CN112480467A - 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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- 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 solvent to prepare a hydrophobic modifier with a hydrophobic modification function; (2) and (3) hydrophobization reaction: adding the hydrophobizing agent into a phenolic aldehyde heat-insulating material for heat preservation so as to perform hydrophobizing reaction; (3) and (3) drying: after the hydrophobization reaction is completed, removing the redundant hydrophobization reagent in an in-situ condition by a heating mode to obtain the moisture-proof modified phenolic thermal insulation material. The heat insulating material of the present invention is excellent in moisture resistance.
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 preparation method of a moisture-proof modified phenolic aldehyde heat-insulating material, which comprises the following steps:
(1) preparing a water repellent agent: mixing a hydrophobic modifier with a solvent to prepare a hydrophobic modifier with a hydrophobic modification function;
(2) and (3) hydrophobization reaction: adding the hydrophobizing agent into a phenolic aldehyde heat-insulating material for heat preservation so as to perform hydrophobizing reaction;
(3) and (3) drying: after the hydrophobization reaction is completed, removing the redundant hydrophobization reagent in an in-situ condition by a heating mode to obtain the moisture-proof modified phenolic thermal insulation material.
Further, in the step (1), the hydrophobic modifier is selected from agents having a molecular structure represented by formula (1) or formula (2):
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.
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 solvent is selected from one or more of acetonitrile, acetone, ethyl acetate, toluene, xylene and alcohol compounds with 1-10 carbons; the dosage of the solvent is 0-5 times of the mass of the hydrophobic modifier.
Further, the phenolic aldehyde heat-insulating material is a phenolic aldehyde resin-based porous composite 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.
Furthermore, the hydrophobizing agent is added in a gas phase fumigation introduction mode, the gas phase fumigation introduction is realized by placing the phenolic aldehyde heat insulation material in a closed container, and then the container is vacuumized and then is sucked into the hydrophobizing agent.
Further, in the step (2), the heat preservation temperature is 30-300 ℃, and the heat preservation time is 0.1-96 hours.
Further, in the step (3), the heating temperature for heating is 0-90 ℃; the heating time is 0.1-96 h; the heating mode is selected from one or more of blast heating and vacuum heating.
In a second aspect, the invention provides a moisture-proof modified phenolic aldehyde heat-insulating material, which is prepared by the method; 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 breaks through the bottleneck problem that the existing phenolic thermal insulation material moisture-proof method cannot form a molecular level stable hydrophobic structure on the surface of the material through the selection of a special reagent and a hydrophobic reaction type, and greatly reduces the technical difficulty of moisture-proof treatment of the thermal insulation material. 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 hydrophobic reaction has good compatibility, the whole reaction process always keeps neutral and low-toxicity environment, and the method has no corrosive influence on members such as metal, rubber and the like, can be suitable for hydrophobic moisture-proof treatment of multi-component phenolic aldehyde heat-insulating members, and has wide applicability.
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 preparation method of a moisture-proof modified phenolic aldehyde heat-insulating material comprises the following steps:
(1) preparing a water repellent agent: mixing a hydrophobic modifier with a solvent to prepare a hydrophobic modifier with a hydrophobic modification function;
(2) and (3) hydrophobization reaction: adding the hydrophobizing agent into a phenolic aldehyde heat-insulating material for heat preservation so as to perform hydrophobizing reaction;
(3) and (3) drying: after the hydrophobization reaction is completed, removing the redundant hydrophobization reagent in an in-situ condition by a heating mode to obtain the moisture-proof modified phenolic thermal insulation material.
Further, in the step (1), the hydrophobic modifier is selected from the group consisting of agents having a molecular structure represented by formula (1) or formula (2):
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 selected from the group consisting of-H, -CN, -NO2、-SO2R7、-SO2NR7R8、-COR7、-COOR7、-CONR7R8Or a carbon chain radical having from 1 to 10 carbons, R7And R8Are each selected from the group consisting of-H or a carbon chain group having 1 to 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 solvent is selected from one or more of acetonitrile, acetone, ethyl acetate, toluene, xylene and alcohol compounds with 1-10 carbons; the dosage of the solvent is 0-5 times of the mass of the hydrophobic modifier.
Further, the phenolic aldehyde heat-insulating material is a phenolic aldehyde resin-based porous composite 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.
Furthermore, the hydrophobizing agent is added in a gas phase fumigation introduction mode, the gas phase fumigation introduction is realized by placing the phenolic aldehyde heat insulation material in a closed container, and then the container is vacuumized and then is sucked into the hydrophobizing agent.
Further, in the step (2), the heat preservation temperature is 30-300 ℃, and the heat preservation time is 0.1-96 hours.
