CN113150368A - Moisture-proof modified phenolic aldehyde heat-insulating material and preparation method thereof - Google Patents
Moisture-proof modified phenolic aldehyde heat-insulating material and preparation method thereof Download PDFInfo
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- CN113150368A CN113150368A CN202011321126.0A CN202011321126A CN113150368A CN 113150368 A CN113150368 A CN 113150368A CN 202011321126 A CN202011321126 A CN 202011321126A CN 113150368 A CN113150368 A CN 113150368A
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
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Abstract
The invention belongs to the technical field of thermal protection, and discloses a moisture-proof modified phenolic aldehyde heat-insulating material and a preparation method thereof. The method comprises the following steps: (1) preparing a water repellent agent: mixing a hydrophobic modifier with a catalyst and a solvent to prepare a hydrophobic agent with a hydrophobic modification function; (2) and (3) hydrophobization reaction: and adding the hydrophobization reagent into the phenolic thermal insulation material for soaking at room temperature to perform hydrophobization reaction. (3) And (3) drying: after the hydrophobization reaction is finished, removing redundant hydrophobization reagents in a drying mode under the in-situ condition to obtain the moisture-proof modified phenolic aldehyde heat-insulating material. The moisture-proof modified phenolic aldehyde heat-insulating material has excellent moisture-proof performance.
Description
Technical Field
The invention relates to the technical field of thermal protection, in particular to a moisture-proof modified phenolic aldehyde heat-insulating material and a preparation method thereof.
Background
The description of the background of the invention pertaining to the related art to which this invention pertains is given for the purpose of illustration and understanding only of the summary of the invention and is not to be construed as an admission that the applicant is explicitly or implicitly admitted to be prior art to the date of filing this application as first filed with this invention.
The porous heat-insulating material represented by the phenolic aldehyde heat-insulating material, particularly the phenolic aldehyde aerogel composite material, has the advantages of ablation resistance, light weight, excellent heat-insulating property, stable performance, low cost and the like, and is widely applied to the fields of aerospace, deep space exploration and civil heat insulation at home and abroad at present. However, the material has high porosity, rich internal pore structure, large specific surface area and rich surface hydroxyl, so that the material has strong hygroscopicity, and if the material is not subjected to moisture-proof treatment, the material is influenced by moisture, fog or rainwater in the air in the long-term storage or use process, so that a large amount of moisture is enriched in the pore structure of the material, the material structure is gradually aged and damaged, and the service life of the material is finally influenced.
Compared with the mature moisture-proof technology of silica-based inorganic porous materials (such as aerogel, fibrofelt, porous ceramic tile and the like), the commonly adopted hydrophobizing agent (trimethyl methoxysilane, trimethyl chlorosilane, hexamethyldisilazane and the like) can form a stable hydrophobic structure with silicon hydroxyl, but is difficult to react with phenolic hydroxyl in the phenolic composite material to form a stable moisture-proof structure, and cannot well play a long-term and efficient moisture-proof effect. In addition, the reagent can generate corrosive atmosphere such as acid (chlorosilane), alkali (hexamethyldisilazane) and the like in the hydrophobic reaction process, and is not beneficial to hydrophobic moisture-proof operation after the material and the metal member are integrally formed. Thus, there is currently no suitable moisture barrier treatment for such materials.
In the known reports related to the waterproof modification of phenolic materials, the hydrophobic treatment of the materials is mainly realized by compounding a hydrophobic coating on the outer surface of the materials, and the treatment mode can prevent liquid water from contacting with the phenolic insulation materials in a physical blocking mode and prevent the materials from absorbing the liquid water, but cannot fundamentally solve the problem that the residual phenolic hydroxyl on the surfaces of pores inside the materials absorbs and enriches gaseous water, so that the service life and the storage life of the high-performance insulation materials in a large-scale and highly integrated thermal protection system are influenced.
Disclosure of Invention
The embodiment of the invention aims to provide a moisture-proof modified phenolic aldehyde heat-insulating material and a preparation method thereof.
