or more of 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl triethoxy silane, 3-glycidoxypropyl methyl diethoxy silane, and gamma-aminopropyl triethoxy silane.
In some preferred embodiments, the amino polymer includes, but is not limited to, collagen and its degradation products, chitosan, and polyethyleneimine.
In some preferred embodiments, the functional auxiliary agents are biobased aldehydes and polyhydroxy phosphates. As a further preferred embodiment, the bio-based aldehydes include dialdehyde polysaccharides, dialdehyde oligosaccharides and dialdehyde small molecule sugars.
The second embodiment of the invention provides a preparation method of a bio-based organic tanning agent, which comprises the steps of carrying out grafting reaction on hydroxyl groups and amino groups of biomass raw materials and methoxy groups or ethoxy groups or epoxy groups of epoxy compounds, introducing amino polymers and functional auxiliary agents, adjusting the types and the dosage of the functional auxiliary agents according to the types of the biomass raw materials, the epoxy compounds and the amino polymers, and realizing effective chemical bonding among the biomass raw materials, the epoxy compounds and the functional auxiliary agents by utilizing covalent crosslinking reaction among the methoxy groups or ethoxy groups, the hydroxyl groups, the epoxy groups, the amino groups and the aldehyde groups and the amino groups.
According to the second embodiment of the invention, on the basis of fully understanding the structural characteristics of biomass raw materials, a synthesis route is designed and synthesis conditions are optimized in a targeted manner, renewable biomass is used as a raw material, and the multifunctional bio-based aerogel is prepared by effective chemical bonding with an epoxy compound, an amino polymer and a functional auxiliary agent and is applied to leather processing, so that the problem that the existing functional leather is single in functionality is solved.
In some embodiments, the specific method of preparing a biobased aerogel comprises: firstly, uniformly mixing a biomass raw material, an epoxy compound, an amino polymer and a functional auxiliary agent, adding water at normal temperature to 60 ℃, then adjusting the pH of a system to 6.5 to 8.0, reacting for 1-4 hours to obtain a sol, and rapidly freezing at-80 ℃ to-20 ℃; and (3) after freezing for 48-72 hours, aging and crosslinking the freeze-dried product at 80-120 ℃ for 30-60 minutes to finally obtain the bio-based aerogel.
The third embodiment of the invention provides an application of the bio-based organic tanning agent in tanning leather blank, namely, crushing the bio-based aerogel of the first embodiment, then soaking the crushed bio-based aerogel in a hydrophobic finishing agent, and preparing a homogeneous emulsion by a high-speed shearing mode; and then, uniformly coating the bio-based aerogel coating liquid on crust leather in a spraying, brushing, roller coating and other modes, and constructing a bio-based aerogel leather coating by combining a conventional coating process, so that the crust leather is endowed with excellent heat insulation, hydrophobicity and flame retardance.
In order to better understand the technical scheme provided by the invention, the following specific examples are used for respectively describing the bio-based aerogel, the preparation method and the performance test provided by the embodiment of the invention.
Also worth mentioning is:
1) In the following examples and comparative examples, "parts" refer to "parts by weight";
2) The thermal conductivity of crust leather in the following application examples and comparative examples was measured by a thermal constant analyzer;
3) The hydrophobicity of crust leather is evaluated by measuring the change of the static contact angle of water drops on the leather surface at different times;
4) The flame retardant property of crust leather is evaluated by measuring the limiting oxygen index of the crust leather by using a plastic combustion property test standard (GB/T2406-1993) method.
Example 1
Preparation of biobased aerogel:
firstly, 100 parts of cellulose, 100 parts of 3-glycidoxypropyl trimethoxy silane, 100 parts of polyethylenimine, 40 parts of dialdehyde cyclodextrin and 10 parts of sodium 4-hydroxyphenyl phosphate are uniformly mixed, water is added at normal temperature, then the pH value of the system is regulated to 8.0, sol is obtained after reaction of 1. 1 h, and freezing is carried out at the temperature of minus 80 ℃; after 48 and h are frozen, the freeze-dried product is aged and crosslinked for 30min at 120 ℃ to finally obtain the bio-based aerogel.
Example 2
Preparation of biobased aerogel:
firstly, 100 parts of sodium alginate, 80 parts of 3-glycidoxypropyl triethoxysilane, 50 parts of chitosan and 20 parts of 4-hydroxyphenyl sodium phosphate are uniformly mixed, water is added at 60 ℃, then the pH value of the system is regulated to 7.0, sol is obtained after reaction 2h, and freezing is carried out at minus 60 ℃; after 60h of freezing, aging and crosslinking the freeze-dried product for 45min at 100 ℃ to finally obtain the bio-based aerogel.
