CN117247654B - Water-soluble benzoxazine and inorganic fiber composite aerogel and preparation method thereof - Google Patents

Water-soluble benzoxazine and inorganic fiber composite aerogel and preparation method thereof Download PDF

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CN117247654B
CN117247654B CN202311533669.2A CN202311533669A CN117247654B CN 117247654 B CN117247654 B CN 117247654B CN 202311533669 A CN202311533669 A CN 202311533669A CN 117247654 B CN117247654 B CN 117247654B
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water
benzoxazine
soluble
composite aerogel
parts
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CN117247654A (en
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赵春霞
侯昭润
李辉
武元鹏
向东
程金波
李东
黄浩然
张学忠
陈卓
刘晏
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Southwest Petroleum 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
    • 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
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2361/04, C08J2361/18, and C08J2361/20
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

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Abstract

The application relates to the technical field of composite materials, in particular to a water-soluble benzoxazine and inorganic fiber composite aerogel and a preparation method thereof; the composite aerogel comprises the following raw materials in parts by weight: water-soluble benzoxazine monomer: 4-25 parts of acid catalyst: 1-8 parts of inorganic fiber: 0.3 to 3.5 parts of polymer: 0.25 to 2 parts of solvent: 40-90 parts; wherein the molecular structure of the polymer includes at least one of the following structural formulas 1 to 6; by designing a composite aerogel raw material comprising a water-soluble benzoxazine monomer, an acid catalyst, inorganic fibers, a polymer and a solvent, the whole raw material does not contain an organic solvent and does not consume the organic solvent, so that the consumption of the organic solvent by the benzoxazine aerogel in the preparation stage and the application stage can be reduced.

Description

Water-soluble benzoxazine and inorganic fiber composite aerogel and preparation method thereof
Technical Field
The application relates to the technical field of composite materials, in particular to a water-soluble benzoxazine and inorganic fiber composite aerogel and a preparation method thereof.
Background
The aerogel is a solid material with low density, low heat conductivity and three-dimensional nano-pore network structure, has considerable advantages when applied to the field of light material heat preservation and heat insulation, wherein the characteristics of the heat insulation material can be improved due to the nano-porous network structure of the benzoxazine aerogel, the low density and the low heat conductivity and the excellent comprehensive properties of the benzoxazine resin serving as a raw material of the benzoxazine aerogel, and the novel polymer aerogel material with enhanced flame retardance, excellent heat insulation performance and mechanical strength can be prepared, and has important practical significance in the aspects of building energy conservation and fire prevention.
Benzoxazine is a novel high-performance resin with excellent mechanical property, thermal property, corrosion resistance, low dielectric constant, strong structural molecule designability and the like; since benzoxazines have chemical properties that can be modified intrinsically during the synthesis and polymerization stages, many of the disadvantages of conventional phenolic resins can be overcome. According to various use environments, different benzoxazine synthetic raw materials and different use conditions can be used, so that benzoxazine resin with expected performance can be obtained, the resin material can be stored at room temperature under normal conditions, zero release of byproducts and close to zero volume shrinkage rate can be realized in the polymerization process, and the ever-increasing green environment-friendly requirement and daily use requirement can be met.
However, benzoxazine aerogel as a porous material, CO is commonly used in the preparation stage 2 Supercritical drying or normal temperature and normal pressure drying, wherein the supercritical drying needs to use high-pressure equipment, so that the supercritical drying has the defects of high energy consumption and the like, and the normal temperature and normal pressure drying needs to be replaced by using a large amount of organic solvents, so that the recovery and the discarding of the solvents in the preparation process all need additional expenditure, do not meet the requirements of green and environment protection, and in the current commercial benzoxazine resin, only the organic solvents can be generally used for dissolution. Therefore, how to provide a water-soluble benzoxazine and inorganic fiber composite aerogel and a preparation method thereof, so as to reduce the consumption of organic solvents in the preparation stage and the application stage of the benzoxazine aerogel, is a technical problem which needs to be solved at present.
Disclosure of Invention
The application provides a water-soluble benzoxazine and inorganic fiber composite aerogel and a preparation method thereof, which are used for solving the technical problem that a large amount of organic solvents are required to be consumed in the preparation stage and the application stage of the benzoxazine aerogel in the prior art.