The purpose of the invention is realized by the following scheme:
in a first aspect, the invention provides a moisture-proof modified phenolic aldehyde heat-insulating material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) preparing a water repellent agent: mixing a hydrophobic modifier with a catalyst and a solvent to prepare a hydrophobic agent with a hydrophobic modification function;
(2) and (3) hydrophobization reaction: and adding the hydrophobization reagent into the phenolic thermal insulation material for soaking at room temperature to perform hydrophobization reaction.
(3) And (3) drying: after the hydrophobization reaction is finished, removing redundant hydrophobization reagents in a drying mode under the in-situ condition to obtain the moisture-proof modified phenolic aldehyde heat-insulating material.
Further, in the step (1), the modifying agent is an agent having the formula (1), (2) or (3),
wherein R is1Selected from the group consisting of-H, -CN, -NO2、-SO2R7、-SO2N R7R8、-COR7、-COOR7、 -CONR7R8One of (1), R2Selected from the group consisting of-CN, -NO2、-SO2R7、-SO2N R7R8、-COR7、 -COOR7、-CONR7R8One of (1), R3,R4,R5And R6Are all independently selected from the group consisting of-H, -CN, -NO2、 -SO2R7、-SO2NR7R8、-COR7、-COOR7、-CONR7R8Or one of carbon chain groups having 1 to 10 carbons, R7And R8Are each independently selected from the group consisting of-H or a carbon chain group having 1-10 carbons.
Further, in the step (1), the amount of the hydrophobic modifier is 1-20% of the total weight of the phenolic aldehyde heat insulation material.
Further, in the step (1), the catalyst is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, sodium hydroxide, potassium carbonate, ammonia water, triethylamine, ethylenediamine and methylamine.
Further, in the step (1), the amount of the catalyst is 0.1-20% of the mass of the modifier.
Further, in the step (1), the solvent is selected from one or more of acetonitrile, acetone, ethyl acetate, toluene, xylene and C1-C10 alcohol compounds, and the amount of the solvent is 2-5 times of the mass of the phenolic aldehyde heat-insulating material.
Further, the phenolic insulation material is a phenolic ablative composite, a phenolic aerogel composite, or a porous composite of a mixture of multiple resins or polymers containing phenolic resin.
Further, the soaking time in the step (2) is 0.1-12 hours.
Further, the drying treatment time in the step (3) is 0.1-96 hours.
In a second aspect, the present invention provides a modified phenolic insulation material prepared by the method of any one of claims 1 to 9; the moisture-proof modified phenolic aldehyde heat-insulating material has the mass weight percentage of less than or equal to 3 percent relative to the phenolic aldehyde heat-insulating material used as the raw material, the moisture absorption rate change is less than or equal to 1 percent, and the thermal conductivity change is less than 1 percent.
The embodiment of the invention has the following beneficial effects:
(1) the moisture-proof technology provided by the invention can be used for performing moisture-proof treatment on the phenolic material under the room-temperature normal-pressure environment through the introduction of catalytic reaction and the selection of a special reagent, greatly simplifies the technical difficulty and the treatment time of the moisture-proof treatment, breaks through the bottleneck problem that the existing moisture-proof method for phenolic heat-insulating materials can not completely realize the formation of molecular-level stable hydrophobic structures on the surface of the materials, and greatly reduces the technical difficulty of the moisture-proof treatment of the heat-insulating materials. The heat-insulating property of the moisture-proof heat-insulating material obtained after treatment is not changed, the moisture-proof property is excellent, and the mass moisture absorption rate is less than or equal to 1 percent; the introduction amount of moisture-proof impurities is controllable, and the total residual amount of reagents and byproducts of the material after moisture-proof treatment is less than 1 percent, which is obviously superior to the existing surface spraying type moisture-proof treatment method; the material has stable and controllable weight gain after moisture-proof treatment, and the basic thermophysical property of the material is basically unchanged.
