CN111234298B - Method for preparing composite aerogel flame-retardant material by using waste leather - Google Patents

Method for preparing composite aerogel flame-retardant material by using waste leather Download PDF

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CN111234298B
CN111234298B CN202010047940.1A CN202010047940A CN111234298B CN 111234298 B CN111234298 B CN 111234298B CN 202010047940 A CN202010047940 A CN 202010047940A CN 111234298 B CN111234298 B CN 111234298B
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waste leather
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CN111234298A (en
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李怡俊
张桐瑞
袁斌
白时兵
王琪
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/048—Elimination of a frozen liquid phase
    • C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00—Characterised by the use of proteins; Derivatives thereof
    • C08J2389/04—Products derived from waste materials, e.g. horn, hoof or hair
    • C08J2389/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2489/00—Characterised by the use of proteins; Derivatives thereof
    • C08J2489/04—Products derived from waste materials, e.g. horn, hoof or hair
    • C08J2489/06—Products derived from waste materials, e.g. horn, hoof or hair derived from leather or skin

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
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Abstract

The invention provides a method for preparing a composite aerogel flame retardant material by utilizing waste leather. The invention introduces the waste leather as the main raw material of the aerogel flame retardant material for the first time, realizes the recycling of the waste leather, and has the characteristics of simple operation and lower cost, and the prepared composite aerogel flame retardant material has the limited oxygen index of 40 and better mechanical property.

Description

Method for preparing composite aerogel flame-retardant material by using waste leather
Technical Field
The invention belongs to the technical field of recovery and treatment of high polymer materials and waste leather, and particularly relates to a method for preparing a composite aerogel flame retardant material by using waste leather.
Background
Leather is an important natural resource in modern society, and is widely applied to the light industrial fields of furniture, clothes and the like. China is a big country for leather production, and the produced leather exceeds hundreds of millions of square meters every year, but a large amount of leather products not only can generate a large amount of waste leather scraps in the production process, but also can be discarded or recycled as solid wastes after being used for a certain period. However, the waste leather scraps and leather products are tanned, have no reprocessing performance, and are difficult to treat and recycle. At present, no ideal treatment and disposal method exists for a large amount of waste leather leftover materials and leather products, and landfill, incineration and chemical treatment methods are generally adopted. Among them, the incineration method generates toxic gases, which pose a great threat to the environment and human health. If the waste leather leftover materials and leather products can be reasonably recycled, the waste leather leftover materials and the leather products can be changed into valuables.
The aerogel consists of a rigid framework and internal holes, and is novel in structure and wide in application range. It has the features of high porosity, small density, great specific surface area, low heat conductivity, high sound absorbing and damping capacity, etc. In recent years, the research on aerogels has become more extensive, and the aerogels have potential beneficial application in many fields due to the excellent physicochemical properties. Although aerogels have many outstanding properties, their low strength, low modulus, and brittleness limit their further applications.
Moreover, the nano network of the aerogel can effectively limit the propagation of local thermal excitation, and the nano micropores effectively inhibit the contribution of gas molecules to the thermal conductivity, so that the solid thermal conductivity of the aerogel is 2 to 3 orders of magnitude lower than that of a corresponding glassy material. However, in the prior art, the preparation process of the aerogel is limited by the addition amount of the flame-retardant filler, so that the flame retardant property of the aerogel is limited, and the further application of the aerogel is limited.
Disclosure of Invention
The invention provides a method for preparing a composite aerogel flame-retardant material by using waste leather aiming at the problems in the background art, the method introduces the waste leather as the main raw material of the aerogel flame-retardant material for the first time, realizes the recycling of the waste leather, and has the characteristics of simple operation and low cost, the limit oxygen index of the prepared composite aerogel flame-retardant material can reach 40, and the composite aerogel flame-retardant material has better mechanical property.
In order to achieve the purpose, the invention adopts the technical scheme formed by the following technical measures.