In a first aspect, the present application provides a water-soluble benzoxazine and inorganic fiber composite aerogel and a preparation method thereof, wherein the composite aerogel comprises the following raw materials in parts by weight: water-soluble benzoxazine monomer: 4-25 parts of acid catalyst: 1-8 parts of inorganic fiber: 0.3 to 3.5 parts of polymer: 0.25 to 2 parts of solvent: 40-90 parts; wherein the molecular structure of the polymer comprises at least one of the following structural formulas:
；
；
，
in the formula 3, the components are mixed,
r is H or；
，
。
Optionally, the molecular structure of the water-soluble benzoxazine monomer includes at least one of the following:
；
。
optionally, the inorganic fiber comprises at least one of:
glass fibers, basalt fibers, silicon carbide fibers, and carbon fibers.
Optionally, the acid catalyst comprises at least one of:
phosphoric acid, hydrochloric acid, acetic acid, oxalic acid and citric acid.
Optionally, the solvent comprises at least one of:
deionized water, ultrapure water, and distilled water.
Optionally, the composite aerogel has a density of 0.1g/cm 3 ～0.4g/cm 3 。
In a second aspect, the present application provides a method of preparing the composite aerogel of the first aspect, the method comprising:
dissolving a polymer in a solvent to obtain a polymer solution;
mixing the polymer solution and the inorganic fibers, and performing ultrasonic dispersion to obtain a fiber mixed solution;
dissolving a water-soluble benzoxazine monomer in the fiber mixed solution to obtain a water-soluble benzoxazine solution;
adding an acid catalyst into the water-soluble benzoxazine solution, and stirring under ice bath conditions to obtain water-soluble benzoxazine sol;
and (3) performing freeze molding on the water-soluble benzoxazine sol, and performing vacuum freeze drying and curing reaction to obtain the water-soluble benzoxazine and inorganic fiber composite aerogel.
Optionally, the stirring time is 10 min-30 min.
Optionally, the vacuum freeze drying time is 24-72 h.
Optionally, the temperature of the curing reaction is 50-80 ℃, and the time of the curing reaction is 24-72 h.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the water-soluble benzoxazine and inorganic fiber composite aerogel and the preparation method thereof, the composite aerogel raw materials comprising the water-soluble benzoxazine monomer, the acid catalyst, the inorganic fiber, the polymer and the solvent are designed, the polymer and the solvent are used as dispersing agents, so that the inorganic fiber can be uniformly dispersed into the water-soluble benzoxazine monomer, the water-soluble benzoxazine monomer can improve the hydrophilicity of the whole composite aerogel, the dispersion uniformity degree of the inorganic fiber is further improved, physical and chemical combination effects of a benzoxazine network and the polymer network on the surface of the inorganic fiber can be generated through the subsequent freeze-drying matched curing reaction, the water-soluble benzoxazine and inorganic fiber composite aerogel is obtained, the whole raw materials do not contain organic solvents and do not consume the organic solvents, and therefore the consumption of the benzoxazine aerogel to the organic solvents in the preparation stage and the application stage can be reduced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a schematic diagram of a scanning electron microscope of a water-soluble benzoxazine and inorganic fiber composite aerogel provided in example 2 of the present application;
FIG. 2 is a schematic flow chart of a method for preparing a water-soluble benzoxazine and inorganic fiber composite aerogel according to an embodiment of the present application;
FIG. 3 is a graph showing the comparison of infrared absorption spectra of water-soluble benzoxazine and inorganic fiber composite aerogel provided in example 2 and comparative example of the present application;
fig. 4 is a schematic diagram showing a comparison of a surface scanning electron microscope of the water-soluble benzoxazine and inorganic fiber composite aerogel provided in example 2 and comparative example 1 of the present application, wherein fig. 4a is a surface scanning electron microscope of the water-soluble benzoxazine and inorganic fiber composite aerogel provided in example 2 of the present application, and fig. 4b is a surface scanning electron microscope of the water-soluble benzoxazine and inorganic fiber composite aerogel provided in comparative example 1 of the present application;
FIG. 5 is a comparative schematic diagram of stress-strain curves of the water-soluble benzoxazine and inorganic fiber composite aerogels provided in example 2, example 5 and comparative example herein;
FIG. 6 is a comparative schematic diagram of nitrogen atmosphere thermogravimetric analysis data of the water-soluble benzoxazine and inorganic fiber composite aerogel provided in example 2 and comparative example herein;
fig. 7 is an infrared thermal imaging data graph of the water-soluble benzoxazine and inorganic fiber composite aerogel provided in example 2 of the present application.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, and the like used in this application are commercially available or may be prepared by existing methods.