(2) The hydrophobic reaction adopted by the technical method is an addition reaction, no new waste gas and waste solid are generated, no catalyst residue is generated, the reagent is a mature neutral industrialized product, the raw material source is wide and cheap, the environment is friendly, and the material compatibility is good.
(3) The reaction compatibility is good, the formed phenolic aldehyde heat-insulating material can be subjected to hydrophobization modification again, the hydrophobization modification can be completed in the gel stage of the phenolic aldehyde heat-insulating material, and the process compatibility is good.
Detailed Description
The present application is further described below with reference to examples.
In the following description, different "one embodiment" or "an embodiment" may not necessarily refer to the same embodiment, in order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art. Various embodiments may be replaced or combined, and other embodiments may be obtained according to the embodiments without creative efforts for those skilled in the art.
A moisture-proof modified phenolic aldehyde heat-insulating material and a preparation method thereof comprise the following steps:
(1) preparing a water repellent agent: mixing a hydrophobic modifier with a catalyst and a solvent to prepare a hydrophobic agent with a hydrophobic modification function;
(2) and (3) hydrophobization reaction: and adding the hydrophobization reagent into the phenolic thermal insulation material for soaking at room temperature to perform hydrophobization reaction.
(3) And (3) drying: after the hydrophobization reaction is finished, removing redundant hydrophobization reagents in a drying mode under the in-situ condition to obtain the moisture-proof modified phenolic aldehyde heat-insulating material.
In some embodiments of the invention, in step (1), the modifying agent is an agent having formula (1), (2) or (3),
wherein R is1Selected from the group consisting of-H, -CN, -NO2、-SO2R7、-SO2N R7R8、-COR7、-COOR7、 -CONR7R8One of (1), R2Selected from the group consisting of-CN, -NO2、-SO2R7、-SO2N R7R8、-COR7、 -COOR7、-CONR7R8One of (1), R3,R4,R5And R6Are all independently selected from the group consisting of-H, -CN, -NO2、 -SO2R7、-SO2NR7R8、-COR7、-COOR7、-CONR7R8Or one of carbon chain groups having 1 to 10 carbons, R7And R8Are independently selected from one of-H or a carbon chain group having 1-10 carbons.
In some embodiments of the present invention, in step (1), the hydrophobic modifier is used in an amount of 1% to 20% by weight based on the total weight of the phenolic insulation material.
In some embodiments of the present invention, in step (1), the catalyst is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, sodium hydroxide, potassium carbonate, ammonia, triethylamine, ethylenediamine, methylamine, and acidic or basic substances known in the art with equivalent catalytic efficiency.
In some embodiments of the invention, in step (1), the amount of the catalyst is 0.1 to 20% by mass of the modifier.
In some embodiments of the present invention, in the step (1), the solvent is selected from one or more of acetonitrile, acetone, ethyl acetate, toluene, xylene and 1-10 carbon alcohol compounds, and the amount of the solvent is 2-5 times of the mass of the phenolic insulation material.
In some embodiments of the present invention, the phenolic insulation material in the step (2) is a phenolic resin-based porous composite material, preferably a phenolic ablative composite material, a phenolic aerogel composite material, and a porous composite material comprising a mixture of multiple resins or polymers of phenolic resin.
In some embodiments of the present invention, the soaking time in step (2) is 0.1-12 h.
In some embodiments of the present invention, the drying time in step (3) is 0.1 to 96 hours.
A modified phenolic insulation material prepared by the method of any one of claims 1 to 9; the moisture-proof modified phenolic aldehyde heat-insulating material has the mass weight percentage of less than or equal to 3 percent relative to the phenolic aldehyde heat-insulating material used as the raw material, the moisture absorption rate change is less than or equal to 1 percent, and the thermal conductivity change is less than 1 percent.
