CN113817219A - Modified oxide hybrid phenolic insulation material and preparation method thereof - Google Patents
Modified oxide hybrid phenolic insulation material and preparation method thereof Download PDFInfo
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- CN113817219A CN113817219A CN202111177732.4A CN202111177732A CN113817219A CN 113817219 A CN113817219 A CN 113817219A CN 202111177732 A CN202111177732 A CN 202111177732A CN 113817219 A CN113817219 A CN 113817219A
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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
- C08J9/36—After-treatment
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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
- 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
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Abstract
The invention belongs to the technical field of thermal protection, and discloses a modified oxide hybrid phenolic aldehyde heat-insulating material and a preparation method thereof. The method comprises the following steps: (1) preparing a modifier: mixing the modifying agent with an optional solvent to prepare a modifying agent with a hydrophobic modification function; (2) modification reaction: introducing the modifier into an oxide hybrid phenolic aldehyde heat-insulating material for heat preservation so as to carry out modification reaction; (3) and (3) drying: after the modification reaction is finished, removing redundant reagents and byproducts in a heating mode under an in-situ condition to obtain the oxide hybrid phenolic aldehyde heat-insulating material with the moisture-proof performance. The heat insulation performance of the heat insulation material is hardly affected adversely, and the heat insulation material has excellent moisture resistance, and after modification treatment, the mass weight gain percentage is less than or equal to 3%, the mass moisture absorption rate is less than or equal to 1%, and/or the heat conductivity change is less than 1%.
Description
Technical Field
The invention relates to the technical field of thermal protection, in particular to a modified oxide hybrid 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 for the purpose of facilitating an understanding of the summary of the invention, and should not be read as an admission or suggestion that the applicant would consider prior art to the filing date of the first filed application.
The porous heat-insulating material represented by the phenolic aldehyde heat-insulating material, particularly the oxide hybrid phenolic aldehyde heat-insulating 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 surface modification treatment is not carried out, the material is influenced by moisture, fog or rainwater in the air in the long-term storage or use process, a large amount of moisture can be 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.
For the oxide hybrid phenolic insulation material, in order to take ablation resistance and efficient heat insulation performance into consideration, the oxide and phenolic components account for a certain proportion, the moisture absorption characteristics can be independently generated due to the existence of a plurality of components, and the requirement for single modification of a single component can not be met gradually.
In contrast, at present, there are mature moisture-proof technologies for oxide components (such as aerogel, quartz fiber felt, alumina fiber, porous ceramic tile, etc.), but although the commonly used hydrophobing agents (such as trimethylmethoxysilane, trimethylchlorosilane, hexamethyldisilazane, etc.) can form a stable hydrophobic structure with hydroxyl on the surface of the oxide to complete surface modification, the hydrophobing agents are difficult to react with other organic components in the phenolic composite material, and cannot well achieve a long-term and efficient moisture-proof effect. Therefore, for phenolic composite materials, no proper modified moisture-proof treatment method exists at present.
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 and prevent the materials from absorbing the liquid water in a physical blocking mode, but cannot fundamentally solve the problem that the surfaces of pores in the materials absorb and enrich the gaseous water. Meanwhile, due to the large difference of surface reactivity among the components, the modification methods suitable for the components interfere with each other when used together. The use and shelf life of the high performance insulation materials in large, highly integrated thermal protection systems is compromised.
Disclosure of Invention
The embodiment of the invention aims to provide a modified oxide hybrid phenolic insulation material and a preparation method thereof, wherein the modified phenolic insulation material has excellent moisture resistance.
To achieve the object of the present invention, the present invention provides in a first aspect a method for preparing a modified oxide hybrid phenolic thermal insulation material, the method comprising the steps of:
(1) preparing a modifier: mixing a modifying agent with a solvent to prepare a modifying agent with a hydrophobic modification function;
(2) modification reaction: adding the modifier into an oxide hybridized phenolic aldehyde heat-insulating material, and keeping the temperature to perform modification reaction;
(3) and (3) drying: after the modification reaction is finished, removing the redundant modifier in a heating mode under the in-situ condition to obtain the modified oxide hybrid phenolic aldehyde heat-insulating material with the moisture-proof performance.