The inventive thinking of this application is:
benzoxazine aerogel as a porous material, CO is commonly used in the preparation stage 2 Supercritical drying or normal temperature and normal pressure drying, wherein the supercritical drying needs to use high-pressure equipment, so that the supercritical drying has the defects of high energy consumption and the like, and the normal temperature and normal pressure drying needs to be replaced by using a large amount of organic solvents, so that the recovery and the discarding of the solvents in the preparation process need additional expenditure, and the requirements of environmental protection are not met. Most of vacuum freeze drying uses water as solvent, energy is eliminatedThe drying mode and molecular design of the benzoxazine aerogel need to be further improved, and the existing defects prevent the benzoxazine aerogel from further developing in the field of green manufacturing.
Moreover, in the benzoxazine resins currently in commercial use, only organic solvents are generally used for dissolution. Therefore, how to provide a water-soluble benzoxazine and inorganic fiber composite aerogel and a preparation method thereof, so as to reduce the consumption of organic solvents in the preparation stage and the application stage of the benzoxazine aerogel, is a technical problem which needs to be solved at present.
As shown in fig. 1, an embodiment of the present application provides a water-soluble benzoxazine and inorganic fiber composite aerogel, wherein the raw materials of the composite aerogel include, in parts by weight: water-soluble benzoxazine monomer: 4-25 parts of acid catalyst: 1-8 parts of inorganic fiber: 0.3 to 3.5 parts of polymer: 0.25 to 2 parts of solvent: 40-90 parts; wherein the molecular structure of the polymer comprises at least one of the following structural formulas:
；
；
，
in the formula 3, the components are mixed,
r is H or；
，
。
In the embodiment of the application, the positive effect of limiting the weight part of the water-soluble benzoxazine monomer to 4-25 parts is that the water-soluble benzoxazine monomer can be subjected to ring opening through an acid catalyst in the weight part range, and a sufficient benzoxazine network is formed after subsequent crosslinking and curing, so that the benzoxazine aerogel and the polymer network can generate physical and chemical combination on the surface of inorganic fibers conveniently, further, the benzoxazine aerogel with excellent performance is obtained, and the consumption of an organic solvent of the benzoxazine aerogel in the preparation stage can be effectively reduced.
The positive effect of limiting the weight part of the acid catalyst to 1-8 parts is that in the weight part range, the water-soluble benzoxazine monomer can be opened through enough acid catalyst, so that the subsequent crosslinking and curing are facilitated to form a benzoxazine network.
The inorganic fiber is limited to be 0.3-3.5 parts by weight, so that the inorganic fiber in the benzoxazine aerogel can be fully dispersed into the benzoxazine aerogel, and meanwhile, the benzoxazine network and the polymer network can generate physical and chemical combination action on the surface of the inorganic fiber, so that the benzoxazine aerogel with excellent performance is obtained, and the consumption of an organic solvent of the benzoxazine aerogel in a preparation stage can be effectively reduced.
The positive effect of limiting the weight part of the polymer to 0.25-2 parts is that in the weight part range, the water-soluble benzoxazine monomer can be uniformly dispersed through the polymer, meanwhile, the polymer can form a polymer network in the subsequent crosslinking and curing stage, and the polymer and the benzoxazine network generate physical and chemical combination effects on the surface of the inorganic fiber, so that the benzoxazine aerogel with excellent performance is obtained, and the consumption of an organic solvent of the benzoxazine aerogel in the preparation stage can be effectively reduced.
The limiting solvent has the polar effect that in the range of 40-90 parts by weight, a polymer solution with enough concentration can be formed with the polymer, so that the water-soluble benzoxazine monomer can be uniformly dispersed, a polymer network and a benzoxazine network can be conveniently formed later, and physical and chemical combination effects are generated on the surface of the inorganic fiber together, so that the benzoxazine aerogel with excellent performance is obtained.
The R in the structure shown in the formula 3 is H or。
The polymerization degree n in the above-mentioned structural formulae 1 to 6 is not particularly limited, and only the polymer represented by the structural formula is in a polymerized state.
In some alternative embodiments, the molecular structure of the water-soluble benzoxazine monomer comprises at least one of the following:
；
。
in the embodiment of the application, a specific water-soluble benzoxazine monomer structure is limited, the benzoxazine monomer structure can be more uniformly dispersed into a polymer solution, a polymer network and a benzoxazine network are conveniently formed subsequently, and physical and chemical combination actions are generated on the surface of an inorganic fiber together, so that the benzoxazine aerogel with excellent performance is obtained, and the use of an organic solvent in the preparation stage of the benzoxazine aerogel is reduced.