A method for preparing a composite aerogel flame-retardant material by using waste leather comprises the following steps:
(1) preparing waste leather powder:
firstly, crushing waste leather into single waste leather fibers with the length of 100 nm-300 mu m, then adding the single waste leather fibers into a solid-phase mechanochemical reactor for grinding, introducing cooling circulating water in the grinding process, controlling the temperature of the disc surface of a grinding disc of the solid-phase mechanochemical reactor to be 15-30 ℃, controlling the pressure to be 3-15 KN and the rotating speed to be 100-300 r/min, and circularly grinding for 1-9 times to obtain waste leather powder;
(2) preparing a hydrogel:
according to the weight parts, 100 parts of polyhydroxy polymer which can be used as a raw material for preparing aerogel is dissolved in water, and then 15-200 parts of waste leather powder is mixed to prepare hydrogel;
(3) preparing aerogel:
and (3) preparing the hydrogel obtained in the step (2) into aerogel to obtain the composite aerogel flame-retardant material.
Wherein, the waste leather in the step (1) can be selected from waste leftover materials after leather tanning processing and recycled waste leather products.
The step (1) of pulverizing the waste leather into single waste leather fibers with the length of 100 nm-300 μm is to satisfy the subsequent grinding treatment of the solid-phase mechanochemical reactor, and generally a commercially available pulverizer or other equipment is adopted.
Wherein, the solid-phase mechanochemical reactor in the step (1) is a millstone type solid-phase mechanochemical reactor disclosed in a patent "mechanochemical reactor" (application No. 95111258.9) previously granted by the applicant of the present invention.
The polyhydroxy polymer which can be used as a raw material for preparing the aerogel in the step (2) is a raw material of the aerogel which is well known in the technical field, such as polyvinyl alcohol, cellulose and sodium alginate, and preferably polyvinyl alcohol. The preferable polyhydroxy polymer has water solubility, so that the waste leather powder has good dispersibility after being added, and the prepared aerogel is more uniform.
It is worth noting that the polyhydroxy polymer is dissolved in water to prepare the aqueous solution/hydrogel, so that the polyhydroxy polymer is uniformly dispersed and has proper viscosity, and the waste leather powder is fully dispersed in the aqueous solution/hydrogel after being added. In addition, when the polyhydroxy polymer is selected from polyvinyl alcohol and cellulose, the polyhydroxy polymer is dissolved in water to form an aqueous solution, and is added with the waste leather powder to form hydrogel; when the polyhydroxy polymer is selected to be sodium alginate, the polyhydroxy polymer is hydrogel after being dissolved in water and is still hydrogel after being added with the waste leather powder. One skilled in the art can distinguish the state of the aqueous hydrogel/solution of the polyhydroxypolymer dissolved in water in step (2) according to the choice of the actual polyhydroxypolymer.
Generally speaking, the waste leather powder in 15-200 parts is mixed in the step (2) to prepare hydrogel, and in order to fully disperse the waste leather powder in the aqueous solution/hydrogel, in order to better illustrate the present invention, a preferred technical scheme is provided, and mechanical stirring and mixing are preferred, and the stirring process parameters are as follows: the stirring speed is 30-100 r/min, and the stirring is carried out for 0.5-2 h.
Wherein, the aerogel prepared in step (3) is usually prepared by the prior art aerogel preparation methods, such as freeze drying method, solution gel method (Bai H, Li C, Wang X, et al.a pH-sensitive graphene oxide hydrogel [ J]Chemical Communications, 2010 (46): 2376) hydrothermal method (Xu Y, Sheng K, Li C, et al. self-assembled graphene hydrogel via a one-step hydrothermal process [ J]ACS Nano, 2010, 4 (7): 4324.), physical infiltration of porous materials (Nguyen DD, Tai N-H, and Lee S-B, et al Superhydrophic and superoleophilic properties of graphene-based nanoparticles using a porous two coating method [ J].Energy&Environmental Science, 2012 (5): 7908.), drying at normal pressure, and supercritical CO2Foaming and supercritical ethanol foaming, preferably freeze-drying and supercritical CO2Foaming method.
In order to better illustrate the present invention and provide a preferred technical solution, the method for preparing a composite aerogel flame retardant material by using waste leather comprises the following steps:
(1) preparing waste leather powder:
firstly, crushing waste leather into single waste leather fibers with the length of 100 nm-300 mu m, then adding the single waste leather fibers into a solid-phase mechanochemical reactor for grinding, introducing cooling circulating water in the grinding process, controlling the temperature of the disc surface of a grinding disc of the solid-phase mechanochemical reactor to be 20-30 ℃, controlling the pressure to be 5-12 KN and the rotating speed to be 150-250 r/min, and circularly grinding for 3-7 times to obtain waste leather powder;
(2) preparing a hydrogel:
dissolving 100 parts by weight of polyvinyl alcohol in water, and then mixing 40-200 parts by weight of waste leather powder to prepare hydrogel;
(3) preparing aerogel:
and (3) preparing the hydrogel obtained in the step (2) into aerogel through a freeze-drying method, and obtaining the composite aerogel flame-retardant material.
