CN115197476A - 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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- C14—SKINS; HIDES; PELTS; LEATHER
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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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- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
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Abstract
The invention belongs to the technical field of leather making materials, and discloses a preparation method of a 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 to 100 parts of epoxy compound, 20 to 100 parts of amino polymer and 0 to 50 parts of functional auxiliary agent; the bio-based aerogel provided by the invention can be used for leather finishing, and endows a leather coating with excellent heat insulation performance, waterproof performance and flame retardant performance.
Description
Technical Field
The invention relates to the technical field of leather making materials, in particular to a bio-based aerogel and a preparation method and application thereof.
Background
The leather industry plays an important role in the light industry manufacturing industry of China, the first global production scale of the leather industry is the pillar industry of the light industry, the leather industry makes a great contribution to earning foreign exchange, employment and economic development of China, and the leather industry is an important industry related to the national civilization. With the improvement of the living standard of people in China, the demand of people on meat is continuously increased, but if the animal skin as a byproduct is not reasonably utilized, the ecological environment in China can be seriously damaged. In recent years, people have a reduced consumption enthusiasm for traditional leather products, and great impact is brought to the whole leather industry, and the traditional leather products need functionality to improve the consumption value thereof, so that transformation and upgrading as well as sustainable development of the traditional leather industry are promoted.
The processing of functional leather materials by using animal skins is an ideal way for solving the problems. The functional leather mainly refers to products with other special functions beyond the functions of keeping warm, covering and beautifying the conventional leather, such as common antibacterial, mildew-proof, odor-resistant, waterproof, oil-proof, antifouling, flame-retardant and the like. The types of functional leather products are 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 at home and abroad is developing to a functional high-end market, particularly in the aspects of shoes, clothes, furniture and automobiles. However, most of the functional leathers have single functional characteristics, and if they have multiple functions, they need to use multiple functional materials. Therefore, the development of new multifunctional leather materials and their application techniques is one of the important directions in the current and future leather fields.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
In order to solve the problems that the functional characteristics of the current functional leather are single and the manufacturing of multifunctional leather is complex, the invention provides the bio-based aerogel and the preparation method and the application thereof.
In order to achieve the above object, the first technical solution provided by the present invention is:
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 material is a polysaccharide substance, 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-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and gamma-aminopropyltriethoxysilane.
Further, the amino polymer includes, but is not limited to, collagen and its degradation products, chitosan, and polyethyleneimine.
Further, the functional auxiliary agent is bio-based aldehyde and polyhydroxy phosphate.
Further, the biobased aldehydes include dialdehyde polysaccharide, dialdehyde oligosaccharide and dialdehyde small molecular sugar.
The second technical scheme adopted by the invention is as follows:
a method for preparing a bio-based aerogel is characterized in that a hydroxyl group and an amino group of a biomass raw material are subjected to a grafting reaction with a methoxy group or an ethoxy group or an epoxy group of an epoxy compound, an amino polymer and a functional assistant are introduced simultaneously, the type and the amount of the functional assistant are adjusted according to the type and the molecular structure characteristics of the biomass raw material, the epoxy compound and the amino polymer, and effective chemical bonding among the biomass raw material, the epoxy compound and the functional assistant is realized and a stable three-dimensional cross-linked network is constructed by utilizing covalent cross-linking reactions among the methoxy group or the ethoxy group, the hydroxyl group, the epoxy group, the amino group and an aldehyde group and the amino group, so that a stable micro-nano pore structure of the final bio-based aerogel is endowed with 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 assistant, adding water at normal temperature to 60 ℃, adjusting the pH of the system to 6.5-8.0, and reacting for 1-4 h to obtain sol;
rapidly freezing at-80 ℃ to-20 ℃ for 48 to 72 hours 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 bio-based aerogel in leather processing.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, by controlling the molecular structure and molecular weight of the biomass raw material and introducing the functional assistant, a stable micro-nano pore structure can be endowed to the bio-based aerogel, and a guarantee is provided for the excellent heat insulation and flame retardant performance of the bio-based aerogel.
