CN113637138A - Low-cost phase-change thermal-insulation composite board and preparation method thereof - Google Patents

Low-cost phase-change thermal-insulation composite board and preparation method thereof Download PDF

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CN113637138A
CN113637138A CN202111084096.0A CN202111084096A CN113637138A CN 113637138 A CN113637138 A CN 113637138A CN 202111084096 A CN202111084096 A CN 202111084096A CN 113637138 A CN113637138 A CN 113637138A
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phase
change
composite board
low
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罗亿江
林志华
戢超
池佩富
黄金登
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Fujian Ten Lead Advanced Material Co ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4804Two or more polyethers of different physical or chemical nature
    • C08G18/482Mixtures of polyethers containing at least one polyether containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/50Polyethers having heteroatoms other than oxygen
    • C08G18/5021Polyethers having heteroatoms other than oxygen having nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009Use of pretreated compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143Halogen containing compounds
    • C08J9/147Halogen containing compounds containing carbon and halogen atoms only
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C08J2203/144Perhalogenated saturated hydrocarbons, e.g. F3C-CF3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • C08J2375/08Polyurethanes from polyethers

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Abstract

The invention discloses a low-cost phase-change heat-insulation composite board which is prepared from the following raw materials in parts by weight: 200-450 parts of inorganic phase-change material, 30-80 parts of porous adsorption material, 220 parts of isocyanate, 100 parts of polyether polyol, 2-6 parts of organosilicon stabilizer, 4-10 parts of triethylene diamine and 40-55 parts of trichloro-fluoromethane; also discloses a preparation method of the low-cost phase-change heat-insulation composite board. Compared with the phase-change material in the current market, the phase-change heat-insulation composite board prepared by the invention has the characteristics of low manufacturing cost, large phase-change enthalpy value, difficult leakage, long service life and the like.