In the preferable scheme, the polyvinyl alcohol in the step (2) is selected from polyvinyl alcohol with the polymerization degree of 500-2400 and the alcoholysis degree of 85-99%; further preferably, polyvinyl alcohol with the polymerization degree of 700-2000 and the alcoholysis degree of 90-99% is selected.
In the preferable scheme, the polyvinyl alcohol in the step (2) is dissolved in water, and is stirred for 1-2 hours at the temperature of 70-100 ℃.
In the preferable scheme, the polyvinyl alcohol in the step (2) is dissolved in water, and the mass concentration of the polyvinyl alcohol is 5-30%; more preferably, the mass concentration of the polyvinyl alcohol is 5 to 15%. Wherein, the excessive addition of the polyvinyl alcohol can cause the viscosity of the PVA aqueous solution to be too high and the PVA aqueous solution cannot be fully mixed; similarly, too low a concentration of PVA can prevent the waste leather powder from being uniformly mixed with the subsequent PVA solution.
In the preferable embodiment, the step (2) of mixing 40 to 200 parts of the waste leather powder to prepare the hydrogel is to add the waste leather powder into a PVA aqueous solution in which polyvinyl alcohol is dissolved in water at a temperature of 70 to 100 ℃, and to mix the waste leather powder uniformly by means of mechanical stirring at the temperature. Generally, the polyvinyl alcohol in the step (2) is dissolved in water, and 40 to 200 parts of waste leather powder is mixed to prepare hydrogel, and the hydrogel can be continuously prepared under the same temperature condition.
In the preferable scheme, the waste leather powder in the step (2) is preferably 40 to 200 parts. Wherein, if the added waste leather powder is less than 15 parts, the polyvinyl alcohol is excessive, and the excessive polyvinyl alcohol can cause collapse due to insufficient content of the distributed waste leather powder during freeze drying, thereby leading to the failure of aerogel formation. When the amount of the waste leather powder added exceeds 300 parts and the amount of polyvinyl alcohol added is insufficient, the viscosity of the solution is too high to disperse the waste leather powder in the hydrogel well. In the actual operation process, the proportion of the polyvinyl alcohol to the leather powder can be reasonably adjusted according to the performance requirement of the composite aerogel flame-retardant material so as to obtain the required aerogel.
In the preferable scheme, the aerogel prepared by the freeze-drying method in the step (3) is prepared by putting the PVA/leather powder hydrogel mixed with the waste leather powder into a vacuum freeze-drying oven for freezing and hardening, and then freezing for 48-72 h at the temperature of-25 to-100 ℃; preferably, the freezing condition is-25 to-80 ℃.
The main innovation point of the invention is that the inventor accidentally finds that the aerogel prepared by grinding the waste leather into ultrafine powder by using a solid-phase mechanochemical reactor has good flame retardant property and mechanical property. The inventor researches and discovers that the reason is that the hydrogen bonds are formed by the interaction of a large amount of amino contained in the waste leather ultrafine powder and hydroxyl in the polyhydroxy polymer, the compatibility of the waste leather ultrafine powder and the polyhydroxy polymer is greatly improved, and meanwhile, the novel flame retardant material with excellent mechanical properties is prepared by utilizing the extraction point of the waste leather ultrafine powder containing a large amount of amino.
The composite aerogel flame-retardant material prepared by the invention has the average pore skeleton size of 100-300 mu m, the limited oxygen index of 40 and the elastic modulus of 30 MPa.
The invention has the following beneficial effects:
1. the technical scheme of the invention firstly introduces the waste leather as the main raw material of the aerogel flame-retardant material, realizes the recycling of the waste leather and provides a new way for recycling the waste leather.
2. The method is mature, has the characteristics of simple operation and low cost, and the prepared composite aerogel flame-retardant material has the limited oxygen index of 40 and good mechanical property.