(2) When the bio-based aerogel provided by the invention is used for leather coating, the leather can be endowed with excellent heat insulation and flame retardant properties, a micro-nano composite structure can be formed on the surface of the leather, and the leather is endowed with excellent hydrophobicity by utilizing the characteristic of low surface energy of aerogel particles subjected to hydrophobization treatment.
(3) The bio-based aerogel provided by the invention has good social and economic benefits because the bio-based aerogel provided by the invention is prepared by using renewable biomass raw materials with wide sources.
Drawings
FIG. 1 shows, from left to right, the thermal conductivity, limiting oxygen index and surface water drop penetration (1 min) of an unpainted crust leather, the thermal conductivity, limiting oxygen index and surface water drop penetration (1 min) of a three-proofing finish-coated crust leather and the thermal conductivity, limiting oxygen index and surface water drop penetration (1 min) of a bio-based aerogel-coated crust leather.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It is to be understood that these descriptions are only illustrative and are not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
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 current functional leathers have a problem of single functionality. In view of the above, based on the intensive research of the applicant on the structural characteristics of the biomass for many years, the first embodiment of the present invention is proposed, that is, the preparation of the bio-based aerogel with various functional characteristics is realized by using the biomass as the raw material, utilizing the abundant characteristic groups of hydroxyl, amino, and active methoxy or ethoxy groups of epoxy compounds, and assisting the regulation and control of the types and the dosage of the functional additives, based on the covalent crosslinking reaction between the methoxy or ethoxy groups and the hydroxyl, epoxy groups and the amino, and aldehyde groups and the amino groups, and the bio-based aerogel is further applied to leather processing, and meanwhile, the leather is endowed with excellent heat insulation, hydrophobicity and flame retardant properties.
The biomass material is a polysaccharide material, 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-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and gamma-aminopropyltriethoxysilane.
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 adjuvants are biobased aldehydes and polyhydroxy phosphates. As a further preferred embodiment, the biobased aldehyde comprises dialdehyde polysaccharide, dialdehyde oligosaccharide and dialdehyde small molecular sugar.
The second embodiment of the invention provides a preparation method of a bio-based organic tanning agent, which comprises the steps of carrying out graft reaction on hydroxyl and amino of a biomass raw material and methoxy or ethoxy or epoxy of an epoxy compound, simultaneously introducing an amino polymer and a functional assistant, adjusting the type and the dosage of the functional assistant according to the types of the biomass raw material, the epoxy compound and the amino polymer, and realizing effective chemical bonding among the biomass raw material, the epoxy compound and the functional assistant by utilizing covalent crosslinking reaction among the methoxy or ethoxy and the hydroxyl, the epoxy and the amino and covalent crosslinking reaction among aldehyde and the amino.
The second embodiment of the invention is based on fully understanding the structural characteristics of biomass raw materials, through the targeted design of a synthetic route and the optimization of synthetic conditions, renewable biomass is used as a raw material, and through the effective chemical bonding with an epoxy compound, an amino polymer and a functional assistant, the multifunctional bio-based aerogel is prepared and applied to leather processing, and the problem that the existing functional leather has single functionality is solved.
In some embodiments, the specific method of preparation of the bio-based 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 the system to 6.5-8.0, reacting for 1-4 h to obtain sol, and quickly freezing at-80 ℃ to-20 ℃; and (3) after freezing for 48 to 72 hours, carrying out aging crosslinking on the product obtained by freeze-drying at 80 to 120 ℃ for 30 to 60min to finally obtain the bio-based aerogel.
The third embodiment of the invention provides an application of a bio-based organic tanning agent in tanning leather blanks, namely crushing the bio-based aerogel of the first embodiment, then soaking the crushed bio-based aerogel in a hydrophobic finishing agent, and preparing the crushed bio-based aerogel into homogeneous emulsion by a high-speed shearing mode; and then, uniformly coating the bio-based aerogel coating liquid on the crust leather in a spraying, brushing, roll coating and other modes, and constructing a bio-based aerogel leather coating by combining a conventional coating process to endow the crust leather with excellent heat insulation, hydrophobicity and flame retardant properties.