The polymerization degree n in the above structural formula 7 is not particularly limited, and merely indicates that the water-soluble benzoxazine monomer represented by the structural formula is in a polymerized state.
In some alternative embodiments, the inorganic fibers comprise at least one of the following:
glass fibers, basalt fibers, silicon carbide fibers, and carbon fibers.
In the embodiment of the application, specific types of the inorganic fibers are limited, the polymer network and the benzoxazine network can be fully combined through the bridging action of the inorganic fibers, the bridging action of the inorganic fibers can be further improved, the combination of the polymer network and the benzoxazine network is promoted, the benzoxazine aerogel with excellent performance is further obtained, and the use of an organic solvent in the preparation stage of the benzoxazine aerogel is reduced.
In some alternative embodiments, the acid catalyst comprises at least one of the following:
phosphoric acid, hydrochloric acid, acetic acid, oxalic acid and citric acid.
In the embodiment of the application, the specific type of the acid catalyst is limited, so that the water-soluble benzoxazine monomer can be further opened, and subsequent crosslinking and curing are facilitated to form a benzoxazine network.
In some alternative embodiments, the solvent comprises at least one of the following:
deionized water, ultrapure water, and distilled water.
In the embodiment of the application, the specific types of the solvents are limited, so that the polymers are fully dissolved in the solvents and uniformly dispersed.
In some alternative embodiments, the composite aerogel has a density of 0.1g/cm 3 ～0.4g/cm 3 。
In the embodiment of the application, the specific density of the composite aerogel is limited, which can indicate that the composite aerogel has enough polymer network and benzoxazine network, so that the excellent performance of the benzoxazine aerogel can be demonstrated.
As shown in fig. 2, an embodiment of the present application provides a method for preparing the composite aerogel, the method comprising:
s1, dissolving a polymer in a solvent to obtain a polymer solution;
s2, mixing the polymer solution and the inorganic fibers, and performing ultrasonic dispersion to obtain a fiber mixed solution;
s3, dissolving a water-soluble benzoxazine monomer in the fiber mixed solution to obtain a water-soluble benzoxazine solution;
s4, adding an acid catalyst into the water-soluble benzoxazine solution, and stirring under ice bath conditions to obtain water-soluble benzoxazine sol;
s5, performing freeze molding on the water-soluble benzoxazine sol, and performing vacuum freeze drying and curing reaction to obtain the water-soluble benzoxazine and inorganic fiber composite aerogel.
The method is directed to the preparation method of the composite aerogel, and the specific composition of the composite aerogel can refer to the above embodiment, and because the method adopts part or all of the technical solutions of the above embodiment, the method at least has all the beneficial effects brought by the technical solutions of the above embodiment, and the detailed description is omitted herein.
The method is characterized in that a polymer solution is prepared firstly, inorganic fibers are uniformly dispersed into the polymer solution in an ultrasonic dispersion mode, then a water-soluble benzoxazine monomer is added into a fiber mixed solution to form a water-soluble benzoxazine solution, then an acid catalyst is added to promote the ring opening of the water-soluble benzoxazine monomer, the benzoxazine monomer is stirred and frozen into a shape through an ice bath, and then the polymer solution is subjected to vacuum freeze-drying, so that the polymerization temperature of the benzoxazine monomer can be greatly reduced, and the curing reaction can be promoted to be carried out at a lower temperature through the vacuum freeze-drying mode, so that a new research idea can be provided for the preparation of the benzoxazine aerogel, meanwhile, an organic solvent is not adopted in the whole process, and the consumption of the organic solvent in the preparation process can be reduced.
In some alternative embodiments, the stirring time is from 10 minutes to 30 minutes.
In the embodiment of the application, the specific stirring time is limited, and the acid catalyst can catalyze the water-soluble benzoxazine monomer to open the loop in a stirring mode, so that the subsequent benzoxazine network and the polymer network can generate physical and chemical combination effect on the surface of the inorganic fiber.
The stirring time may be 10min, 15min, 20min, 25min, or 30min.
In some alternative embodiments, the vacuum freeze drying time is 24 hours to 72 hours.