3. According to the invention, the rigid framework is provided for the aerogel through the collagen fibers, so that the dimensional stability and the scouring resistance stability of the aerogel can be ensured, and the service life of the aerogel is prolonged. The composite aerogel flame-retardant material prepared by the invention has obvious advantages in both the self flame-retardant property and the carrier used for the flame-retardant material, and meanwhile, the aerogel is easily used for the carrier of other materials due to the porous structure, so that various performances can be realized by coating different materials, and the composite aerogel flame-retardant material has potential favorable application in the fields of high-strength technical lasers, flame-retardant materials, energy storage devices, ultralight materials and the like.
Drawings
FIG. 1 is a photograph of a composite aerogel flame retardant material prepared in example 1 of the present invention.
FIG. 2 is a compressive stress-strain curve diagram of the composite aerogel flame retardant material prepared in example 1 of the present invention.
FIG. 3 is an electron microscope photograph of the composite aerogel flame retardant material prepared in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
Average pore framework size test method: and placing the obtained aerogel sample in liquid nitrogen for about 20 minutes, taking out the aerogel sample to be brittle, testing the aerogel sample by using an SEM (scanning electron microscope) to obtain an electron microscope picture, and measuring the electron microscope picture by using nanomeasure software.
The limiting oxygen index test method comprises the following steps: GB/T5454 or GB/T2406
Compressive strain: preparing aerogel into the height of 2-3 cm; and (3) testing a cylinder with the diameter of 2-3 cm by using a universal mechanical tester, and compressing at the speed of 0.02 mm/s.
Elastic modulus test method: the final elastic modulus of the material can be obtained by dividing the stress by the strain at the end of the linear part of the stress-strain curve obtained in the compressive strain experiment.
Example 1
In this embodiment, the method for preparing the composite aerogel flame retardant material by using the waste leather includes the following steps:
(1) preparing waste leather powder:
firstly, crushing waste leather into single waste leather fiber with the length of 100 nm-300 mu m, then adding the single waste leather fiber into a solid-phase mechanochemical reactor for grinding, introducing cooling circulating water in the grinding process, controlling the temperature of the disc surface of a grinding disc of the solid-phase mechanochemical reactor to be 25 ℃, the pressure to be 10KN and the rotating speed to be 200 r/min, and circularly grinding for 7 times to obtain waste leather powder;
(2) preparing a hydrogel:
according to the weight portion, 100 portions of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 97 percent are dissolved in 900 portions of distilled water at the temperature of 99 ℃, stirred for 2 hours under the heat preservation condition to prepare PVA water solution, then 200 portions of waste leather powder are mixed in continuously at the temperature of 99 ℃, and the PVA/leather powder hydrogel is prepared by even mixing;
(3) preparing aerogel:
and (3) putting the PVA/leather powder hydrogel obtained in the step (2) into a vacuum freeze drying oven for freezing and hardening, and freezing for 48 hours at the temperature of minus 50 ℃ to obtain the composite aerogel flame-retardant material.
Through detection, the average pore skeleton size of the composite aerogel flame retardant material prepared by the embodiment is about 100-300 μm, the limiting oxygen index is 40, and the elastic modulus is 30 MPa.
Example 2
In this embodiment, the method for preparing the composite aerogel flame retardant material by using the waste leather includes the following steps:
(1) preparing waste leather powder:
firstly, crushing waste leather into single waste leather fiber with the length of 100 nm-300 mu m, then adding the single waste leather fiber into a solid-phase mechanochemical reactor for grinding, introducing cooling circulating water in the grinding process, controlling the temperature of the disc surface of a grinding disc of the solid-phase mechanochemical reactor to be 25 ℃, the pressure to be 8KN and the rotating speed to be 200 r/min, and circularly grinding for 7 times to obtain waste leather powder;
(2) preparing a hydrogel:
according to the weight portion, 100 portions of polyvinyl alcohol with the polymerization degree of 1800 and the alcoholysis degree of 97 percent are dissolved in 1000 portions of distilled water at the temperature of 99 ℃, stirred for 2 hours under the heat preservation condition to prepare PVA water solution, then 150 portions of waste leather powder are mixed in continuously at the temperature of 99 ℃, and the PVA/leather powder hydrogel is prepared by even mixing;
(3) preparing aerogel:
and (3) putting the PVA/leather powder hydrogel obtained in the step (2) into a vacuum freeze drying oven for freezing and hardening, and freezing for 48 hours at the temperature of minus 50 ℃ to obtain the composite aerogel flame-retardant material.