In some preferred embodiments, in step (1), the modifying agent comprises a first modifying agent selected from one or more agents having a molecular structure represented by formula (1) or formula (2), and a second modifying agent selected from one or more agents having a molecular structure represented by formula (3) or formula (4):
R1OOMOO R2 (1)，
R3X (2)，
R4R5SiR6R7 (3)，
R4R5R6SiNHSiR4R5R6 (4)，
wherein M is C and/or S; x is selected from-F, -Cl, -Br, -I, -CN, -NO2、-SO2R8One or more of; r1,R2,R3Independently selected from-H, -CN, -NO2、-SO2R8、-SO2NR8R9、-COR8、-COOR8、-CONR8R9One or more of a carbon chain group having 1 to 10 carbons, a silicon chain group having 1 to 10 silicon atoms, or a carbon-silicon heterochain group having 1 to 10 carbon atoms and silicon atoms in total; r8And R9One or more groups independently selected from-H or a carbon chain group having 1-10 carbons, a silicon chain group having 1-10 silicon atoms, or a carbon-silicon heterochain group having a total of 1-10 carbon atoms and silicon atoms; r4,R5,R6,R7Independently selected from-H, -F, -Cl, -Br, -I, -CN, -NO2、-R8,-OR8,-SO2R8、-SO2NR8R9、-COR8、-COOR8、-CONR8R9One or more groups of (a).
In some further preferred or further preferred embodiments, in step (2), the modifier is used in an amount of 1% to 20% by weight based on the total weight of the oxide hybrid phenolic insulation material.
In some further preferred or further preferred embodiments, in the step (1), the solvent is selected from one or more of acetonitrile, acetone, ethyl acetate, toluene, xylene, and alcohol compounds having 1 to 10 carbons; the dosage of the solvent is 0-5 times of the mass of the modifying reagent.
In some further preferred or further preferred embodiments, the oxide hybrid phenolic insulation material is an oxide hybrid phenolic resin based porous composite material.
In some further preferred or further preferred embodiments, the oxide hybrid phenolic insulation material is an oxide hybrid phenolic ablative porous composite, an oxide hybrid phenolic aerogel composite, or a porous composite comprising an oxide hybrid phenolic resin.
In some further preferred or further preferred embodiments, the modifier is introduced by gas phase fumigation by placing the oxide hybrid phenolic insulation material in a closed container and then drawing the modifier into the container after the container is evacuated.
In some other preferred or further preferred embodiments, in the step (2), the heat preservation temperature of the heat preservation is 30-300 ℃, and the heat preservation time of the heat preservation is 0.1-96 h.
In some further preferred or further preferred embodiments, in step (3), the heating temperature of the heating is 25 ℃ to 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 present invention provides a modified oxide hybrid phenolic insulation material prepared by the method of the first aspect of the invention. Preferably, the mass weight percentage of the modified oxide hybrid phenolic insulation material relative to the oxide hybrid phenolic insulation material used as a raw material is less than or equal to 3%, the moisture absorption rate is less than or equal to 1%, and/or the thermal conductivity change is less than 1%.
The embodiment of the invention has the following beneficial effects:
(1) the modification technology provided by the invention breaks through the bottleneck problem that the existing modification method of the oxide hybrid phenolic thermal insulation material cannot form a molecular-level stable hydrophobic structure on the surface of the material and the problem that modification reactions among different components of the material interfere with each other through selection of a special reagent and a modification reaction type, and greatly reduces the technical difficulty of damp-proof modification treatment of the thermal insulation material. The heat insulation performance of the moisture-proof heat insulation material obtained after treatment is hardly influenced adversely, and the moisture-proof heat insulation material has excellent moisture resistance, and the mass moisture absorption rate is less than or equal to 1 percent; the introduction amount of impurities introduced in the process of damp-proof treatment is controllable, and the total residual amount of reagents and byproducts after the materials are modified is less than 1 percent, which is obviously superior to the existing surface spraying type treatment method; the weight gain of the modified material is stable and controllable, and the basic thermophysical property of the material is basically not adversely affected.