Description

Low-cost phase-change thermal-insulation composite board and preparation method thereof
Technical Field
The invention relates to the field of heat-insulating composite materials, in particular to a low-cost phase-change heat-insulating composite board and a preparation method thereof.
Background
The phase change material has the capability of changing the physical state within a certain temperature range, for example, solid-liquid phase change, when the phase change material is heated to a melting temperature, the phase change material generates phase change from a solid state to a liquid state, in the melting process, the phase change material absorbs and stores a large amount of latent heat, and when the phase change material is cooled, the stored heat is radiated to the environment within a certain temperature range to perform reverse phase change from the liquid state to the solid state. The phase-change material mainly comprises three types of inorganic phase-change materials, organic phase-change materials and composite phase-change materials, wherein the inorganic phase-change materials mainly comprise crystalline hydrated salts, molten salts, metals or alloys and the like, the organic phase-change materials mainly comprise paraffin, acetic acid and other organic matters, and the composite phase-change materials can effectively overcome the defects of single inorganic matter or organic phase-change materials, improve the application effect of the phase-change materials and expand the application range of the phase-change materials, so that the development of the composite phase-change energy storage materials becomes a popular research topic.
Composite phase change energy storage materials in the current market generally fall into three types: the first is inorganic phase-change material wrapped by a shell, which has low manufacturing cost, but short service life and leakage caused by aging and damage of the shell; the second method is that the organic phase change material is wrapped by the microcapsule technology, the cost of the method is high, the method is limited to the immature technology at present, the wrapping amount is not large, and the enthalpy value is low; and the third method is that the porous material adsorbs the phase-change material, and the method is easy to leak when the phase-change material is melted.
Therefore, there is a need in the market to find a safe and reliable alternative material with low cost and no easy leakage.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a low-cost phase-change heat-insulation composite board and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the low-cost phase-change thermal-insulation composite board is characterized by being prepared from the following raw materials in parts by weight:
200-450 parts of inorganic phase-change material, 30-80 parts of porous adsorption material, 220 parts of isocyanate, 100 parts of polyether polyol, 2-6 parts of organosilicon stabilizer, 4-10 parts of triethylene diamine and 40-55 parts of trichloro-fluoromethane.
On the basis of the scheme, the low-cost phase-change heat-insulation composite board further comprises the following raw materials in parts by weight: 30-50 parts of ethylenediamine polyether polyol.
On the basis of the scheme, the low-cost phase-change heat-insulation composite board further comprises the following raw materials in parts by weight: 25-40 parts of tri (beta-chloroethylene) phosphate.
On the basis of the scheme, the low-cost phase-change heat-insulation composite board further comprises the following raw materials in parts by weight: 25-40 parts of tri (beta-chloro-ethylbenzene) phosphate and 0.5-1.8 parts of organic aluminum tin.
On the basis of the scheme, further, the inorganic phase change material comprises Mn (NO)3)2·6H2O、CaCl2·6H2O、LiNO3·3H2O、Na2SO4·10H2O、Na2CO3·10H2O、CaBr2·6H2O、Na2HPO4·10H2O、Zn(NO3)2·6H2One or more of O.
On the basis of the scheme, the porous adsorption material further comprises one or more of flower mud powder, porous carbon powder and sodium polyacrylate.
The preparation method of the low-cost phase-change thermal-insulation composite board comprises the following steps:
a. heating and melting the inorganic phase-change material to a liquid state, adding a porous adsorption material, and mixing to obtain a mixture A;
b. b, pouring the mixture A obtained in the step a, isocyanate, polyether polyol, an organic silicon stabilizer, triethylene diamine and trichloro-fluoromethane into a container, and fully stirring and mixing to obtain a mixture B;
c. pouring the mixture B into a preheated mold, and putting the mold into an oven for curing and molding;
d. and taking out the mold, and performing demolding treatment to obtain the phase change energy storage heat preservation composite board.
On the basis of the scheme, one or more of ethylenediamine polyether polyol, tri (beta-chloroethylene) phosphate and organic aluminum tin can be further added in the step b to be fully stirred and mixed with the mixture A.
On the basis of the scheme, the mixture B is further molded for 10-35min at the temperature of 60-75 ℃ in an oven.
On the basis of the scheme, in the step a, the inorganic phase-change material and the porous adsorption material are further mixed in a stirring manner.
After adopting the technical scheme, compared with the background technology, the invention has the following advantages:
compared with the phase-change material in the current market, the phase-change heat-insulation composite board prepared by the invention has the characteristics of low manufacturing cost, large phase-change enthalpy value, difficult leakage, long service life and the like, and has wide application prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention discloses a low-cost phase-change thermal-insulation composite board which is characterized by being prepared from the following raw materials in parts by weight:
200-450 parts of inorganic phase-change material, 30-80 parts of porous adsorption material, 220 parts of isocyanate, 100 parts of polyether polyol, 2-6 parts of organosilicon stabilizer, 4-10 parts of triethylene diamine and 40-55 parts of trichloro-fluoromethane. The inorganic phase-change material provides a phase-change energy storage effect for the phase-change heat-insulation composite board, the porous adsorption material serves as an adsorption carrier of the phase-change material, the isocyanate and the polyether polyol serve as a main framework of the phase-change composite heat-insulation board, the trichloro-fluoromethane serves as a foaming agent, the triethylene diamine serves as a catalyst, and the organosilicon stabilizer enables foam holes to be finer and finer when the board is foamed.