In the embodiment of the application, the specific time of vacuum freeze drying is limited, the water-soluble benzoxazine sol can be primarily solidified in a vacuum freeze drying mode, and the mode of ice bath stirring and freeze forming can be matched, so that the solidification reaction is carried out at a lower temperature, an organic solvent is not adopted in the whole process, and the consumption of the organic solvent in the preparation process can be reduced.
The time for vacuum freeze-drying may be 24 hours, 30 hours, 36 hours, 42 hours, 48 hours, 54 hours, 60 hours, 66 hours, or 72 hours.
In some alternative embodiments, the temperature of the curing reaction is 50 ℃ to 80 ℃ and the time of the curing reaction is 24 hours to 72 hours.
In the embodiment of the application, the specific temperature and the specific time of the curing reaction are limited, the water-soluble benzoxazine monomer and the polymer can be crosslinked and cured through the curing reaction, so that a benzoxazine network and a polymer network are obtained, the benzoxazine network and the polymer network generate physical and chemical combination action on the surface of the inorganic fiber through the bridging action of the inorganic fiber, the performance of the benzoxazine aerogel is improved, an organic solvent is not adopted in the whole process, and the consumption of the organic solvent in the preparation process can be reduced.
The curing reaction may be carried out at a temperature of 50℃or 55℃or 60℃or 65℃or 70℃or 75℃or 80 ℃.
The curing reaction time may be 24 hours, 30 hours, 36 hours, 42 hours, 48 hours, 54 hours, 60 hours, 66 hours, or 72 hours.
The present application is further illustrated below in conjunction with specific examples. It should be understood that these examples are illustrative only of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
A method of preparing a water-soluble benzoxazine and inorganic fiber composite aerogel comprising:
s1, adding 0.5 part by weight of a polymer shown in a structural formula 2 and 65 parts by weight of deionized water into a container, and stirring at normal temperature until the polymer is dissolved to obtain a polymer solution;
s2, adding 2 parts by weight of glass fibers into the polymer solution, and performing ultrasonic treatment until the glass fibers are uniformly dispersed to obtain a fiber mixed solution;
s3, adding 17 parts by weight of a water-soluble benzoxazine monomer shown in a formula 6 into the fiber mixed solution, and stirring at normal temperature until the water-soluble benzoxazine monomer is dissolved to obtain a water-soluble benzoxazine solution;
s4, adding 3 parts by weight of citric acid into the water-soluble benzoxazine solution, and continuously stirring for 20min under the ice bath condition to obtain water-soluble benzoxazine sol;
s5, pouring the obtained water-soluble benzoxazine sol into a mould, placing the mould in a low-temperature constant-temperature reaction bath for cold forming, then placing the mould in a vacuum freeze dryer for 48 hours, and then placing the mould in a 70 ℃ for curing reaction for 36 hours to obtain the water-soluble benzoxazine and inorganic fiber composite aerogel, wherein the synthesis principle of the composite aerogel is as follows:
。
the density of the obtained composite aerogel is 0.2674g/cm 3 。
Example 2
A method of preparing a water-soluble benzoxazine and inorganic fiber composite aerogel comprising:
s1, adding 1 part by weight of a polymer shown in a structural formula 4 and 45 parts by weight of deionized water into a container, and stirring at normal temperature until the polymer is dissolved to obtain a polymer solution;
s2, adding 1.5 parts by weight of basalt fiber into the polymer solution, and carrying out ultrasonic treatment until the basalt fiber is uniformly dispersed to obtain a fiber mixed solution;
s3, adding 10 parts by weight of a water-soluble benzoxazine monomer shown in a formula 6 into the fiber mixed solution, and stirring at normal temperature until the water-soluble benzoxazine monomer is dissolved to obtain a water-soluble benzoxazine solution;
s4, adding 2 parts by weight of phosphoric acid into the water-soluble benzoxazine solution, and continuously stirring for 15min under the ice bath condition to obtain water-soluble benzoxazine sol;
s5, pouring the obtained water-soluble benzoxazine sol into a mould, placing the mould in a low-temperature constant-temperature reaction bath for cold forming, then placing the mould in a vacuum freeze dryer for 72h, and then placing the mould in a 75 ℃ for curing reaction for 48h to obtain the water-soluble benzoxazine and inorganic fiber composite aerogel, wherein the synthesis principle of the composite aerogel is as follows:
。