Further, in the step (3), the heating temperature for heating is 0-90 ℃; the heating time is 0.1-96 h; the heating mode is selected from one or more of blast heating and vacuum heating.
The moisture-proof modified phenolic aldehyde heat-insulating material is prepared by the method; 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 invention provides a moisture-proof treatment method for phenolic insulation materials, wherein the phenolic insulation materials comprise phenolic matrixes or fibersThe heat insulation material is processed by the processing method under the condition of heat preservation in a gas phase environment, the processing process is non-corrosive, and the compatibility of the heat insulation material to materials such as metal, rubber and the like is good. After the material is dried, the other properties of the material are not obviously affected, and the drying treatment can be repeatedly carried out for many times. The hydrophobization modifying agent selected in the method is an agent with a molecular structure of formula (1) or (2), wherein R1Is 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 1-20% (e.g. 1%, 2%, 5%, 10%, 20%) of the total weight of the phenolic insulation material. In the method, the selected diluting agent is one or more of acetonitrile, acetone, ethyl acetate, toluene, xylene and C1-C10 alcohol compounds, and the dosage of the solvent is 0-5 times (for example, 0, 1, 1.5, 2 and 5 times) of the mass of the modifier. The reagent is introduced in a vacuum mode and is fumigated in a gas phase mode. The temperature of the hydrophobic treatment is 30-300 ℃ (such as 35 ℃, 45 ℃, 55 ℃, 65 ℃, 75 ℃, 85 ℃, 90 ℃, 100 ℃, 150 ℃, 200 ℃ and 300 ℃), and the heat preservation time is 0.1-96 h (such as one or more of 6h, 12h, 18h, 24h, 30h, 36h, 42h, 48h, 60h, 72h and 96 h). The drying mode is one or more of blast heating and vacuum heating, the drying temperature is 0-90 ℃ (for example, one or more of 25 ℃, 35 ℃, 45 ℃, 55 ℃, 65 ℃, 75 ℃ and 85 ℃), and the drying heat time is 0.1-96 h (for example, one or more of 6h, 12h, 18h, 24h, 30h, 36h, 42h, 48h, 60h, 72h and 96 h).
The inventor finds that the modifier with the molecular structure characteristics in the molecular formula (1) or (2) can react with the exposed phenolic hydroxyl on the surface of the phenolic composite material under certain conditions to form a stable hydrophobic structure which is not easy to hydrolyze on the molecular level, so that the hydrophobic and moisture-proof operation of the phenolic porous heat-insulating material is realized. The reagent is a good neutral and low-toxicity commercialized reagent, and the reaction is an addition reaction and does not generate byproducts, so the process has good compatibility with parts such as metal, rubber and the like, can be widely applied to moisture-proof treatment of phenolic-based heat-insulating materials, porous composite materials containing phenolic aldehyde and parts, and the moisture absorption rate of the treated materials can be reduced to within 1%.
In some preferred embodiments, the optimal content of the moisture-proof layer is effectively adjusted by adjusting the type or the addition amount of the modifier, the solvent ratio, the reaction temperature and the reaction time, so that the stability of the hydrophobic property and the good moisture resistance of the material are ensured.
Specifically, the invention provides a moisture-proof method of phenolic aldehyde heat-insulating material and modified phenolic aldehyde heat-insulating material prepared by the method, wherein the method comprises the following steps:
(1) preparation of hydrophobing agent
A hydrophobizing agent having a good hydrophobizing modification function is formed by mixing a specific modifier having a molecular structure represented by the formula (1) or (2) with a solvent consisting of one or more of acetonitrile, acetone, ethyl acetate, toluene, xylene and a C1-10 alcohol compound at a ratio of 1: 0-1: 5 (e.g., 1:0, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:4, 1: 5).
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; 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: placing the phenolic aldehyde heat-insulating material into a container, introducing the prepared water repellent agent into the container, and carrying out heat preservation treatment.
Wherein the heat preservation temperature is 30-300 ℃ (such as 35 ℃, 45 ℃, 55 ℃, 65 ℃, 75 ℃, 85 ℃, 90 ℃, 100 ℃, 150 ℃, 200 ℃ and 300 ℃), and the heat preservation time is 0.1-96 h (such as one or more of 6h, 12h, 18h, 24h, 30h, 36h, 42h, 48h, 60h, 72h and 96 h).
(3) And (3) drying: after the hydrophobization reaction is finished, removing redundant hydrophobization reagents in a heating mode under the in-situ condition to obtain the high-efficiency moisture-proof modified phenolic aldehyde heat-insulating material with low moisture absorption rate.