The inorganic phase change material comprises Mn (NO)3)2·6H2O、CaCl2·6H2O、LiNO3·3H2O、Na2SO4·10H2O、Na2CO3·10H2O、CaBr2·6H2O、Na2HPO4·10H2O、Zn(NO3)2·6H2One or more of O. The porous adsorption material comprises one or more of flower mud powder, porous carbon powder and sodium polyacrylate.
On the basis of the scheme, the low-cost phase-change heat-insulation composite board further comprises the following raw materials in parts by weight: 30-50 parts of ethylenediamine polyether polyol.
On the basis of the scheme, the low-cost phase-change heat-insulation composite board further comprises the following raw materials in parts by weight: 25-40 parts of tri (beta-chloroethylene) phosphate.
On the basis of the scheme, the low-cost phase-change heat-insulation composite board further comprises the following raw materials in parts by weight: 25-40 parts of tri (beta-chloro-ethylbenzene) phosphate and 0.5-1.8 parts of organic aluminum tin.
The invention also discloses a preparation method of the low-cost phase-change heat-insulation composite board, which comprises the following steps:
a. heating and melting the inorganic phase-change material to a liquid state, adding the porous adsorption material, and mixing to obtain a mixture A, wherein after the porous adsorption material is added, stirring the inorganic phase-change material, so that the inorganic phase-change material and the porous adsorption material are fully mixed, and the adsorption rate of the porous adsorption material on the inorganic phase-change material is improved.
b. And B, pouring the mixture A obtained in the step a, isocyanate, polyether polyol, an organic silicon stabilizer, triethylene diamine and trichloro-fluoromethane into a container, and fully stirring and mixing to obtain a mixture B. Wherein, one or more of ethylenediamine polyether polyol, tri (beta-chloroethylbenzene) phosphate and organic aluminum tin can be added in the step b to be fully stirred and mixed with the mixture A.
c. And pouring the mixture B into a preheated mold, and putting the mold into an oven for curing and molding, wherein the mixture B is molded for 10-35min at the temperature of 60-75 ℃ in the oven.
d. And taking out the mold, and performing demolding treatment to obtain the phase change energy storage heat preservation composite board.
The present invention will be described in further detail with reference to examples.
Example one
Taking Na2CO3·10H2And (3) adding 250g of O into a 55 ℃ oven for heating and melting, adsorbing by using 60g of porous carbon powder, stirring and mixing in the adsorption process to accelerate adsorption, and thus obtaining a mixture A.
Pouring the mixture A prepared in the step one, 180g of isocyanate, 100g of polyether polyol, 4g of organic silicon stabilizer, 8g of triethylene diamine and 40g of trichloro-fluoromethane into a container, fully stirring and mixing to obtain a mixture B, pouring the mixture B into a preheated mold, placing the mold into an oven at 70 ℃ for foaming, curing and molding, and demolding to obtain the phase-change heat-preservation composite board.
Thirdly, the phase change heat insulation composite board is placed in a high-temperature environment of 110 ℃ to be baked for 2 hours, and no liquid flows out. Through detection, the density of the phase-change heat-insulation composite plate is 60kg/m, the compressive strength is 100kPa, and the phase-change enthalpy value is 97J/g.
Example two
Taking Na2CO3·10H2And (3) adding 250g of O into a 55 ℃ oven to be heated and melted, adsorbing with 60g of porous carbon powder, and stirring and mixing in the adsorption process to accelerate adsorption to obtain a mixture A.
Pouring the mixture A prepared in the step one, 180g of isocyanate, 100g of polyether polyol, 40g of ethylenediamine polyol, 4g of organic silicon stabilizer, 8g of triethylene diamine and 40g of trichloro-fluoromethane into a container, fully stirring and mixing to obtain a mixture B, pouring the mixture B into a preheated mold, placing the mold into a 70 ℃ oven for foaming, curing and molding, and demolding to obtain the phase-change heat-preservation composite board.
Thirdly, the phase change heat insulation composite board is placed in a high-temperature environment of 110 ℃ to be baked for 2 hours, and no liquid flows out. Through detection, the density of the phase-change heat-insulation composite plate is 58kg/m, the compressive strength is 180kPa, and the phase-change enthalpy value is 93J/g.
EXAMPLE III
Taking Na2CO3·10H2And (3) adding 250g of O into a 55 ℃ oven to be heated and melted, adsorbing with 60g of porous carbon powder, and stirring and mixing in the adsorption process to accelerate adsorption to obtain a mixture A.
Pouring the mixture A prepared in the step one, 180g of isocyanate, 100g of polyether polyol, 4g of organic silicon stabilizer, 8g of triethylene diamine, 30g of tri (beta-chloroethylene) phosphate and 40g of trichloro-fluoromethane into a container, fully stirring and mixing to obtain a mixture B, pouring the mixture B into a preheated mold, placing the mold in a 70 ℃ oven for foaming, curing and molding, and demolding to obtain the phase-change heat-preservation composite board.
Thirdly, the phase change heat insulation composite board is placed in a high-temperature environment of 110 ℃ to be baked for 2 hours, and no liquid flows out. Through detection, the density of the phase-change heat-insulation composite plate is 63kg/m, the compressive strength is 220kPa, and the phase-change enthalpy value is 90J/g.
Example four
Taking Na2CO3·10H2And (3) putting 400g of O into a 55-DEG C oven for heating and melting, adsorbing by using 60g of porous carbon powder, stirring and mixing in the adsorption process to accelerate adsorption, and obtaining a mixture A.
Pouring the mixture A prepared in the step one, 180g of isocyanate, 100g of polyether polyol, 4g of organic silicon stabilizer, 8g of triethylene diamine, 30g of tri (beta-chloroethylene) phosphate, 1.2g of organic aluminum tin and 40g of trichloro-fluoromethane into a container, fully stirring and mixing to obtain a mixture B, pouring the mixture B into a preheated mold, placing the mold into a 70 ℃ oven for foaming, curing and molding, and demolding to obtain the phase-change heat-preservation composite board.