The moisture-proof treatment method of the phenolic aldehyde heat-insulating material comprises the steps of carrying out the treatment under the conditions of room temperature, normal pressure and liquid phase, wherein the treatment has no significant influence on other properties of the material and can be repeatedly carried out for multiple times. The hydrophobization modifying agent selected in the method is an agent with a molecular structure shown in a molecular formula (1), (2) or (3), wherein R is1Is represented by-H, -CN, -NO2、-SO2R7、-SO2N R7R8、-COR7、-COOR7、 -CONR7R8One of (1), R2Is represented by-CN, -NO2、-SO2R7、-SO2N R7R8、-COR7、-COOR7、 -CONR7R8One of (1), R3,R4,R5,R6Is represented by-H, -CN, -NO2、-SO2R7、-SO2N R7R8、 -COR7、-COOR7、-CONR7R8Or a carbon chain radical of 1 to 10 carbons, R7,R8The modifier is a carbon chain group with-H or 1-10 carbon atoms, n is 1-10%, and the amount of the modifier is 1-20% (such as 1%, 2%, 5%, 10%, 20%) of the total weight of the phenolic insulation material. The catalyst is prepared from hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, sodium hydroxide, potassium carbonate, ammonia water, triethylamine, ethylenediamine, methylamine and acidic or basic substances which are commonly known in the field and have the same catalytic efficiency, and the dosage of the catalyst is 0.1-20% (such as 0.1%, 2%, 5%, 15%, 20%) of that of the modifier. The solvent is one or more of acetonitrile, acetone, ethyl acetate, toluene, xylene and C1-C10 alcohol compounds, and the amount of the solvent is 2-5 times (for example, 2, 3, 4 and 5 times) of the mass of the phenolic aldehyde heat-insulating material. In the method, the treatment temperature and pressure are not particularly required, the treatment temperature and pressure are preferably consistent with the environmental conditions, the temperature range is-20 ℃ to 50 ℃ (-10 ℃, 5 ℃, 25 ℃, 35 ℃ and 50 ℃), the pressure can be 0 to 2Mpa, and the total treatment can be carried outThe time is 0.1-12 h (for example, 2h, 4h, 6h, 12 h).
The inventor finds that the introduction of the catalyst can greatly improve the establishment rate of the moisture-proof layer of the non-hydrophobic area and reduce the reaction temperature and the total dosage of the reagent; by introducing the specific hydrophobic reagent, the room-temperature moisture-proof treatment efficiency can be greatly improved under the catalysis condition, so that the reaction can be rapidly carried out under the room-temperature normal-pressure condition, and the excellent moisture-proof treatment efficiency of the process is ensured.
In some preferred embodiments, the optimal content and the minimum impurity content of the moisture-proof layer can be effectively adjusted by adjusting the type or the addition amount of the catalyst and the type or the addition amount of the hydrophobic reagent, so that the hydrophobic performance of the material is stable, and the material has excellent repeatability.
Specifically, the invention provides a rapid moisture-proof method for phenolic aldehyde heat-insulating materials at room temperature and normal pressure, which comprises the following steps:
(1) preparation of hydrophobing agent
Mixing a specific modifier with a molecular structure shown in a molecular formula (1), (2) or (3) with a catalyst consisting of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, sodium hydroxide, potassium carbonate, ammonia water, triethylamine, ethylenediamine, methylamine and acidic or basic substances with the same catalytic efficiency, which are commonly recognized in the field, and a solvent consisting of one or more of acetonitrile, acetone, ethyl acetate, toluene, xylene and alcohol compounds with 1-10 carbon atoms according to a proportion to form the hydrophobic agent with a good hydrophobic modification function.
In the present invention, acrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, nitroethylene, alpha-cyano-methyl acrylate, and alpha-cyano-ethyl acrylate are used as examples but not limited thereto as modifiers; hydrochloric acid, acetic acid, oxalic acid, sodium hydroxide, potassium carbonate, ammonia water and triethylamine are taken as examples and are not limited to the above as catalysts; acetonitrile, acetone, ethyl acetate, toluene, xylene, ethanol are taken as examples, but the solvents are not limited to the above.
