WO2023109869A1 - Thermal insulation material, and refrigerator, refrigerated storage, or freezer using same - Google Patents

Thermal insulation material, and refrigerator, refrigerated storage, or freezer using same Download PDF

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Publication number
WO2023109869A1
WO2023109869A1 PCT/CN2022/139036 CN2022139036W WO2023109869A1 WO 2023109869 A1 WO2023109869 A1 WO 2023109869A1 CN 2022139036 W CN2022139036 W CN 2022139036W WO 2023109869 A1 WO2023109869 A1 WO 2023109869A1
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WIPO (PCT)
Prior art keywords
polyurethane foam
insulating material
heat insulating
hydrophilic
polyol
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PCT/CN2022/139036
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French (fr)
Chinese (zh)
Inventor
大汤英树
上田勉
星野仁
馆野恭也
Original Assignee
海尔智家股份有限公司
青岛海尔电冰箱有限公司
Aqua 株式会社
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Application filed by 海尔智家股份有限公司, 青岛海尔电冰箱有限公司, Aqua 株式会社 filed Critical 海尔智家股份有限公司
Priority to CN202280059877.0A priority Critical patent/CN117916317A/en
Publication of WO2023109869A1 publication Critical patent/WO2023109869A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features
    • F25D23/06—Walls
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features
    • F25D23/08—Parts formed wholly or mainly of plastics materials