the density of the obtained composite aerogel is 0.1574g/cm 3 。
Example 3
A method of preparing a water-soluble benzoxazine and inorganic fiber composite aerogel comprising:
s1, adding 2 parts by weight of a polymer shown in a structural formula 1 and 40 parts by weight of deionized water into a container, and stirring at normal temperature until the polymer is dissolved to obtain a polymer solution;
s2, adding 3 parts by weight of carbon fibers into the polymer solution, and performing ultrasonic treatment until the carbon fibers are uniformly dispersed to obtain a fiber mixed solution;
s3, adding 20 parts by weight of a water-soluble benzoxazine monomer shown in a formula 7 into the fiber mixed solution, and stirring at normal temperature until the water-soluble benzoxazine monomer is dissolved to obtain a water-soluble benzoxazine solution;
s4, adding 6 parts by weight of oxalic acid into the water-soluble benzoxazine solution, and continuously stirring for 25 minutes under the ice bath condition to obtain water-soluble benzoxazine sol;
s5, pouring the obtained water-soluble benzoxazine sol into a mould, placing the mould in a low-temperature constant-temperature reaction bath for cold forming, then placing the mould in a vacuum freeze dryer for 24 hours, and then placing the mould in a temperature of 50 ℃ for curing reaction for 24 hours to obtain the water-soluble benzoxazine and inorganic fiber composite aerogel, wherein the synthesis principle of the composite aerogel is as follows:
。
the density of the obtained composite aerogel is 0.2501g/cm 3 。
Example 4
A method of preparing a water-soluble benzoxazine and inorganic fiber composite aerogel comprising:
s1, adding 1.6 parts by weight of a polymer shown in a structural formula 5 and 80 parts by weight of deionized water into a container, and stirring at normal temperature until the polymer is dissolved to obtain a polymer solution;
s2, adding 0.4 part by weight of silicon carbide fibers into the polymer solution, and carrying out ultrasonic treatment until the silicon carbide fibers are uniformly dispersed to obtain a fiber mixed solution;
s3, adding 5 parts by weight of a water-soluble benzoxazine monomer shown in a formula 7 into the fiber mixed solution, and stirring at normal temperature until the water-soluble benzoxazine monomer is dissolved to obtain a water-soluble benzoxazine solution;
s4, adding 4 parts by weight of hydrochloric acid into the water-soluble benzoxazine solution, and continuously stirring for 30min under the ice bath condition to obtain water-soluble benzoxazine sol;
s5, pouring the obtained water-soluble benzoxazine sol into a mould, placing the mould in a low-temperature constant-temperature reaction bath for cold forming, then placing the mould in a vacuum freeze dryer for 48 hours, and then placing the mould in a 70 ℃ for curing reaction for 36 hours to obtain the water-soluble benzoxazine and inorganic fiber composite aerogel, wherein the synthesis principle of the composite aerogel is as follows:
。
the density of the obtained composite aerogel is 0.1496 g/cm 3 。
Example 5
A method of preparing a water-soluble benzoxazine and inorganic fiber composite aerogel comprising:
s1, adding 2 parts by weight of a polymer shown in a structural formula 3 and 60 parts by weight of deionized water into a container, and stirring at normal temperature until the polymer is dissolved to obtain a polymer solution, wherein R groups in the structural formula 3 areThe concrete structure is that：/>
；
S2, adding 1 part by weight of carbon fiber into the polymer solution, and performing ultrasonic treatment until the carbon fiber is uniformly dispersed to obtain a fiber mixed solution;
s3, adding 12 parts by weight of a water-soluble benzoxazine monomer shown in a formula 6 into the fiber mixed solution, and stirring at normal temperature until the water-soluble benzoxazine monomer is dissolved to obtain a water-soluble benzoxazine solution;
s4, adding 5 parts by weight of acetic acid into the water-soluble benzoxazine solution, and continuously stirring for 20min under the ice bath condition to obtain water-soluble benzoxazine sol;
s5, pouring the obtained water-soluble benzoxazine sol into a mould, placing the mould in a low-temperature constant-temperature reaction bath for cold forming, then placing the mould in a vacuum freeze dryer for 72h, and then placing the mould in a 60 ℃ for curing reaction for 48h to obtain the water-soluble benzoxazine and inorganic fiber composite aerogel, wherein the synthesis principle of the composite aerogel is as follows:
。
the density of the obtained composite aerogel is 0.1756g/cm 3 。
The polymerization degree n in examples 1 to 5 indicates only that the product represented by the structural formula is in a polymerized state.