(2) The modification reaction adopted by the technical method of the invention does not need a catalyst and has no byproduct residue, the adopted reagent is a mature industrialized product, the raw material source is wide and cheap, and the method can be used in a large scale.
(3) The modification reaction has good compatibility, can be suitable for surface modification treatment of oxide hybrid phenolic aldehyde heat-insulating members of multi-component types, 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.
The invention provides a preparation method of a modified oxide hybrid phenolic aldehyde heat-insulating material in a first aspect, which comprises the following steps:
(1) preparing a modifier: mixing a modifying agent with an optional solvent to prepare a modifying agent with a hydrophobic modification function;
(2) modification reaction: introducing the modifier into an oxide hybrid phenolic aldehyde heat-insulating material for heat preservation so as to carry out modification reaction;
(3) and (3) drying: after the modification reaction is finished, removing redundant modifying reagents in a heating mode under the in-situ condition to obtain the modified oxide hybrid phenolic aldehyde heat-insulating material with the moisture-proof performance.
In some preferred embodiments, in step (1), the modifying agent comprises a first modifying agent selected from one or more agents having a molecular structure represented by formula (1) or formula (2), and a second modifying agent selected from one or more agents having a molecular structure represented by formula (3) or formula (4):
R1OOMOO R2 (1)，
R3X (2)，
R4R5SiR6R7 (3)，
R4R5R6SiNHSiR4R5R6 (4)，
wherein M is C and/or S; x is selected from-F, -Cl, -Br, -I, -CN, -NO2、-SO2R8One or more of; r1,R2,R3Independently selected from-H, -CN, -NO2、-SO2R8、-SO2NR8R9、-COR8、-COOR8、-CONR8R9A carbon chain group having 1 to 10 carbons, a silicon chain group having 1 to 10 silicon atoms, or a carbon silicon heterochain group having a total of 1 to 10 carbon atoms and silicon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10); r8And R9One or more groups independently selected from-H or a carbon chain group having 1-10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbons, a silicon chain group having 1-10 silicon, or a carbon-silicon heterochain group having a total of 1-10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon and silicon atoms; r4,R5,R6,R7Independently selected from-H, -F, -Cl, -Br, -I, -CN, -NO2、-R8,-OR8,-SO2R8、-SO2NR8R9、-COR8、-COOR8、-CONR8R9One or more groups of (a).
The invention provides a method for preparing an oxide hybrid phenolic aldehyde heat-insulating materialThe oxide hybrid phenolic aldehyde heat insulation material is all heat insulation materials containing an oxide hybrid phenolic aldehyde matrix or fibers, the treatment method is carried out under the condition of heat preservation in a gas phase environment, and the compatibility of the treatment process 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 hydrophobic modifier is selected from the group consisting of one or more reagents having molecular structures represented by formulas (1) and (2) and one or more reagents having molecular structures represented by formulas (3) and (4), wherein M is selected from the group consisting of C, S, and X is selected from the group consisting of-F, -Cl, -Br, -I; r1,R2,R3Independently selected from the group consisting of-H, -CN, -NO2、-SO2R8、-SO2NR8R9、-COR8、-COOR8、-CONR8R9Or a carbon chain or silicon chain or carbo-silicon heterochain group having 1-10 carbons or silicon; r8And R9Independently selected from the group consisting of-H or a carbon chain or silicon chain or carbo-silicon heterochain group having 1-10 carbons or silicon; r4,R5,R6,R7Independently selected from the group consisting of-H, -F, -Cl, -Br, -I, -CN, -NO2、-R8,-OR8,-SO2R8、-SO2NR8R9、-COR8、-COOR8、-CONR8R9Group (d) of (a).