The drying method is one or more of blast heating and vacuum heating, the drying temperature is 0-90 ℃ (for example, one or more of 25 ℃, 35 ℃, 45 ℃, 55 ℃, 65 ℃, 75 ℃ and 85 ℃), and the drying heat time is 0.1-96 h (for example, one or more of 6h, 12h, 18h, 24h, 30h, 36h, 42h, 48h, 60h, 72h and 96 h).
The modified phenolic aldehyde heat-insulating material and the component with good moisture-proof property are characterized by comprising the moisture-proof layer structure prepared by the method, the heat protection component is subjected to moisture-proof treatment by the method, the weight gain is less than or equal to 3%, the moisture absorption rate is less than or equal to 1%, and the change of the heat conductivity is less than 1%.
In some embodiments, the modified phenolic insulation materials and components have the following characteristics: (1) the modified phenolic aldehyde heat-insulating material does not generate corrosive influence on parts such as metal, rubber and the like contained in the material and the member in the moisture-proof treatment process, and can realize moisture-proof treatment of a complex structure; (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);
the present invention is described in detail below with reference to specific examples, but the scope of the present invention is not limited to these examples.
Example 1
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3And placing 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 into a tank body with the height of 800mm and the diameter of phi 800mm, and keeping the atmosphere communicated state and keeping the temperature at 60 ℃ for 4 hours. And (3) vacuumizing the tank under the condition of keeping the temperature unchanged, sucking 187.5g of methyl acrylate, sealing the tank, keeping the temperature at 60 ℃ for 12 hours, taking out the plate, and drying by blowing at 90 ℃ for 6 hours. The surface of the material is in a hydrophobic state, the weight of the material is increased by 2 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 2
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3And placing 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 into a tank body with the height of 800mm and the diameter of phi 800mm, and keeping the atmosphere communicated state and keeping the temperature at 60 ℃ for 4 hours. And (3) vacuumizing the tank under the condition of keeping the temperature unchanged, sucking a mixed solution of 187.5g of methyl acrylate and 187.5g of acetone, sealing the tank, keeping the temperature at 60 ℃ for 12 hours, taking out the plate, and drying by blowing at 90 ℃ for 6 hours. The surface of the material is in a hydrophobic state, the weight of the material is increased by 2.5%, 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/cm3And placing 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 into a tank body with the height of 800mm and the diameter of phi 800mm, and keeping the atmosphere communicated state and keeping the temperature at 60 ℃ for 4 hours. And (3) vacuumizing the tank under the condition of keeping the temperature unchanged, sucking 187.5g of ethyl acrylate, sealing the tank, keeping the temperature at 60 ℃ for 12 hours, taking out the plate, and drying by blowing at 90 ℃ for 6 hours. The surface of the material is in a hydrophobic state, the weight of the material is increased by 2.3%, the moisture absorption rate is 0.8%, and the change of the heat conductivity at room temperature is less than 1%.
Example 4
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3A commercial phenolic aerogel composite material plate with room temperature thermal conductivity of 0.06W/(m.K) and without moisture-proof treatment is placed in a tank body with the height of 800mm and the diameter of phi 800mmKeeping the atmosphere connected state and keeping the temperature at 90 ℃ for 4 h. And (3) vacuumizing the tank under the condition of keeping the temperature unchanged, sucking 187.5g of acrylonitrile, sealing the tank, keeping the temperature at 90 ℃ for 12 hours, taking out the plate, and drying the plate by blowing at 90 ℃ for 6 hours. The surface of the material is in a hydrophobic state, the weight of the material is increased by 1.6%, the moisture absorption rate is 0.9%, and the change of the heat conductivity at room temperature is less than 1%.
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 material plate which has the room temperature thermal conductivity of 0.06W/(m.K) and is not subjected to moisture-proof treatment is internally riveted with an aluminum alloy hemispherical component with the thickness of 2mm, and the aluminum alloy hemispherical component is placed in a tank body with the height of 800mm and the diameter of 800mm, and is kept in an atmosphere communication state for heat preservation for 4 hours at the temperature of 90 ℃. And (3) vacuumizing the tank under the condition of keeping the temperature unchanged, sucking 362g of acrylonitrile, sealing the tank, keeping the temperature at 90 ℃ for 12 hours, taking out the hemispherical member, and drying by blowing at 90 ℃ for 6 hours. The surface of partial material of the phenolic aldehyde heat-insulating material is in a hydrophobic state, the weight of the material is increased by 1.6%, the moisture absorption rate is 0.9%, 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/cm3And placing 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 into a tank body with the height of 800mm and the diameter of phi 800mm, and keeping the atmosphere communicated state and keeping the temperature at 60 ℃ for 4 hours. And (3) vacuumizing the tank under the condition of keeping the temperature unchanged, sucking 187.5g of trimethyl methoxysilane, sealing the tank, keeping the temperature for 12 hours, taking out the plate, and drying by blowing at 90 ℃ for 6 hours. The surface of the material is locally hydrophobic, and the moisture absorption rate of the material is 8%.