Comparative example 1
A method of preparing a water-soluble benzoxazine and inorganic fiber composite aerogel comprising:
s1, adding 0.8 part by weight of a polymer shown in a structural formula 4 and 50 parts by weight of deionized water into a container, and stirring at normal temperature until the polymer is dissolved to obtain a polymer solution;
s2, adding 10 parts by weight of a water-soluble benzoxazine monomer shown in a formula 6 into the polymer solution, and stirring at normal temperature until the water-soluble benzoxazine monomer is dissolved to obtain a water-soluble benzoxazine solution;
s3, adding 3 parts by weight of phosphoric acid into the water-soluble benzoxazine solution, and continuously stirring for 15min under the ice bath condition to obtain water-soluble benzoxazine sol;
s4, pouring the obtained water-soluble benzoxazine sol into a mould, placing the mould in a low-temperature constant-temperature reaction bath for cold forming, then placing the mould in a vacuum freeze dryer for 72h, and then placing the mould in a 75 ℃ for curing reaction for 48h to obtain the water-soluble benzoxazine and inorganic fiber composite aerogel, wherein the synthesis principle of the composite aerogel is as follows:
。
comparative example 2
A method of preparing a water-soluble benzoxazine and inorganic fiber composite aerogel comprising:
s1, adding 3 parts by weight of a polymer shown in a structural formula 4 and 50 parts by weight of deionized water into a container, and stirring at normal temperature until the polymer is dissolved to obtain a polymer solution;
s2, adding 0.3 part by weight of carbon fiber into the polymer solution, and carrying out ultrasonic treatment until the carbon fiber is uniformly dispersed to obtain a fiber mixed solution;
s3, adding 2 parts by weight of a water-soluble benzoxazine monomer shown in a formula 6 into the fiber mixed solution, and stirring at normal temperature until the water-soluble benzoxazine monomer is dissolved to obtain a water-soluble benzoxazine solution;
s4, adding 1 part by weight of hydrochloric acid into the water-soluble benzoxazine solution, and continuously stirring for 30min under the ice bath condition to obtain water-soluble benzoxazine sol;
s5, pouring the obtained water-soluble benzoxazine sol into a mould, placing the mould in a low-temperature constant-temperature reaction bath for cold forming, then placing the mould in a vacuum freeze dryer for 48 hours, and then placing the mould in a temperature of 80 ℃ for curing reaction for 72 hours to obtain the water-soluble benzoxazine and inorganic fiber composite aerogel, wherein the synthesis principle of the composite aerogel is as follows:
。
related experiment and effect data:
obtained for example 2 and comparative exampleThe infrared absorption spectrum of the water-soluble benzoxazine-inorganic fiber composite aerogel was measured, and the results are shown in FIG. 3, which shows that 1000 cm in example 2 -1 Because of the introduction of the inorganic fiber, a wider absorption peak is generated; in comparative example 2, however, 1233 cm was produced due to the ring-opening crosslinking of the monomer -1 Reduced peak at the same time as in comparative example 1 and example 2, the introduction of phosphoric acid was at 2725 cm -1 A broad hydroxyl absorption peak is generated.
The surface of the water-soluble benzoxazine and inorganic fiber composite aerogel obtained in example 2 and comparative example 1 was observed by using a scanning electron microscope, and as a result, as shown in fig. 4, it can be seen from fig. 4a that the layered structure of example 2, to which inorganic fibers are added, is penetrated by more inorganic fibers, whereas the layered structure of comparative example 1 in fig. 4b, which is only freeze-dried, shows that the inorganic fibers can play a bridging role, and the structural stability of the composite aerogel is enhanced.
The results of measuring the stress-strain curves of the water-soluble benzoxazine and inorganic fiber composite aerogels obtained in example 2, example 5, comparative example 1 and comparative example 2 are shown in fig. 5, and it can be seen from the figures that the inorganic fiber-introduced examples 2 and 5 can exhibit stronger mechanical properties. And, since the concentration of the resin of comparative example 2 is lower, it shows weaker mechanical properties than that of comparative example 1.
The water-soluble benzoxazine and inorganic fiber composite aerogel obtained in example 2 and comparative example were subjected to nitrogen atmosphere thermogravimetric analysis, and the results are shown in fig. 6, and it is seen from the graph that comparative example 1 and example 2 have lower initial decomposition temperature and higher carbon residue ratio than comparative example 2 due to the phosphoric acid catalysis. Meanwhile, as can be seen from fig. 6, the carbon residue ratio of example 2 is higher at 800 ℃, which indicates that the water-soluble benzoxazine and inorganic fiber composite aerogel can show higher residue weight than the water-soluble benzoxazine aerogel, and the inorganic fiber plays a role of supporting a carbon layer, phosphoric acid is beneficial to carbonization of a surface layer, and further thermal decomposition of organic matters can be prevented, so that the combustion process is inhibited.