In order to better understand the technical solutions provided by the present invention, the following specific examples are provided to respectively illustrate the bio-based aerogel, the preparation method, and the performance test, which are provided by applying the above embodiments of the present invention.
It is further worth mentioning that:
1) In the following examples and comparative examples, "parts" means "parts by weight";
2) The thermal conductivity of the crust leather in the following application examples and application comparative examples was measured using a thermal constant analyzer;
3) The hydrophobicity of crust leather is evaluated by measuring the change of the static contact angle of a water drop on the leather surface at different times;
4) The flame retardant property of the crust leather is evaluated by measuring the limit oxygen index of the leather blank by a plastic combustion property test standard (GB/T2406-1993).
Example 1
Preparation of the bio-based aerogel:
firstly, 100 parts of cellulose, 100 parts of 3-glycidoxypropyltrimethoxysilane, 100 parts of polyethyleneimine, 40 parts of dialdehyde cyclodextrin and 10 parts of 4-hydroxyphenyl sodium phosphate are uniformly mixed, water is added at normal temperature, then the pH value of a system is adjusted to be 8.0, sol is obtained after reaction for 1 hour, and the sol is frozen at minus 80 ℃; and after freezing for 48 hours, aging and crosslinking the product obtained by freeze-drying at 120 ℃ for 30min to finally obtain the bio-based aerogel.
Example 2
Preparation of the bio-based aerogel:
firstly, uniformly mixing 100 parts of sodium alginate, 80 parts of 3-glycidyl ether oxypropyltriethoxysilane, 50 parts of chitosan and 20 parts of 4-hydroxyphenyl sodium phosphate, adding water at 60 ℃, then adjusting the pH of a system to 7.0, reacting for 2 hours to obtain sol, and quickly freezing at-60 ℃; and after freezing for 60 hours, aging and crosslinking the product obtained by freeze-drying at 100 ℃ for 45min to finally obtain the bio-based aerogel.
Example 3
Preparation of the bio-based aerogel:
firstly, uniformly mixing 100 parts of xanthan gum, 60 parts of 3-glycidyl ether oxypropyldimethoxysilane, 40 parts of gelatin and 20 parts of dialdehyde cellulose, adding water at 40 ℃, then adjusting the pH of the system to 8.0, reacting for 3 hours to obtain sol, and quickly freezing at-40 ℃; and after freezing for 48 hours, aging and crosslinking the product obtained by freeze-drying at 80 ℃ for 60min to finally obtain the bio-based aerogel.
Example 4
Preparation of the bio-based aerogel:
firstly, 100 parts of chitosan, 40 parts of 3-glycidyl ether oxypropyldimethoxysilane, 20 parts of 3-glycidyl ether oxypropyldiethoxysilane, 20 parts of collagen and 10 parts of dialdehyde alpha-methyl glucoside are uniformly mixed, water is added at 50 ℃, then the pH of the system is adjusted to 8.0, sol is obtained after reaction for 2 hours, and the sol is rapidly frozen at the temperature of minus 20 ℃; after freezing for 72h, aging and crosslinking the product obtained by freeze-drying at 100 ℃ for 30min to finally obtain the bio-based aerogel.
Example 5
Preparation of the bio-based aerogel:
firstly, 100 parts of starch, 20 parts of 3-glycidyl ether oxypropyltrimethoxysilane, 20 parts of polyethyleneimine and 10 parts of 4-hydroxyphenyl sodium phosphate are uniformly mixed, water is added at 60 ℃, then the pH value of a system is adjusted to be 6.5, sol is obtained after reaction for 1 hour, and the sol is quickly frozen at minus 80 ℃; and after freezing for 48 hours, aging and crosslinking the product obtained by freeze-drying at 120 ℃ for 45min to finally obtain the bio-based aerogel.