(2) And (3) hydrophobization reaction: putting the phenolic aldehyde heat insulating material into a container, introducing the prepared hydrophobing agent into the container, and carrying out room-temperature normal-pressure treatment.
Wherein the room temperature is between-20 deg.C and 50 deg.C (-10 deg.C, -5 deg.C, 25 deg.C, 35 deg.C, 50 deg.C) and ambient temperature, the pressure is 0-2 MPa, and the total treatment time is 0.1-12 h (such as 2h, 4h, 6h, 12 h).
(3) And (3) drying: the drying mode is one or more of forced air drying, forced air heating drying, freeze drying, vacuum heating drying or supercritical drying.
The drying time is 0.1-96 h, preferably one or more of 6h, 12h, 18h, 24h, 30h, 36h, 42h, 48h, 60h, 72h and 96 h. .
The invention provides a modified phenolic aldehyde heat-insulating material and a component with good moisture-proof property in a second aspect, which are characterized in that the modified phenolic aldehyde heat-insulating material and the component comprise the moisture-proof layer structure prepared by the method in the first aspect, the heat protection component has the mass weight gain of less than or equal to 5 percent, the moisture absorption rate of less than or equal to 1 percent and the thermal conductivity change of less than 1 percent after the moisture-proof treatment in the method in the first aspect;
preferably, the modified phenolic aldehyde heat insulation material and the member have the following characteristics: (1) the moisture-proof treatment can be carried out at room temperature and normal pressure, so that the moisture-proof treatment process is greatly simplified. (2) The moisture absorption rate of the mass of the heat insulating material and the component is less than or equal to 1 percent, the structure of the moisture-proof layer is stable, and the destruction behaviors such as decomposition, natural degradation and the like do not occur in the environment of natural state to 150 ℃; (3) the moisture-proof treatment has no obvious influence on the heat-insulating property of the heat-protecting component, and the change of the room-temperature heat conductivity after the moisture-proof treatment is less than 1 percent; (4) the residual quantity of impurities of the thermal protection component except the moisture-proof layer is lower than 1 percent (after drying treatment, the mass change rate is lower than 1 percent after 2 hours of drying treatment in a 120 ℃ oven);
(1) the moisture-proof technology provided by the invention can be used for performing moisture-proof treatment on the phenolic material under the room-temperature normal-pressure environment through the introduction of catalytic reaction and the selection of a special reagent, greatly simplifies the technical difficulty and the treatment time of the moisture-proof treatment, breaks through the bottleneck problem that the existing moisture-proof method for phenolic heat-insulating materials can not completely realize the formation of molecular-level stable hydrophobic structures on the surface of the materials, and greatly reduces the technical difficulty of the moisture-proof treatment of the heat-insulating materials. The heat-insulating property of the moisture-proof heat-insulating material obtained after treatment is not changed, the moisture-proof property is excellent, and the mass moisture absorption rate is less than or equal to 1 percent; the introduction amount of moisture-proof impurities is controllable, and the total residual amount of reagents and byproducts of the material after moisture-proof treatment is less than 1 percent, which is obviously superior to the existing surface spraying type moisture-proof treatment method; the material has stable and controllable weight gain after moisture-proof treatment, and the basic thermophysical property of the material is basically unchanged.
(2) The hydrophobic reaction adopted by the technical method is an addition reaction, no new waste gas and waste solid are generated, no catalyst residue is generated, the reagent is a mature neutral industrialized product, the raw material source is wide and cheap, the environment is friendly, and the material compatibility is good.
(3) The reaction compatibility is good, the formed phenolic aldehyde heat-insulating material can be subjected to hydrophobization modification again, the hydrophobization modification can be completed in the gel stage of the phenolic aldehyde heat-insulating material, and the process compatibility is good.