The modifier can be used in an amount of 1% to 20% (e.g., 1%, 2%, 5%, 10%, 20%) of the total weight of the insulation material. In the method, the selected diluting reagent, i.e., the solvent, may be one or more selected from acetonitrile, acetone, ethyl acetate, toluene, xylene, and alcohol compounds having 1 to 10 carbon atoms (e.g., methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, or isomers of alcohol compounds having three or more carbon atoms). The amount of the solvent used may be 0 to 5 times (e.g., 0, 1, 1.5, 2, 5 times) the mass of the modifier. The reagent is introduced in a vacuum introduction mode or a gas phase fumigation mode.
In some further preferred or further preferred embodiments, the oxide hybrid phenolic insulation material is an oxide hybrid phenolic resin based porous composite material. In some further preferred or further preferred embodiments, the oxide hybrid phenolic insulation material is an oxide hybrid phenolic ablative porous composite, an oxide hybrid phenolic aerogel composite, or a porous composite comprising an oxide hybrid phenolic resin; among them, the porous composite material containing the oxide hybrid phenol resin may include a porous composite material containing other resins in addition to the oxide hybrid phenol resin.
In some further preferred or further preferred embodiments, the modifier is introduced by gas phase fumigation by placing the oxide hybrid phenolic insulation material in a closed container and then drawing the modifier into the container after the container is evacuated.
In the step (2), the temperature of the incubation may be 30 ℃ to 300 ℃ (e.g., 35 ℃, 45 ℃, 55 ℃, 65 ℃, 75 ℃, 85 ℃, 90 ℃, 100 ℃, 150 ℃, 200 ℃, 300 ℃). The heat preservation time can be 0.1-96 h (for example, one or more of 6h, 12h, 18h, 24h, 30h, 36h, 42h, 48h, 60h, 72h and 96 h). The drying mode can be one or more of air blast heating and vacuum heating, the drying temperature can be 25-90 ℃ (for example, one or more of 25 ℃, 26, 27, 28, 29, 30, 35 ℃, 45 ℃, 55 ℃, 65 ℃, 75 ℃ and 85 ℃), and the drying time can be 0.1-96 h (for example, one or more of 6h, 12h, 18h, 24h, 30h, 36h, 42h, 48h, 60h, 72h and 96 h).
The present inventors have found that a modifying agent having the molecular structural characteristics of formula (1) or (2) can react with the organic hydroxyl groups of an oxide-modified phenolic material under certain conditions and form a stable hydrophobic structure that is not easily hydrolyzed at the molecular level, thereby achieving modification. Meanwhile, the modifying agent with the molecular structure characteristics in the molecular formula (3) or (4) can successfully modify the oxide component in the oxide modified phenolic material and is compatible with the modification reaction of the organic hydroxyl in the invention. The method has universality, can be widely applied to the moisture-proof treatment of oxide hybrid 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 be within 1 percent.
In some preferred embodiments, the optimal content of the moisture-proof layer can be more 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 hydrophobic property of the material is more stable and the moisture-proof property is better.
In some embodiments, the present invention provides a method for modifying the surface of an oxide hybrid phenolic insulation material and a modified oxide hybrid phenolic insulation material made thereby, the method comprising the steps of:
(1) preparation of modifier
One or more first modifying reagents with molecular structures shown as formulas (1) and (2) are mixed with one or more second modifying reagents with molecular structures shown as formulas (3) and (4) to form a modifying agent formed by mixing the first modifying reagents and the second modifying reagents. Optionally, the modifier can be mixed with a solvent consisting of one or more of acetonitrile, acetone, ethyl acetate, toluene, xylene and alcohol compounds with 1-10 carbon atoms in 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) to form the modifier, and the modifier has a good modifying function.