The infrared thermal imaging test was performed on the water-soluble benzoxazine and inorganic fiber composite aerogel obtained in example 2, and the result is shown in fig. 7, and it can be seen from fig. 7 that the upper surface of the composite aerogel is raised from the initial 31.8 ℃ and stabilized at 43.9 ℃ after the composite aerogel in example 2 is placed on a heat table at 100 ℃ and heated for 10min, which indicates that the water-soluble benzoxazine and inorganic fiber composite aerogel has a good heat insulation effect.
In summary, according to the water-soluble benzoxazine and inorganic fiber composite aerogel and the preparation method thereof provided by the embodiment of the application, by designing the composite aerogel raw materials including the water-soluble benzoxazine monomer, the acid catalyst, the inorganic fiber, the polymer and the solvent are utilized to serve as dispersing agents, so that the inorganic fiber can be uniformly dispersed into the water-soluble benzoxazine monomer, the water-soluble benzoxazine monomer is adopted to improve the hydrophilicity of the whole composite aerogel, the dispersion uniformity degree of the inorganic fiber is further improved, and the benzoxazine resin is synthesized by using the raw materials containing hydrophilic groups, so that the benzoxazine resin has the characteristic of water solubility, therefore, the benzoxazine aerogel is prepared in a freeze-drying mode, the whole raw materials do not contain organic solvents and do not consume the organic solvents, and therefore, the consumption of the benzoxazine aerogel to the organic solvents in the preparation stage and the application stage can be reduced.
Meanwhile, according to the preparation method of the water-soluble benzoxazine and inorganic fiber composite aerogel, provided by the embodiment of the application, through ice bath stirring and freeze molding, and then through vacuum freeze drying, the polymerization temperature of benzoxazine monomers can be greatly reduced, and the curing reaction can be promoted to be carried out at a lower temperature in a vacuum freeze drying mode, so that a new research thought can be provided for the benzoxazine aerogel.
Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present application, the terms "include", "comprise", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. The water-soluble benzoxazine and inorganic fiber composite aerogel is characterized by comprising the following raw materials in parts by weight: water-soluble benzoxazine monomer: 4-25 parts of acid catalyst: 1-8 parts of inorganic fiber: 0.3 to 3.5 parts of polymer: 0.25 to 2 parts of solvent: 40-90 parts; wherein the solvent comprises at least one of the following:
deionized water, ultrapure water and distilled water;
the molecular structure of the polymer includes at least one of the following structural formulas:
；
；
，
in the formula 3, the components are mixed,
r is H or；
；
。
2. The composite aerogel of claim 1, wherein the molecular structure of the water-soluble benzoxazine monomer comprises at least one of:
；
。
3. the composite aerogel of claim 1, wherein the inorganic fibers comprise at least one of:
glass fibers, basalt fibers, silicon carbide fibers, and carbon fibers.
4. The composite aerogel of claim 1, wherein the acid catalyst comprises at least one of:
phosphoric acid, hydrochloric acid, acetic acid, oxalic acid and citric acid.
5. The composite aerogel of claim 1, wherein the composite aerogel has a density of 0.1g/cm 3 ～0.4g/cm 3 。
6. A method of preparing the composite aerogel of any of claims 1-5, comprising:
dissolving a polymer in a solvent to obtain a polymer solution;
mixing the polymer solution and the inorganic fibers, and performing ultrasonic dispersion to obtain a fiber mixed solution;
dissolving a water-soluble benzoxazine monomer in the fiber mixed solution to obtain a water-soluble benzoxazine solution;
adding an acid catalyst into the water-soluble benzoxazine solution, and stirring under ice bath conditions to obtain water-soluble benzoxazine sol;
and (3) performing freeze molding on the water-soluble benzoxazine sol, and performing vacuum freeze drying and curing reaction to obtain the water-soluble benzoxazine and inorganic fiber composite aerogel.
7. The method of claim 6, wherein the stirring time is from 10 minutes to 30 minutes.
8. The method of claim 6, wherein the vacuum freeze drying is for a period of 24 hours to 72 hours.
9. The method of claim 6, wherein the temperature of the curing reaction is 50 ℃ to 80 ℃ and the time of the curing reaction is 24 hours to 72 hours.
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