Example 1
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3A commercial phenolic aerogel composite plate which has room temperature thermal conductivity of 0.06W/(m.K) and is not subjected to moisture-proof treatment is placed in a tank body with the height of 1000mm multiplied by 500 mm. A mixed solvent of 94g of methyl acrylate, 9.4g of triethylamine and 7500g of acetone is added into the tank, the mixture is kept at room temperature and normal pressure for 6h, and then the plate is taken out and dried by air blowing at 120 ℃ for 12 h. The surface of the material is in a hydrophobic state, the weight of the material is increased by 3 percent, the moisture absorption rate is 0.7 percent, and the change of the heat conductivity at room temperature is less than 1 percent.
Example 2
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3A commercial phenolic aerogel composite plate which has room temperature thermal conductivity of 0.06W/(m.K) and is not subjected to moisture-proof treatment is placed in a tank body with the height of 1000mm multiplied by 500 mm. A mixed solvent of 94g of methyl acrylate, 9.4g of ammonia water and 7500g of acetone was added to the pot, the mixture was kept at room temperature under normal pressure for 6 hours, and then the plate was taken out and dried by blowing at 120 ℃ for 12 hours. The surface of the material is in a hydrophobic state, the weight of the material is increased by 3.5%, the moisture absorption rate is 0.6%, and the thermal conductivity at room temperature is unchanged and is less than 1%.
Example 3
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3A commercial phenolic aerogel composite plate which has room temperature thermal conductivity of 0.06W/(m.K) and is not subjected to moisture-proof treatment is placed in a tank body with the height of 1000mm multiplied by 500 mm. Adding mixed solvent of 94g ethyl acrylate, 9.4g concentrated hydrochloric acid and 7500g ethanol into the tank, maintaining at room temperature and normal pressure for 6h, taking out the plate, and vacuum drying at 120 deg.C for 12 h. The surface of the material is in a hydrophobic state, the weight of the material is increased by 4 percent, the moisture absorption rate is 0.7 percent, and the change of the heat conductivity at room temperature is less than 1 percent.
Example 4
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3A commercial phenolic aerogel composite plate which has room temperature thermal conductivity of 0.06W/(m.K) and is not subjected to moisture-proof treatment is placed in a tank body with the height of 1000mm multiplied by 500 mm. A mixed solvent of 94g of acrylonitrile, 18.8g of triethylamine and 7500g of acetonitrile is added into the tank, the mixture is kept at room temperature and normal pressure for 6h, and then the plate is taken out and dried in vacuum for 12h at 120 ℃. The surface of the material is in a hydrophobic state, the weight of the material is increased by 2.8 percent, the moisture absorption rate is 0.8 percent, and the change of the heat conductivity at room temperature is less than 1 percent.
Example 5
Taking the outer diameter of 500mm, the wall thickness of 20mm and the density of 0.5g/cm3And one hemispherical phenolic aerogel composite plate which has the room temperature thermal conductivity of 0.06W/(m.K) and is not subjected to moisture-proof treatment is placed in a tank body with the height of 1000mm multiplied by 500 mm. A mixed solvent of 362g of acrylonitrile, 72g of triethylamine and 75000g of acetonitrile was added to the pot, and the mixture was kept at room temperature under normal pressure for 6 hours, and then taken out and vacuum-dried at 120 ℃ for 12 hours. The material is in a hydrophobic state, the weight of the material is increased by 2.8%, the moisture absorption rate is 0.8%, and the change of the heat conductivity at room temperature is less than 1%.
Comparative example 1
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3A commercial phenolic aerogel composite plate which has room temperature thermal conductivity of 0.06W/(m.K) and is not subjected to moisture-proof treatment is placed in a tank body with the height of 1000mm multiplied by 500 mm. A mixed solvent of 94g of trimethylmethoxysilane, 18.8g of triethylamine and 7500g of acetonitrile was added to the pot, and the mixture was kept at room temperature and normal pressure for 6 hours. Then taking out the plate, and drying the plate by air blow at 120 ℃ for 24 h. Partial hydrophobicity on material surfaceAnd the moisture absorption rate of the material is 9 percent.