Example 3
Preparation of biobased aerogel:
firstly, 100 parts of xanthan gum, 60 parts of 3-glycidoxypropyl dimethoxy silane, 40 parts of gelatin and 20 parts of dialdehyde cellulose are uniformly mixed, water is added at 40 ℃, then the pH value of the system is regulated to 8.0, sol is obtained after reaction 3 h, and freezing is carried out at minus 40 ℃; after freezing for 48 hours, aging and crosslinking the freeze-dried product for 60 minutes at 80 ℃ to finally obtain the bio-based aerogel.
Example 4
Preparation of biobased aerogel:
firstly, uniformly mixing 100 parts of chitosan, 40 parts of 3-glycidoxypropyl dimethoxy silane, 20 parts of 3-glycidoxypropyl diethoxy silane, 20 parts of collagen and 10 parts of dialdehyde alpha-methyl glucoside, adding water at 50 ℃, then adjusting the pH of a system to 8.0, reacting 2. 2h to obtain sol, and rapidly freezing at-20 ℃; after freezing for 72 hours, aging and crosslinking the freeze-dried product for 30 minutes at 100 ℃ to finally obtain the bio-based aerogel.
Example 5
Preparation of biobased aerogel:
firstly, 100 parts of starch, 20 parts of 3-glycidoxypropyl trimethoxy silane, 20 parts of polyethyleneimine and 10 parts of 4-hydroxyphenyl sodium phosphate are uniformly mixed, water is added at 60 ℃, the pH of the system is regulated to 6.5, sol is obtained after reaction of 1. 1 h, and freezing is carried out at 80 ℃ below zero; after freezing for 48 hours, aging and crosslinking the freeze-dried product for 45 minutes at 120 ℃ to finally obtain the bio-based aerogel.
Example 6
Preparation of biobased aerogel:
firstly, uniformly mixing 100 parts of sodium carboxymethyl cellulose, 100 parts of gamma-aminopropyl triethoxysilane, 80 parts of chitosan, 30 parts of dialdehyde cellulose and 20 parts of sodium 4-hydroxyphenyl phosphate, adding water at normal temperature, then adjusting the pH of a system to 6.5, reacting 3. 3 h to obtain sol, and rapidly freezing at-60 ℃; after freezing for 60 hours, aging and crosslinking the freeze-dried product for 60 minutes at 100 ℃ to finally obtain the bio-based aerogel.
Example 7
Preparation of biobased aerogel:
firstly, uniformly mixing 100 parts of chitosan, 100 parts of gamma-aminopropyl triethoxysilane and 50 parts of dialdehyde cellulose, adding water at 60 ℃, then adjusting the pH of a system to 7.5, reacting 4. 4 h to obtain sol, and rapidly freezing at-80 ℃; after freezing for 48 hours, aging and crosslinking the freeze-dried product for 60 minutes at 80 ℃ to finally obtain the bio-based aerogel.
Example 8
Preparation of biobased aerogel:
firstly, uniformly mixing 50 parts of cellulose, 50 parts of chitosan, 100 parts of 3-glycidoxypropyl trimethoxy silane, 30 parts of dialdehyde cyclodextrin and 10 parts of sodium 4-hydroxyphenyl phosphate, adding water at 40 ℃, then adjusting the pH of a system to 8.0, reacting 2. 2h to obtain sol, and rapidly freezing at-60 ℃; after freezing for 72 hours, aging and crosslinking the freeze-dried product for 30 minutes at 120 ℃ to finally obtain the bio-based aerogel.
Example 9
Preparation of biobased aerogel:
firstly, 100 parts of cellulose, 100 parts of 3-glycidoxypropyl trimethoxy silane and 50 parts of collagen are uniformly mixed, water is added at normal temperature, then the pH value of the system is regulated to 8.0, sol is obtained after 2h reaction, and freezing is carried out at 80 ℃ below zero; after freezing for 72 hours, aging and crosslinking the freeze-dried product for 45 minutes at 100 ℃ to finally obtain the bio-based aerogel.
Example 10
Preparation of biobased aerogel:
firstly, 100 parts of cellulose, 100 parts of 3-glycidoxypropyl triethoxysilane, 50 parts of polyethyleneimine and 50 parts of gelatin are uniformly mixed, water is added at normal temperature, then the pH value of the system is regulated to 7.0, sol is obtained after reaction 4. 4 h, and freezing is carried out at minus 60 ℃; after freezing for 72 hours, aging and crosslinking the freeze-dried product for 30 minutes at 120 ℃ to finally obtain the bio-based aerogel.
The following application examples used bio-based aldehyde tannage as an application object.