Through detection, the average pore skeleton size of the composite aerogel flame retardant material prepared by the embodiment is about 150-300 μm, the limiting oxygen index is 28, and the elastic modulus is 20 MPa.
Example 3
In this embodiment, the method for preparing the composite aerogel flame retardant material by using the waste leather includes the following steps:
(1) preparing waste leather powder:
firstly, crushing waste leather into single waste leather fiber with the length of 100 nm-300 mu m, then adding the single waste leather fiber into a solid-phase mechanochemical reactor for grinding, introducing cooling circulating water in the grinding process, controlling the temperature of the disc surface of a grinding disc of the solid-phase mechanochemical reactor to be 25 ℃, the pressure to be 10KN and the rotating speed to be 200 r/min, and circularly grinding for 7 times to obtain waste leather powder;
(2) preparing a hydrogel:
according to the weight portion, 100 portions of polyvinyl alcohol with the polymerization degree of 1800 and the alcoholysis degree of 97 percent are dissolved in 1000 portions of distilled water at the temperature of 99 ℃, stirred for 2 hours under the heat preservation condition to prepare PVA water solution, then 100 portions of waste leather powder are mixed in continuously at the temperature of 99 ℃, and the PVA/leather powder hydrogel is prepared by even mixing;
(3) preparing aerogel:
and (3) putting the PVA/leather powder hydrogel obtained in the step (2) into a vacuum freeze drying oven for freezing and hardening, and freezing for 48 hours at the temperature of minus 50 ℃ to obtain the composite aerogel flame-retardant material.
Through detection, the average pore skeleton size of the composite aerogel flame retardant material prepared by the embodiment is about 200-370 μm, the limiting oxygen index is 26, and the elastic modulus is 16 MPa.
Example 4
In this embodiment, the method for preparing the composite aerogel flame retardant material by using the waste leather includes the following steps:
(1) preparing waste leather powder:
firstly, crushing waste leather into single waste leather fiber with the length of 100 nm-300 mu m, then adding the single waste leather fiber into a solid-phase mechanochemical reactor for grinding, introducing cooling circulating water in the grinding process, controlling the temperature of the disc surface of a grinding disc of the solid-phase mechanochemical reactor to be 25 ℃, the pressure to be 8KN and the rotating speed to be 200 r/min, and circularly grinding for 7 times to obtain waste leather powder;
(2) preparing a hydrogel:
according to the weight portion, 100 portions of polyvinyl alcohol with the polymerization degree of 1800 and the alcoholysis degree of 97 percent are dissolved in 1000 portions of distilled water at the temperature of 99 ℃, stirred for 2 hours under the heat preservation condition to prepare PVA water solution, then 50 portions of waste leather powder are mixed in continuously at the temperature of 99 ℃, and the PVA/leather powder hydrogel is prepared by even mixing;
(3) preparing aerogel:
and (3) putting the PVA/leather powder hydrogel obtained in the step (2) into a vacuum freeze drying oven for freezing and hardening, and freezing for 48 hours at the temperature of minus 50 ℃ to obtain the composite aerogel flame-retardant material.
Through detection, the average pore skeleton size of the composite aerogel flame retardant material prepared by the embodiment is about 300-370 μm, the limiting oxygen index is 23, and the elastic modulus is 13 MPa.
Example 5
In this embodiment, the method for preparing the composite aerogel flame retardant material by using the waste leather includes the following steps:
(1) preparing waste leather powder:
firstly, crushing waste leather into single waste leather fiber with the length of 100 nm-300 mu m, then adding the single waste leather fiber into a solid-phase mechanochemical reactor for grinding, introducing cooling circulating water in the grinding process, controlling the temperature of the disc surface of a grinding disc of the solid-phase mechanochemical reactor to be 25 ℃, the pressure to be 8KN and the rotating speed to be 200 r/min, and circularly grinding for 7 times to obtain waste leather powder;
(2) preparing a hydrogel:
according to the weight portion, 100 portions of polyvinyl alcohol with the polymerization degree of 1800 and the alcoholysis degree of 97 percent are dissolved in 1000 portions of distilled water at the temperature of 99 ℃, stirred for 2 hours under the heat preservation condition to prepare PVA water solution, then 15 portions of waste leather powder are mixed in continuously at the temperature of 99 ℃, and the PVA/leather powder hydrogel is prepared by even mixing;
(3) preparing aerogel:
and (3) putting the PVA/leather powder hydrogel obtained in the step (2) into a vacuum freeze drying oven for freezing and hardening, and freezing for 48 hours at the temperature of minus 50 ℃ to obtain the composite aerogel flame-retardant material.