Comparative example 2
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3A commercial phenolic aerogel composite plate which has room temperature thermal conductivity of 0.06W/(m.K) and is not subjected to moisture-proof treatment is placed in a tank body with the height of 1000mm multiplied by 500 mm. A mixed solvent of 94g of trimethylchlorosilane, 18.8g of triethylamine and 7500g of acetonitrile is added into a tank, the mixed solvent is kept at room temperature and normal pressure for 6 hours, and then the plate is taken out and is dried by air blowing at 120 ℃ for 6 hours. The surface of the material is not hydrophobic, and the moisture absorption rate is 12%.
Comparative example 3
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3A commercial phenolic aerogel composite plate which has room temperature thermal conductivity of 0.06W/(m.K) and is not subjected to moisture-proof treatment is placed in a tank body with the height of 1000mm multiplied by 500 mm. A mixed solvent of 18.8g of triethylamine and 7500g of acetonitrile is added into the tank, the mixture is kept at room temperature and normal pressure for 6h, and then the plate is taken out and dried by air blowing at 120 ℃ for 12 h. The surface of the material is not hydrophobic, and the moisture absorption rate is 22%.
Comparative example 4
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3And the surface of a commercial phenolic aerogel composite material plate which has room temperature thermal conductivity of 0.06W/(m.K) and is not subjected to moisture-proof treatment is sprayed with a commercial waterproof coating and dried. The outer surface of the material is hydrophobic, the moisture absorption rate is 18%, and the interior of the material does not have hydrophobic performance after being cut.
From the comparison of the material properties of the above examples with the comparative examples, it can be seen that:
the moisture-proof technology provided by the invention can be used for performing moisture-proof treatment on the phenolic material under the room-temperature normal-pressure environment through the introduction of catalytic reaction and the selection of a special reagent, greatly simplifies the technical difficulty and the treatment time of the moisture-proof treatment, breaks through the bottleneck problem that the existing moisture-proof method for phenolic heat-insulating materials can not completely realize the formation of molecular-level stable hydrophobic structures on the surface of the materials, and greatly reduces the technical difficulty of the moisture-proof treatment of the heat-insulating materials. The heat-insulating property of the moisture-proof heat-insulating material obtained after treatment is not changed, the moisture-proof property is excellent, and the mass moisture absorption rate is less than or equal to 1 percent; the introduction amount of moisture-proof impurities is controllable, and the total residual amount of reagents and byproducts of the material after moisture-proof treatment is less than 1 percent, which is obviously superior to the existing surface spraying type moisture-proof treatment method; the material has stable and controllable weight gain after moisture-proof treatment, and the basic thermophysical property of the material is basically unchanged.
(2) The hydrophobic reaction adopted by the technical method is an addition reaction, no new waste gas and waste solid are generated, no catalyst residue is generated, the reagent is a mature neutral industrialized product, the raw material source is wide and cheap, the environment is friendly, and the material compatibility is good.
(3) The reaction compatibility is good, the formed phenolic aldehyde heat-insulating material can be subjected to hydrophobization modification again, the hydrophobization modification can be completed in the gel stage of the phenolic aldehyde heat-insulating material, and the process compatibility is good.
It should be noted that the above embodiments can be freely combined as necessary. The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The moisture-proof modified phenolic aldehyde heat-insulating material is characterized by comprising the following steps of:
(1) preparing a water repellent agent: mixing a hydrophobic modifier with a catalyst and a solvent to prepare a hydrophobic agent with a hydrophobic modification function;
(2) and (3) hydrophobization reaction: and adding the hydrophobization reagent into the phenolic thermal insulation material for soaking at room temperature to perform hydrophobization reaction.
(3) And (3) drying: after the hydrophobization reaction is finished, removing redundant hydrophobization reagents in a drying mode under the in-situ condition to obtain the moisture-proof modified phenolic aldehyde heat-insulating material.