In some preferred embodiments, the first modifying agent may be, for example, but not limited to, dimethyl carbonate, dimethyl sulfate, or methyl iodide. In some further preferred or further preferred embodiments, the second modifying agent may be, for example, but not limited to, trimethylmethoxysilane, methyltrimethoxysilane, hexamethyldisilazane or dimethyldimethoxysilane, triethylethoxysilane, ethyltriethoxysilane, hexaethyldisilazane or diethyldiethoxysilane, trimethylethoxysilane, methyltriethoxysilane or dimethyldiethoxysilane, triethylmethoxysilane, ethyltrimethoxysilane or diethyldimethoxysilane. The solvent may be, for example, but not limited to, acetonitrile, acetone, ethyl acetate, toluene, xylene, and/or ethanol.
(2) Modification reaction: and (3) placing the oxide hybrid phenolic aldehyde heat-insulating material into a container, introducing the prepared modifier into the container, and carrying out heat preservation treatment.
Wherein the heat preservation temperature can be 30-300 ℃ (such as 35 ℃, 45 ℃, 55 ℃, 65 ℃, 75 ℃, 85 ℃, 90 ℃, 100 ℃, 150 ℃, 200 ℃ and 300 ℃), and the heat preservation time can be 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 modification reaction is finished, removing redundant modifying reagents and products in a heating mode under the in-situ condition to obtain the high-efficiency moisture-proof modified oxide hybrid phenolic insulation material with low moisture absorption rate.
The drying mode can be air blast heating and/or vacuum heating, the drying temperature can be 25-90 ℃ (for example, one or more of 25 ℃, 26, 27, 28, 29, 30, 35 ℃, 45 ℃, 55 ℃, 65 ℃, 75 ℃ and 85 ℃), and the drying time can be 0.1-96 h (for example, one or more of 6h, 12h, 18h, 24h, 30h, 36h, 42h, 48h, 60h, 72h and 96 h).
In a second aspect, the present invention provides a modified oxide hybrid phenolic insulation material or component (which may comprise or consist of the insulation material) having good moisture barrier properties, such as a moisture barrier structure comprising the insulation material produced by the above method, which has a mass gain of 3% or less, a moisture absorption of 1% or less and/or a thermal conductivity change of 1% or less after modification of the insulation material produced by the above method.
In some embodiments, the modified oxide hybrid phenolic insulation material or component has the following characteristics: (1) the modification treatment process is completed in one step, and the moisture-proof treatment of materials or constructed complex structures can be realized; (2) the moisture absorption rate of the heat insulation material or the component such as the heat protection component is less than or equal to 1 percent, the moisture-proof layer structure 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 modification treatment has no obvious influence on the heat insulation performance of heat insulation materials or components such as heat protection components, and the change of the heat conductivity at room temperature after the moisture-proof treatment is less than 1 percent; (4) the heat insulating material or member such as a heat protective member has an impurity remaining amount of less than 1% except for a moisture-proof layer (mass change rate of less than 1% after drying treatment, oven treatment at 120 ℃ for 2 hours).
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 piece of commercially available unmodified oxide hybrid phenolic aerogel composite material plate with room temperature thermal conductivity of 0.06W/(m.K) in 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 modifier containing 94g of dimethyl carbonate and 94g of trimethyl methoxysilane, sealing the tank, keeping the temperature of the tank at 60 ℃ for 12 hours, taking out the plate, and drying the plate by blowing at 90 ℃ for 6 hours. The surface of the obtained material is in a hydrophobic state, the weight of the material is increased by 2 percent (the mass change rate is tested by baking oven treatment for 2h at 120 ℃, the same is shown below), the moisture absorption rate is 0.40 percent, and the heat conductivity change 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 piece of commercially available unmodified oxide hybrid phenolic aerogel composite material plate with room temperature thermal conductivity of 0.06W/(m.K) in 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 containing 94g of dimethyl carbonate, 94g of trimethyl methoxy silane and 187.5g of acetone, sealing the tank, keeping the temperature at 60 ℃ for 12h, taking out the plate, and drying by blowing at 90 ℃ for 6 h. 