Through detection, the average pore skeleton size of the composite aerogel flame retardant material prepared by the embodiment is about 300-370 μm, the limiting oxygen index is 21, and the elastic modulus is 5 MPa.
Example 6
In this embodiment, the method for preparing the composite aerogel flame retardant material by using the waste leather includes the following steps:
(1) preparing waste leather powder:
firstly, crushing waste leather into single waste leather fiber with the length of 100 nm-300 mu m, then adding the single waste leather fiber into a solid-phase mechanochemical reactor for grinding, introducing cooling circulating water in the grinding process, controlling the disc surface temperature of a grinding disc of the solid-phase mechanochemical reactor to be 15 ℃, the pressure to be 3KN and the rotating speed to be 100 revolutions per minute, and circularly grinding for 1 time to obtain waste leather powder;
(2) preparing a hydrogel:
according to the weight portion, 100 portions of polyvinyl alcohol with the polymerization degree of 500 and the alcoholysis degree of 85 percent are dissolved in 2000 portions of distilled water at the temperature of 70 ℃, stirred for 1 hour under the heat preservation condition to prepare PVA water solution, then 15 portions of waste leather powder are mixed in at the temperature of 70 ℃, and the PVA/leather powder hydrogel is prepared by even mixing;
(3) preparing aerogel:
and (3) putting the PVA/leather powder hydrogel obtained in the step (2) into a vacuum freeze drying oven for freezing and hardening, and freezing for 48 hours at the temperature of minus 20 ℃ to obtain the composite aerogel flame-retardant material.
Example 7
In this embodiment, the method for preparing the composite aerogel flame retardant material by using the waste leather includes the following steps:
(1) preparing waste leather powder:
firstly, crushing waste leather into single waste leather fiber with the length of 100 nm-300 mu m, then adding the single waste leather fiber into a solid-phase mechanochemical reactor for grinding, introducing cooling circulating water in the grinding process, controlling the temperature of the disc surface of a grinding disc of the solid-phase mechanochemical reactor to be 30 ℃, controlling the pressure to be 15KN and the rotating speed to be 300 r/min, and circularly grinding for 9 times to obtain waste leather powder;
(2) preparing a hydrogel:
according to the weight portion, 100 portions of polyvinyl alcohol with the polymerization degree of 2400 and the alcoholysis degree of 99% are dissolved in 350 portions of distilled water at the temperature of 99 ℃, stirred for 2 hours under the heat preservation condition to prepare PVA water solution, then 200 portions of waste leather powder are mixed in continuously at the temperature of 99 ℃, and the PVA/leather powder hydrogel is prepared by uniformly mixing;
(3) preparing aerogel:
and (3) putting the PVA/leather powder hydrogel obtained in the step (2) into a vacuum freeze drying oven for freezing and hardening, and freezing for 72 hours at the temperature of-100 ℃ to obtain the composite aerogel flame-retardant material.
Comparative example 1
In this comparative example, the milled waste leather powder was not added, and the aerogel was prepared directly using polyvinyl alcohol, comprising the steps of:
(1) preparing a hydrogel:
according to parts by weight, 100 parts of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 97 percent are dissolved in 900 parts of distilled water at the temperature of 99 ℃, and the mixture is stirred for 2 hours under the condition of heat preservation to prepare PVA aqueous solution;
(2) preparing aerogel:
and (3) putting the PVA aqueous solution obtained in the step (2) into a vacuum freeze drying oven, freezing for 48 hours at the temperature of 50 ℃ below zero, and then, causing the collapse phenomenon and preventing the aerogel from being formed.
Through detection, the composite aerogel flame retardant material prepared by the comparative example has the average pore skeleton size of about 300-500 mu m and the limiting oxygen index of 20.5.