Thirdly, the phase change heat insulation composite board is placed in a high-temperature environment of 110 ℃ to be baked for 2 hours, and no liquid flows out. Through detection, the density of the phase-change heat-insulation composite plate is 61kg/m in high-density thin-walled carbon fiber, the compressive strength is 350kPa, and the phase-change enthalpy value is 121J/g.
Comparative example 1
Taking Na2CO3·10H2And (3) adding 250g of O into a 55 ℃ oven to be heated and melted, adsorbing with 60g of porous carbon powder, and stirring and mixing in the adsorption process to accelerate adsorption.
Pouring the mixture A prepared in the step one, 180g of isocyanate, 100g of polyether polyol and 40g of trichloro-fluoromethane into a container, fully stirring and mixing to obtain a mixture B, pouring the mixture B into a preheated mold, placing the mold in a 70 ℃ oven for foaming, curing and molding, and demolding to obtain the phase-change heat-preservation composite board.
In the process of preparing the phase-change composite insulation board, ethylenediamine polyether polyol, triethylene diamine, organic aluminum tin, an organic silicon stabilizer and tri (beta-chloroethylene) phosphate are not added, and the prepared phase-change composite insulation board is placed in a high-temperature environment of 110 ℃ to be baked for 2 hours, so that a large amount of phase-change liquid flows out, and the wrapping is incomplete.
Comparative example No. two
Taking Na2CO3·10H2And (3) adding 250g of O into a 55 ℃ oven to be heated and melted, adsorbing with 60g of porous carbon powder, and stirring and mixing in the adsorption process to accelerate adsorption.
Pouring the mixture A prepared in the step one, 180g of isocyanate, 100g of polyether polyol, 4g of organic silicon stabilizer and 40g of trichloro-fluoromethane into a container, fully stirring and mixing to obtain a mixture B, pouring the mixture B into a preheated mold, placing the mold in a 70 ℃ oven for foaming, curing and molding, and demolding to obtain the phase-change heat-preservation composite board.
In the process of preparing the phase-change composite insulation board, ethylenediamine polyether polyol, triethylene diamine, organic aluminum tin and tri (beta-chloroethylene) phosphate are not added, and the prepared phase-change composite insulation board is placed in a high-temperature environment of 110 ℃ to be baked for 2 hours, so that a large amount of phase-change liquid flows out, and the wrapping is incomplete.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. The low-cost phase-change thermal-insulation composite board is characterized by being prepared from the following raw materials in parts by weight:
200-450 parts of inorganic phase-change material, 30-80 parts of porous adsorption material, 220 parts of isocyanate, 100 parts of polyether polyol, 2-6 parts of organosilicon stabilizer, 4-10 parts of triethylene diamine and 40-55 parts of trichloro-fluoromethane.
2. The low-cost phase-change thermal-insulation composite board of claim 1, further comprising the following raw materials in parts by weight: 30-50 parts of ethylenediamine polyether polyol.
3. The low-cost phase-change thermal-insulation composite board of claim 1, further comprising the following raw materials in parts by weight: 25-40 parts of tri (beta-chloroethylene) phosphate.
4. The low-cost phase-change thermal-insulation composite board of claim 1, further comprising the following raw materials in parts by weight: 25-40 parts of tri (beta-chloro-ethylbenzene) phosphate and 0.5-1.8 parts of organic aluminum tin.
5. The low cost phase change thermal composite panel according to claim 1, wherein the inorganic phase change material comprises Mn (NO)3)2·6H2O、CaCl2·6H2O、LiNO3·3H2O、Na2SO4·10H2O、Na2CO3·10H2O、CaBr2·6H2O、Na2HPO4·10H2O、Zn(NO3)2·6H2One or more of O.
6. The low-cost phase-change thermal insulation composite board according to claim 1, wherein the porous adsorption material comprises one or more of flower mud powder, porous carbon powder and sodium polyacrylate.
7. The preparation method of the low-cost phase-change thermal insulation composite board according to any one of claims 1 to 6, characterized by comprising the following steps:
a. heating and melting the inorganic phase-change material to a liquid state, adding a porous adsorption material, and mixing to obtain a mixture A;
b. b, pouring the mixture A obtained in the step a, isocyanate, polyether polyol, an organic silicon stabilizer, triethylene diamine and trichloro-fluoromethane into a container, and fully stirring and mixing to obtain a mixture B;
c. pouring the mixture B into a preheated mold, and putting the mold into an oven for curing and molding;
d. and taking out the mold, and performing demolding treatment to obtain the phase change energy storage heat preservation composite board.
8. The method for preparing a low-cost phase-change thermal-insulation composite board according to claim 7, wherein one or more of ethylenediamine polyether polyol, tris (β -chloroethylbenzene) phosphate and organic aluminum tin can be added in the step b to be fully stirred and mixed with the mixture A.
9. The preparation method of the low-cost phase-change thermal insulation composite board as claimed in claim 7, wherein the mixture B is molded for 10-35min at a temperature of 60-75 ℃ in an oven.
10. The method for preparing a low-cost phase-change thermal insulation composite board according to claim 7, wherein the inorganic phase-change material and the porous adsorption material are mixed in a stirring manner in the step a.
CN202111084096.0A 2021-09-16 2021-09-16 Low-cost phase-change thermal-insulation composite board and preparation method thereof Pending CN113637138A (en)

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* Cited by examiner, † Cited by third party
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CN114672299A (en) * 2022-04-20 2022-06-28 中国地质大学(北京) Double-effect transformation slurry for seabed hydrate reservoir, application and application method
CN114672299B (en) * 2022-04-20 2022-12-06 中国地质大学(北京) Double-effect transformation slurry for seabed hydrate reservoir, application and application method

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Application publication date: 20211112