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 0.35%, 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 piece of commercially available unmodified oxide hybrid phenolic aerogel composite material plate with room temperature thermal conductivity of 0.06W/(m.K) in 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 modifier containing 94g of dimethyl sulfate and 94g of trimethyl methoxysilane, sealing the tank, keeping the temperature of the tank 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 in a hydrophobic state, the weight of the material is increased by 2.3%, the moisture absorption rate is 0.6%, 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/cm3And placing a piece of commercially available unmodified oxide hybrid phenolic aerogel composite material plate with room temperature thermal conductivity of 0.06W/(m.K) in a tank body with the height of 800mm and the diameter of phi 800mm, and keeping the temperature of 90 ℃ for 4 hours in an atmosphere communication state. And (3) vacuumizing the tank under the condition of keeping the temperature unchanged, sucking a modifier containing 94g of dimethyl carbonate and 94g of methyltrimethoxysilane, sealing the tank, keeping the temperature of the tank at 90 ℃ for 12h, taking out the plate, and drying the plate by blowing at 90 ℃ for 6 h. 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 unmodified hemispherical oxide hybrid phenolic aerogel composite material plate with the room temperature thermal conductivity of 0.06W/(m.K) is internally riveted with an aluminum alloy hemispherical component with the thickness of 2mm, placed in a tank body with the height of 800mm and the diameter of phi 800mm, and kept in an atmosphere communication state for heat preservation at 90 ℃ for 4 hours. And (3) vacuumizing the tank under the condition of keeping the temperature unchanged, sucking a modifier containing 181g of dimethyl carbonate and 181g of hexamethyldisilazane, 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. Wherein 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 2 percent, the moisture absorption rate is 0.5 percent, and the change of the heat conductivity at room temperature is less than 1 percent.
Comparative example 1
Taking the sample with the size of 500mm multiplied by 30mm and the density of 0.5g/cm3Room temperature thermal conductivityA piece of 0.06W/(m.K) oxide hybrid phenolic aerogel composite material which is sold on the market and is not subjected to modification treatment is placed in a tank body with the height of 800mm and the diameter of phi 800mm, and the temperature is kept for 4 hours at 60 ℃ in an atmosphere communication state. And (3) vacuumizing the tank under the condition of keeping the temperature unchanged, sucking 188g 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 piece of commercially available unmodified oxide hybrid phenolic aerogel composite material plate with room temperature thermal conductivity of 0.06W/(m.K) in 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 188g of trimethylchlorosilane, 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 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 piece of commercially available unmodified oxide hybrid phenolic aerogel composite material plate with room temperature thermal conductivity of 0.06W/(m.K) in 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 188g 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 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/cm3One piece of a commercially available unmodified oxide hybrid phenolic aerogel composite material plate with the room-temperature thermal conductivity of 0.06W/(m.K) is subjected to spraying treatment by using a commercially available waterproof coating (purchased from Beijing Yinuokai Co., Ltd.) on the surface, and is 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 solid is 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 hydrophobization reaction has good compatibility, the low-corrosion environment is always kept in the whole reaction process, and the method is suitable for modified moistureproof 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 modified oxide hybrid phenolic aldehyde heat insulation material is characterized by comprising the following steps:
(1) preparing a modifier: mixing a modifying agent with an optional solvent to prepare a modifying agent with a hydrophobic modification function;
(2) modification reaction: introducing the modifier into an oxide hybrid phenolic aldehyde heat-insulating material for heat preservation so as to carry out modification reaction;
(3) and (3) drying: after the modification reaction is finished, removing redundant modifying reagents in a heating mode under the in-situ condition to obtain the modified oxide hybrid phenolic aldehyde heat-insulating material with the moisture-proof performance.