2. The method according to claim 1, wherein in the step (1), the modifier is an agent having the formula (1), (2) or (3),
wherein R is1Selected from the group consisting of-H, -CN, -NO2、-SO2R7、-SO2N R7R8、-COR7、-COOR7、-CONR7R8One of (1), R2Selected from the group consisting of-CN, -NO2、-SO2R7、-SO2N R7R8、-COR7、-COOR7、-CONR7R8One of (1), R3,R4,R5And R6Are all independently selected from the group consisting of-H, -CN, -NO2、-SO2R7、-SO2NR7R8、-COR7、-COOR7、-CONR7R8Or one of carbon chain groups having 1 to 10 carbons, R7And R8Are independently selected from one of-H or a carbon chain group having 1-10 carbons.
3. The preparation method according to claim 1, wherein in the step (1), the amount of the hydrophobic modifier is 1-20% of the total weight of the phenolic insulation material.
4. The method according to claim 1, wherein in step (1), the catalyst is one or more selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, formic acid, sodium hydroxide, potassium carbonate, ammonia, triethylamine, ethylenediamine, and methylamine.
5. The preparation method according to claim 1, wherein in the step (1), the catalyst is used in an amount of 0.1 to 20% by mass based on the mass of the modifier.
6. The preparation method according to claim 1, wherein in the step (1), the solvent is selected from one or more of acetonitrile, acetone, ethyl acetate, toluene, xylene and C1-C10 alcohol compounds, and the amount of the solvent is 2-5 times of the mass of the phenolic insulation material.
7. The method of claim 1, wherein the phenolic insulation material is a phenolic ablative composite, a phenolic aerogel composite, or a porous composite of multiple resins or polymer blends containing phenolic resin.
8. The preparation method according to claim 1, wherein the soaking time in the step (2) is 0.1-12 h.
9. The method according to claim 1, wherein the drying time in step (3) is 0.1 to 96 hours.
10. A modified phenolic insulation material, characterized in that it is produced by the method of any one of claims 1 to 9; the moisture-proof modified phenolic aldehyde heat-insulating material has the mass weight percentage of less than or equal to 3 percent relative to the phenolic aldehyde heat-insulating material used as the raw material, the moisture absorption rate change is less than or equal to 1 percent, and the thermal conductivity change is less than 1 percent.
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| US20080206545A1 (en) * | 2007-02-26 | 2008-08-28 | Industrial Technology Research Institute | Porous material and method for preparing the same |
| CN105037737A (en) * | 2015-06-18 | 2015-11-11 | 西安理工大学 | Free radical nano-capture material and preparation method thereof |
| CN106867405A (en) * | 2017-03-03 | 2017-06-20 | 北京理工大学 | A kind of hydrophobic coating based on dentritic polyamidoamine and preparation method thereof |
| CN110963820A (en) * | 2019-12-09 | 2020-04-07 | 航天特种材料及工艺技术研究所 | Moisture-proof treatment method for heat-insulating material and application thereof |
| CN111808249A (en) * | 2020-07-22 | 2020-10-23 | 苏州兴业材料科技南通有限公司 | Preparation method of phenolic resin for automobile filter paper |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080206545A1 (en) * | 2007-02-26 | 2008-08-28 | Industrial Technology Research Institute | Porous material and method for preparing the same |
| CN105037737A (en) * | 2015-06-18 | 2015-11-11 | 西安理工大学 | Free radical nano-capture material and preparation method thereof |
| CN106867405A (en) * | 2017-03-03 | 2017-06-20 | 北京理工大学 | A kind of hydrophobic coating based on dentritic polyamidoamine and preparation method thereof |
| CN110963820A (en) * | 2019-12-09 | 2020-04-07 | 航天特种材料及工艺技术研究所 | Moisture-proof treatment method for heat-insulating material and application thereof |
| CN111808249A (en) * | 2020-07-22 | 2020-10-23 | 苏州兴业材料科技南通有限公司 | Preparation method of phenolic resin for automobile filter paper |
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