Comparative example 2
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3And placing 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 into a tank body with the height of 800mm and the diameter of phi 800mm, and keeping the atmosphere communicated state and keeping the temperature at 60 ℃ for 4 hours. And (3) vacuumizing the tank under the condition of keeping the temperature unchanged, sucking 187.5g of trimethylchlorosilane, sealing the tank, keeping the temperature at 60 ℃ for 12 hours, taking out the plate, and drying the plate by blowing at 90 ℃ for 6 hours. The surface of the material is not hydrophobic, and the moisture absorption rate is 15%.
Comparative example 3
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3And placing 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 into a tank body with the height of 800mm and the diameter of phi 800mm, and keeping the atmosphere communicated state and keeping the temperature at 60 ℃ for 4 hours. And (3) vacuumizing the tank under the condition of keeping the temperature unchanged, sucking 187.5g of acetone, sealing the tank, keeping the temperature at 60 ℃ for 12 hours, taking out the plate, and drying the plate by blowing at 90 ℃ for 6 hours. 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 breaks through the bottleneck problem that the existing phenolic thermal insulation material moisture-proof method cannot form a molecular level stable hydrophobic structure on the surface of the material through the selection of a special reagent and a hydrophobic reaction type, and greatly reduces the technical difficulty of moisture-proof treatment of the thermal insulation material. 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.
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.
The hydrophobic reaction has good compatibility, the whole reaction process always keeps neutral and low-toxicity environment, and the method has no corrosive influence on members such as metal, rubber and the like, can be suitable for hydrophobic moisture-proof treatment of multi-component phenolic aldehyde heat-insulating members, and has wide applicability.
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 preparation method of 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 solvent to prepare a hydrophobic modifier with a hydrophobic modification function;
(2) and (3) hydrophobization reaction: adding the hydrophobizing agent into a phenolic aldehyde heat-insulating material for heat preservation so as to perform hydrophobizing reaction;
(3) and (3) drying: after the hydrophobization reaction is completed, removing the redundant hydrophobization reagent in an in-situ condition by a heating mode to obtain the moisture-proof modified phenolic thermal insulation material.
2. The method according to claim 1, wherein in step (1), the hydrophobic modifier is selected from agents having a molecular structure represented by formula (1) or formula (2):
wherein R is1Selected from the group consisting of-H, -CN, -NO2、-SO2R7、-SO2NR7R8、-COR7、-COOR7、-CONR7R8One of (1), R2Selected from the group consisting of-CN, -NO2、-SO2R7、-SO2NR7R8、-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 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 alcohols having 1 to 10 carbons; the dosage of the solvent is 0-5 times of the mass of the hydrophobic modifier.
5. The method according to claim 1, wherein the phenolic insulation material is a phenolic resin-based porous composite material.
6. The method of claim 5, 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.
7. The method of claim 1, wherein the hydrophobizing agent is added by gas phase fumigation by placing the phenolic insulation material in a closed container and then drawing the hydrophobizing agent in after the container is evacuated.
8. The preparation method according to claim 1, wherein in the step (2), the heat preservation temperature is 30-300 ℃, and the heat preservation time is 0.1-96 h.
9. The method of claim 1, wherein:
in the step (3), the heating temperature of the heating is 0-90 ℃; the heating time is 0.1-96 h; the heating mode is selected from one or more of blast heating and vacuum heating.
10. A moisture-resistant modified phenolic insulation material, characterized in that it is 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.
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| CN113817219A (en) * | 2021-10-09 | 2021-12-21 | 航天特种材料及工艺技术研究所 | Modified oxide hybrid phenolic insulation material and preparation method thereof |
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| 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 |
| EP3498672A1 (en) * | 2017-12-15 | 2019-06-19 | EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt | Superinsulating silica aerogel with high stiffness and density |
| 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 |
| CN111659326A (en) * | 2020-06-12 | 2020-09-15 | 浙江岩谷科技有限公司 | Modification method of hydrophobic aerogel material |
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| 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 |
| EP3498672A1 (en) * | 2017-12-15 | 2019-06-19 | EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt | Superinsulating silica aerogel with high stiffness and density |
| 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 |
| CN111659326A (en) * | 2020-06-12 | 2020-09-15 | 浙江岩谷科技有限公司 | Modification method of hydrophobic aerogel material |
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| CN113817219A (en) * | 2021-10-09 | 2021-12-21 | 航天特种材料及工艺技术研究所 | Modified oxide hybrid phenolic insulation material and preparation method thereof |
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