Example 6
Preparation of the bio-based aerogel:
firstly, 100 parts of sodium carboxymethylcellulose, 100 parts of gamma-aminopropyltriethoxysilane, 80 parts of chitosan, 30 parts of dialdehyde cellulose and 20 parts of 4-hydroxyphenyl sodium phosphate are uniformly mixed, water is added at normal temperature, then the pH value of a system is adjusted to 6.5, sol is obtained after reaction for 3 hours, and the sol is quickly frozen at the temperature of 60 ℃ below zero; and after freezing for 60 hours, aging and crosslinking the product obtained by freeze-drying at 100 ℃ for 60min to finally obtain the bio-based aerogel.
Example 7
Preparation of the bio-based aerogel:
firstly, uniformly mixing 100 parts of chitosan, 100 parts of gamma-aminopropyltriethoxysilane and 50 parts of dialdehyde cellulose, adding water at 60 ℃, then adjusting the pH of a system to 7.5, reacting for 4 hours to obtain sol, and quickly freezing at-80 ℃; and after freezing for 48 hours, aging and crosslinking the product obtained by freeze-drying at 80 ℃ for 60min to finally obtain the bio-based aerogel.
Example 8
Preparation of the bio-based aerogel:
firstly, uniformly mixing 50 parts of cellulose, 50 parts of chitosan, 100 parts of 3-glycidoxypropyltrimethoxysilane, 30 parts of dialdehyde cyclodextrin and 10 parts of 4-hydroxyphenyl sodium phosphate, adding water at 40 ℃, then adjusting the pH of the system to 8.0, reacting for 2 hours to obtain sol, and quickly freezing at-60 ℃; after freezing for 72 hours, aging and crosslinking the product obtained by freeze-drying at 120 ℃ for 30min to finally obtain the bio-based aerogel.
Example 9
Preparation of the bio-based aerogel:
firstly, uniformly mixing 100 parts of cellulose, 100 parts of 3-glycidyl ether oxypropyltrimethoxysilane and 50 parts of collagen, adding water at normal temperature, then adjusting the pH of the system to 8.0, reacting for 2 hours to obtain sol, and quickly freezing at-80 ℃; after freezing for 72h, aging and crosslinking the product obtained by freeze-drying at 100 ℃ for 45min to finally obtain the bio-based aerogel.
Example 10
Preparation of the bio-based aerogel:
firstly, uniformly mixing 100 parts of cellulose, 100 parts of 3-glycidyl ether oxypropyltriethoxysilane, 50 parts of polyethyleneimine and 50 parts of gelatin, adding water at normal temperature, then adjusting the pH of a system to 7.0, reacting for 4 hours to obtain sol, and quickly freezing at-60 ℃; after freezing for 72 hours, aging and crosslinking the product obtained by freeze-drying at 120 ℃ for 30min to finally obtain the bio-based aerogel.
The following application examples adopt bio-based aldehyde tanned crust leather as an application object.
Application example
Weighing 0.5 g of the bio-based aerogel prepared in example 1 with excellent performance, crushing the bio-based aerogel, soaking the crushed bio-based aerogel into 250 mL of three-proofing finishing agent, and stirring at a high speed and shearing to prepare homogeneous bio-based aerogel coating emulsion. The method comprises the steps of taking bio-based aldehyde tanned crust leather with the size of about 30 cm multiplied by 30 cm, spraying the bio-based aldehyde tanned crust leather with the prepared bio-based aerogel coating emulsion for the first time, drying the leather in the air, spraying the leather once again, and then constructing the bio-based aerogel leather coating by combining a conventional coating process.
Comparative application
250 mL of the three-proofing finishing agent is stirred at a high speed and sheared to prepare homogeneous coating emulsion. Taking bio-based aldehyde tanned crust leather with the size of about 30 cm multiplied by 30 cm, spraying the bio-based aldehyde tanned crust leather with the prepared finishing emulsion for the first time, drying the leather in the air, then spraying the leather once again, and then constructing the bio-based aerogel leather coating by combining the conventional finishing process.