Comparative example 2
In this comparative example, the milled waste leather powder was not added, and the aerogel was prepared directly using polyvinyl alcohol, comprising the steps of:
(1) preparing a hydrogel:
according to parts by weight, 100 parts of polyvinyl alcohol with the polymerization degree of 1800 and the alcoholysis degree of 97 percent are dissolved in 900 parts of distilled water at the temperature of 99 ℃, and the mixture is stirred for 2 hours under the condition of heat preservation to prepare PVA aqueous solution;
(2) preparing aerogel:
and (3) putting the PVA aqueous solution obtained in the step (2) into a vacuum freeze drying oven, freezing for 48 hours at the temperature of 50 ℃ below zero, and then, causing the collapse phenomenon and preventing the aerogel from being formed.
Through detection, the composite aerogel flame retardant material prepared by the comparative example has the average pore skeleton size of about 300-500 mu m and the limiting oxygen index of 20.5.

Claims (10)

1. A method for preparing a composite aerogel flame-retardant material by using waste leather is characterized by comprising the following steps:
(1) preparing waste leather powder:
firstly, crushing waste leather into single waste leather fibers with the length of 100 nm-300 mu m, then adding the single waste leather fibers into a solid-phase mechanochemical reactor for grinding, introducing cooling circulating water in the grinding process, controlling the temperature of the disc surface of a grinding disc of the solid-phase mechanochemical reactor to be 15-30 ℃, controlling the pressure to be 3-15 KN and the rotating speed to be 100-300 r/min, and circularly grinding for 1-9 times to obtain waste leather powder;
(2) preparing a hydrogel:
according to the weight parts, 100 parts of polyhydroxy polymer which can be used as a raw material for preparing aerogel is dissolved in water, and then 15-200 parts of waste leather powder is mixed to prepare hydrogel;
(3) preparing aerogel:
and (3) preparing the hydrogel obtained in the step (2) into aerogel to obtain the composite aerogel flame-retardant material.
2. The method of claim 1, further comprising: the polyhydroxy polymer which can be used as a raw material for preparing the aerogel in the step (2) is any one of polyvinyl alcohol, cellulose and sodium alginate.
3. The method of claim 1, further comprising: and (3) mixing 15-200 parts of waste leather powder in the step (2) to prepare hydrogel, wherein mechanical stirring and mixing are adopted, and stirring technological parameters are as follows: the stirring speed is 30-100 r/min, and the stirring is carried out for 0.5-2 h.
4. The method of claim 1, further comprising: the aerogel prepared in the step (3) is prepared by adopting a freeze drying method, a solution gel method, a hydrothermal method, a porous material physical infiltration method, a normal pressure drying method and supercritical CO2Foaming or supercritical alcohol foaming.
5. The method of claim 1, further comprising: the method for preparing the composite aerogel flame-retardant material by using the waste leather comprises the following steps:
(1) preparing waste leather powder:
firstly, crushing waste leather into single waste leather fibers with the length of 100 nm-300 mu m, then adding the single waste leather fibers into a solid-phase mechanochemical reactor for grinding, introducing cooling circulating water in the grinding process, controlling the temperature of the disc surface of a grinding disc of the solid-phase mechanochemical reactor to be 20-30 ℃, controlling the pressure to be 5-12 KN and the rotating speed to be 150-250 r/min, and circularly grinding for 3-7 times to obtain waste leather powder;
(2) preparing a hydrogel:
dissolving 100 parts by weight of polyvinyl alcohol in water, and then mixing 40-200 parts by weight of waste leather powder to prepare hydrogel;
(3) preparing aerogel:
and (3) preparing the hydrogel obtained in the step (2) into aerogel through a freeze-drying method, and obtaining the composite aerogel flame-retardant material.
6. The method of claim 5, further comprising: and (3) selecting polyvinyl alcohol with the polymerization degree of 500-2400 and the alcoholysis degree of 85-99% from the polyvinyl alcohol in the step (2).
7. The method of claim 5, further comprising: and (3) dissolving the polyvinyl alcohol in water, and stirring for 1-2 hours at the temperature of 70-100 ℃.
8. The method of claim 5, further comprising: and (3) dissolving the polyvinyl alcohol in water, wherein the mass concentration of the polyvinyl alcohol is 5-30%.
9. The method of claim 5, further comprising: and (3) preparing the aerogel by a freeze-drying method, namely putting the PVA/leather powder hydrogel mixed with the waste leather powder into a vacuum freeze-drying oven, freezing the hydrogel for 48-72 hours at the temperature of-25 to-100 ℃.
10. A composite aerogel flame retardant material prepared according to the method of any of claims 1-9.
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