Application example
The bio-based aerogel prepared in example 1 with excellent performance of 0.5 and g is weighed, crushed and then immersed in the 250 mL three-proofing finishing agent, and the homogeneous bio-based aerogel finishing emulsion is prepared by high-speed stirring and shearing. And (3) taking bio-based aldehyde tannage with the size of about 30 cm multiplied by 30 cm, spraying the bio-based aldehyde tannage for the first time by using the prepared bio-based aerogel coating emulsion, spraying the bio-based aldehyde tannage once again after airing, and then constructing the bio-based aerogel leather coating by combining a conventional coating process.
Comparative examples of application
The 250 mL three-proofing finishing agent is stirred and sheared at high speed to prepare the homogeneous coating emulsion. The bio-based aldehyde tannage leather with the size of about 30 cm multiplied by 30 cm is sprayed for the first time by using the prepared coating emulsion, is sprayed once again after being dried, and is then combined with a conventional coating process to construct the bio-based aerogel leather coating.
The thermal conductivity, limiting oxygen index and surface water drop permeation (permeation time 1 min) of the unfinished crust leather, the crust leather coated with the bio-based aerogel in application example 1 and the crust leather coated with the three-proofing agent in application comparative example were respectively examined, and the specific results are shown in fig. 1.
The shrinkage temperature, whiteness (fatly E), free formaldehyde content and storage resistance of the tanned leather crust in the application examples and the comparative examples were tested and compared, and the results are shown in Table 1:
TABLE 1
。
As can be seen from table 1, the coated crust leather provided in the application example has a lower thermal conductivity, a higher static contact angle and a limiting oxygen index compared with the coated crust leather provided in the application comparative example, that is, the bio-based aerogel of the embodiment of the invention can simultaneously provide good heat insulation, water repellency and flame retardance for the coated crust leather when used for leather coating.
The difference between the application comparative example and the application example is that the three-proofing finishing agent coating emulsion used in the comparative example is not added with aerogel materials, and when the coating is constructed, a relatively hydrophobic film layer is mainly formed on the surface of crust leather, so that the surface energy of the crust leather is reduced to a certain extent. The three-proofing finishing agent coating emulsion of the bio-based aerogel is used in application examples, and because the used aerogel has a stable micro-nano pore structure and good heat insulation, when the coating emulsion is used for coating leather, a layer of rough micro-nano composite structure can be formed on the surface of crust leather, and the characteristic of low surface energy of the aerogel particles subjected to hydrophobization treatment is utilized, so that the crust leather is endowed with excellent hydrophobic performance, and meanwhile, the heat conductivity coefficient of a coating is reduced by virtue of the three-dimensional micro-nano pore structure of the aerogel, so that the heat insulation performance of the coated crust leather is improved. In addition, the prepared bio-based aerogel has a micro-nano porous structure and also contains N, P and other flame retardant elements, so that the flame retardant property of crust leather can be further improved by the aerogel coating.
In summary, when the bio-based aerogel obtained by the raw materials and the preparation method of the embodiment of the invention is used for leather finishing, not only can the tanned leather crust be endowed with excellent heat insulation performance and flame retardant performance, but also good hydrophobic performance can be endowed.
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 (3)
1. The application of the bio-based aerogel in leather processing is characterized in that the bio-based aerogel comprises the following raw materials in parts by weight:
100 parts of biomass raw materials, 20-100 parts of epoxy compounds, 20-100 parts of amino polymers and 0-50 parts of functional auxiliary agents;
wherein the epoxy compound is selected from any one or more of 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl triethoxy silane, 3-glycidoxypropyl methyl diethoxy silane and gamma-aminopropyl triethoxy silane;
the functional auxiliary agents are bio-based aldehyde and polyhydroxy phosphate;
the bio-based aldehydes include dialdehyde polysaccharides and dialdehyde small molecule sugars;
the biomass raw material is polysaccharide substances selected from cellulose, sodium alginate, xanthan gum, starch, chitosan and derivatives thereof;
the amino polymer is selected from collagen and degradation products thereof, chitosan and polyethyleneimine;
the preparation method of the bio-based aerogel comprises the following steps:
uniformly mixing a biomass raw material, an epoxy compound, an amino polymer and a functional auxiliary agent, adding water at normal temperature to 60 ℃, then adjusting the pH of a system to 6.5 to 8.0, and reacting for 1-4 hours to obtain sol;
rapidly freezing at-80 ℃ to-20 ℃ for 48-72 h to obtain a freeze-dried product; and
and aging and crosslinking the freeze-dried product at 80-120 ℃ for 30-60 min to obtain the bio-based aerogel.
2. The use according to claim 1, wherein the dialdehyde-small-molecule sugar is selected from dialdehyde-oligosaccharides.
3. The application of claim 1, wherein the method of application comprises:
crushing the bio-based aerogel, and then soaking the crushed bio-based aerogel in a hydrophobic finishing agent to prepare a homogeneous emulsion;
the bio-based aerogel coating liquid is uniformly coated on crust leather in a spraying, brushing and roller coating mode.
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