The thermal conductivity, limiting oxygen index and surface water drop penetration (penetration time 1 min) of the uncoated crust leather, the crust leather coated with the bio-based aerogel in application example 1 and the crust leather coated with the three-proofing finishing agent in application comparative example were respectively tested, and the specific results are shown in fig. 1.
The shrinkage temperature, whiteness (Δ E), free formaldehyde content and storage resistance of the tanned leather blanks in the corresponding examples and application comparative examples were tested and compared, and the results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the finished leather provided in the examples of application combines lower thermal conductivity, higher static contact angle and limiting oxygen index than the finished leather provided in the comparative examples of application, i.e., it is shown that the bio-based aerogel of the examples of the present invention, when used in leather finishing, can simultaneously impart good thermal insulation, hydrophobicity and flame retardancy to the finished leather.
The application comparison example is different from the application example in that the three-proofing finishing agent finishing emulsion used in the application comparison example is not added with aerogel materials, and a relatively hydrophobic film layer is mainly formed on the surface of the crust leather during coating construction, so that the surface energy of the crust leather is reduced to a certain extent. The three-proofing finishing agent coating emulsion added with the bio-based aerogel provided by the invention is used in an application example, and the used aerogel has a stable micro-nano pore channel structure and good heat insulation, so that when the coating emulsion is used for leather coating, a layer of coarse micro-nano composite structure can be formed on the surface of crust leather, and the characteristic of low surface energy of aerogel particles subjected to hydrophobization treatment is utilized, so that the crust leather is endowed with excellent hydrophobic property, and meanwhile, the heat conductivity coefficient of a coating is reduced by means of the three-dimensional micro-nano pore channel structure of the aerogel, and the heat insulation property of the coated crust leather is improved. In addition, the prepared bio-based aerogel not only has a micro-nano porous structure, but also contains flame retardant elements such as N and P, so that the flame retardant property of crust leather can be further improved by the aerogel coating.
In conclusion, when the bio-based aerogel obtained by adopting the raw materials and the preparation method of the embodiment of the invention is used for leather finishing, the excellent heat insulation performance and flame retardant performance can be endowed to a tanned leather blank, and the good hydrophobic performance can be simultaneously endowed.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The bio-based aerogel is characterized by comprising 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 additive.
2. The bio-based aerogel of claim 1, wherein said biomass material is a polysaccharide material including but not limited to cellulose, sodium alginate, xanthan gum, starch, chitosan and derivatives thereof.
3. The bio-based aerogel according to claim 1, wherein said epoxy compound is selected from any one or more of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and γ -aminopropyltriethoxysilane.
4. The bio-based aerogel of claim 1, wherein said amino polymers include but are not limited to collagen and its degradation products, chitosan and polyethyleneimine.
5. The bio-based aerogel of claim 1, wherein said functional adjuvants are bio-based aldehydes and polyhydroxy phosphates.
6. The bio-based aerogel of claim 5, wherein said bio-based aldehydes comprise dialdehyde polysaccharides, dialdehyde oligosaccharides, and dialdehyde small molecule sugars.
7. A method for preparing the bio-based aerogel according to any one of claims 1 to 6, which comprises the following steps:
uniformly mixing a biomass raw material, an epoxy compound, an amino polymer and a functional assistant, adding water at normal temperature to 60 ℃, then adjusting the pH of the system to 6.5-8.0, and reacting for 1-4 h to obtain sol;
rapidly freezing at-80 ℃ to-20 ℃ for 48 to 72 hours 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.
8. A bio-based aerogel produced by the method of claim 7.
9. Use of the bio-based aerogel according to any of claims 1 to 6 and 8 in leather processing.
10. The application of claim 9, wherein the method of applying comprises:
crushing the bio-based aerogel, and then soaking the crushed bio-based aerogel into a hydrophobic finishing agent to prepare homogeneous emulsion;
the bio-based aerogel finishing liquid is uniformly coated on crust leather in the modes of spraying, brushing and roller coating.
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