2. The production method according to claim 1, wherein in step (1), the modification reagent comprises a first modification reagent selected from one or more reagents having a molecular structure represented by formula (1) or formula (2), and a second modification reagent selected from one or more reagents having a molecular structure represented by formula (3) or formula (4):
R1OOMOO R2 (1)，
R3X (2)，
R4R5SiR6R7 (3)，
R4R5R6SiNHSiR4R5R6 (4)，
wherein M is C and/or S; x is selected from-F, -Cl, -Br, -I, -CN, -NO2、-SO2R8One or more of; r1,R2,R3Independently selected from-H, -CN, -NO2、-SO2R8、-SO2NR8R9、-COR8、-COOR8、-CONR8R9One or more of a carbon chain group having 1 to 10 carbons, a silicon chain group having 1 to 10 silicon atoms, or a carbon-silicon heterochain group having 1 to 10 carbon atoms and silicon atoms in total; r8And R9One or more groups independently selected from-H or a carbon chain group having 1-10 carbons, a silicon chain group having 1-10 silicon atoms, or a carbon-silicon heterochain group having a total of 1-10 carbon atoms and silicon atoms; r4,R5,R6,R7Independently selected from-H, -F, -Cl, -Br, -I, -CN, -NO2、-R8,-OR8,-SO2R8、-SO2NR8R9、-COR8、-COOR8、-CONR8R9In (1)One or more groups.
3. The preparation method according to claim 1, wherein in the step (2), the modifier is used in an amount of 1-20% by weight based on the total weight of the oxide hybrid phenolic thermal insulation material.
4. The preparation method according to claim 1, wherein in the step (1), the solvent is one or more selected from acetonitrile, acetone, ethyl acetate, toluene, xylene, and alcohols having 1 to 10 carbons; preferably, the amount of the solvent is 0-5 times of the mass of the modifying reagent.
5. The method according to claim 1, wherein the oxide hybrid phenolic insulation material is an oxide hybrid phenolic resin-based porous composite material.
6. The method of claim 1, wherein the oxide hybrid phenolic insulation material is an oxide hybrid phenolic ablative composite, an oxide hybrid phenolic aerogel composite, or a porous composite comprising an oxide hybrid phenolic resin.
7. The preparation method of claim 1, wherein the modifier is added by gas phase fumigation, and the gas phase fumigation is introduced by placing the oxide hybrid phenolic thermal insulation material in a closed container, and then sucking the modifier after the container is vacuumized.
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 25-90 ℃; the heating time is 0.1-96 h; the heating mode is blast heating and/or vacuum heating.
10. A modified oxide hybrid phenolic insulation material, characterized in that the modified oxide hybrid phenolic insulation material is produced by the production method according to any one of claims 1 to 9; preferably, the mass weight percentage of the modified oxide hybrid phenolic insulation material relative to the oxide hybrid phenolic insulation material used as a raw material is less than or equal to 3%, the moisture absorption rate is less than or equal to 1%, and/or the thermal conductivity change is less than 1%.
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|---|---|---|---|---|
| EP0585456A1 (en) * | 1992-02-18 | 1994-03-09 | Matsushita Electric Works Ltd | Process for producing hydrophobic aerogel |
| CN109607551A (en) * | 2018-12-11 | 2019-04-12 | 航天特种材料及工艺技术研究所 | A kind of silicon dioxide silica aerogel composite material and its preparation method and application |
| CN111659326A (en) * | 2020-06-12 | 2020-09-15 | 浙江岩谷科技有限公司 | Modification method of hydrophobic aerogel material |
| CN112480467A (en) * | 2020-11-23 | 2021-03-12 | 航天特种材料及工艺技术研究所 | Moisture-proof modified phenolic aldehyde heat-insulating material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0585456A1 (en) * | 1992-02-18 | 1994-03-09 | Matsushita Electric Works Ltd | Process for producing hydrophobic aerogel |
| CN109607551A (en) * | 2018-12-11 | 2019-04-12 | 航天特种材料及工艺技术研究所 | A kind of silicon dioxide silica aerogel composite material and its preparation method and application |
| CN111659326A (en) * | 2020-06-12 | 2020-09-15 | 浙江岩谷科技有限公司 | Modification method of hydrophobic aerogel material |
| CN112480467A (en) * | 2020-11-23 | 2021-03-12 | 航天特种材料及工艺技术研究所 | Moisture-proof modified phenolic aldehyde heat-insulating material and preparation method thereof |
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