Definitions

  • the present invention relates to a heat insulating material provided with polyurethane foam, and a refrigerator, a freezer, or a freezer using the heat insulating material.
  • Rigid polyurethane foam resins are widely used as insulation materials for refrigerators, refrigerators, and freezers. Improvements to this polyurethane foam are needed to develop a new generation of high-performance insulation materials.
  • the resinification time of polyol and polyisocyanate reaction is called gel time.
  • Urethane foam can improve thermal insulation with fine air cells. In general, when the gel time is suppressed, the expansion time of the polyurethane foam is shortened, so the cells of the polyurethane foam become finer.
  • the polyurethane foam will foam before it fills the entire area of the product, resulting in an unfilled portion.
  • a heat-insulating material is described in Patent Document 1, Japanese National Publication No. 2020-515685, which contains a polymer matrix, airgel particles, and expanded microspheres.
  • the total mass of matrix, airgel particles and expanded microspheres, the mass fraction of airgel particles is not less than 30%
  • the mass fraction of polymer matrix is not less than 20%
  • the mass fraction of expanded microspheres is between 0.5% and Between 15%.
  • the thermal conductivity of the insulating material is less than 40mW/m ⁇ K under atmospheric conditions.
  • one object of the present invention is to provide a heat insulating material that has a long gel time, eliminates unfilled parts, suppresses the expansion of air cells, and makes the air cells of polyurethane foam micronized.
  • one of the objects of the present invention is to provide a thermal insulation material formed by foaming polyurethane, the airgel content of which is optimized, and the thermal insulation performance is improved.
  • the present invention solves one of the above-mentioned problems by mixing a hydrophilic aerogel having high thermal insulation performance with a polyurethane foam raw material to increase the viscosity of the material.
  • the present invention solves one of the above-mentioned problems by providing a polyurethane foam with an optimized content of hydrophilic aerogel.
  • the heat insulating material of the present invention is characterized by comprising polyurethane foam containing 0.2% to 3% of hydrophilic airgel.
  • the viscosity of the material is increased by mixing hydrophilic airgel having high heat insulating performance into the raw material of polyurethane foam, thereby suppressing the expansion of air cells.
  • the insulating material of the present invention can extend the gel time, eliminating unfilled parts of the article.
  • the heat insulating material of the present invention optimizes the content of the hydrophilic aerogel, the heat insulating performance is improved.
  • the present invention is characterized in that the polyurethane foam has an average cell diameter of 142 ⁇ m or less.
  • the present invention can make the average cell diameter (the size of the cells) smaller than that of the conventional polyurethane foam.
  • the heat insulating material of the present invention is characterized by containing 0.2% to 0.5% of hydrophilic airgel.
  • the thermal insulation material of the present invention can further improve the thermal insulation performance by adjusting the content of the hydrophilic airgel in the polyurethane foam.
  • the present invention is characterized in that the polyurethane foam has an average cell diameter of 137 ⁇ m or less.
  • the thermal insulating material of the present invention can further reduce the average cell diameter by adjusting the content of the hydrophilic airgel in the polyurethane foam.
  • the present invention is characterized in that the polyurethane foam is composed of polyol mixture of amine polyol, polyester polyol and aliphatic amine compound as a catalyst, polyisocyanate of diphenylmethane diisocyanate, and cyclopentane, etc.
  • the foaming agent is obtained by mixing hydrophilic airgel, wherein the hydrophilic airgel is silica airgel.
  • the refrigerator, refrigerator, or freezer of this invention is characterized by using the said rigid polyurethane foam as a heat insulating material.
  • the thermal insulation performance is improved by using rigid polyurethane foam.
  • the present invention provides a heat insulating material with improved heat insulating properties.
  • the present invention provides a heat insulating material having a smaller average cell diameter than conventional polyurethane foam.
  • the thermal insulation performance is further improved by adjusting the content of the hydrophilic airgel in the polyurethane foam.
  • the present invention can provide a thermal insulation material with further reduced cell average diameter by adjusting the content of the hydrophilic airgel in the polyurethane foam.
  • the present invention it is possible to provide a heat insulating material in which the polyurethane foam is composed of a polyol mixture of an amine polyol, a polyester polyol and an aliphatic amine compound as a catalyst, a polyisocyanate of diphenylmethane diisocyanate , and cyclopentane and other foaming agents are mixed to obtain, and the hydrophilic airgel is silica airgel.
  • the present invention provides a refrigerator, refrigerator, or freezer that uses the rigid polyurethane foam as the heat insulating material to improve heat insulation performance.
  • FIG. 1 is a photograph of the cell diameter measurement of the polyurethane foam of Example 2.
  • FIG. 1 is a photograph of the cell diameter measurement of the polyurethane foam of Example 2.
  • FIG. 2 is a photograph of the cell diameter measurement of the polyurethane foam of Example 4.
  • FIG. 3 is a photograph of the cell diameter measurement of the polyurethane foam of Comparative Example 2.
  • Fig. 4 is a photo of cell diameter measurement of a polyurethane foam of a conventional example.
  • the polyurethane foam of the present invention is obtained by reacting a polyol compound, a polyol mixture as a catalyst, and polyisocyanate as an isocyanate compound in the presence of a foaming agent and a hydrophilic airgel.
  • the structure of the reacted polyurethane foam is complex and generally cannot be determined.
  • the polyol compound of the polyol mixture contains an amine-based polyol.
  • the amine polyol contains one or more of triethanolamine, ethylenediamine, aromatic diamine, and diethylenetriamine.
  • the polyol compound of a polyol mixture contains a polyester type polyol.
  • Polyester-based polyols are produced by dehydrating and condensing several types of carboxylic acids and polyols.
  • carboxylic acid adipic acid, phthalic acid, etc.
  • polyhydric alcohol ethylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.
  • Rigid polyurethane foam mainly uses phthalic acid-based polyester-based polyols.
  • the catalyst of the polyol mixture is used to regulate the synthesis reaction of the polyurethane foam.
  • the catalyst of the polyol mixture according to the embodiment of the present invention contains an aliphatic amine.
  • Aliphatic amines can use methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, triethanolamine, N,N-diisopropylethylamine, tetramethylethylenediamine , Hexamethylenediamine, spermidine, spermine, amantadine, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, one or more.
  • the isocyanate compound of the polyisocyanate according to the embodiment of the present invention one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and m-xylylene diisocyanate can be used. or more.
  • diphenylmethane diisocyanate is preferably used as the isocyanate compound. Moreover, it is preferable to use 124 weight part of the polyisocyanate which concerns on embodiment of this invention.
  • the polyurethane foam according to the embodiment of the present invention is foamed by a blowing agent.
  • Cyclopentane trichlorofluoromethane, 1,1-dichloro-1-fluoromethane, 1,1,1,3,3-pentafluoropropane, 1,1, One or more of 1,3,3-pentafluorobutane and carbon dioxide.
  • Cyclopentane is preferably used as the blowing agent in the embodiment of the present invention.
  • the polyurethane foam of the present invention is preferably formed 100 parts by weight.
  • the foaming of the polyurethane foam according to the embodiment of the present invention is controlled by the hydrophilic aerogel.
  • the hydrophilic aerogel according to the embodiment of the present invention silica aerogel, carbon aerogel, metal aerogel, and polymer aerogel can be used.
  • Silica aerogel is preferably used as the hydrophilic aerogel according to the embodiment of the present invention.
  • Hydrophilic silica airgel has high hydrophilicity due to the hydroxyl groups on the surface.
  • the hydrophilic airgel according to the embodiment of the present invention is preferably in a granular form with a particle diameter of 200 ⁇ m to 400 ⁇ m.
  • the hydrophilic aerogel according to the embodiment of the present invention is preferably used in an amount of 0.2 to 3 parts by weight.
  • the expansion of the air cells is suppressed by adding a hydrophilic airgel having high thermal insulation performance to the raw material of the polyurethane foam to increase the viscosity of the material.
  • the gel time can be extended, and the unfilled portion of the product can be eliminated.
  • the urethane foam with the optimized content of the hydrophilic airgel is used, thermal insulation is improved.
  • the raw materials in Table 1 are used to produce polyurethane foam according to the raw materials in Examples 1-4, Comparative Examples 1, 2 and the conventional example.
  • the polyurethane foams of Examples 1-4 are obtained by reacting polyol mixtures with polyisocyanates in the presence of blowing agents and hydrophilic aerogels.
  • the polyurethane foams of Comparative Examples 1 and 2 are obtained by reacting polyol mixtures and polyisocyanates in the presence of blowing agents and hydrophobic aerogels.
  • the polyol mixture is reacted with polyisocyanate in the presence of a blowing agent to obtain a polyurethane foam of the conventional example.
  • Polyol mixtures and aerogels are as follows.
  • Polyol manufactured by Sumika Covestro Urethane Co., Ltd.
  • Airgel Manufactured by Guangdong Allison High-tech Co., Ltd.
  • the thermal conductivity was measured with FOX200 manufactured by Hideo Seiki Co., Ltd.
  • polyurethane foams 100 parts by weight of polyol mixture, 14 parts by weight of blowing agent, and 124 parts by weight of polyisocyanate were reacted to form 100 parts by weight of polyurethane foam.
  • the polyurethane foam of Example 1 contains 0.2 parts by weight of the hydrophilic airgel, that is, 0.2% of the hydrophilic airgel relative to the polyurethane foam.
  • the polyurethane foam of Example 2 contains 0.5 parts by weight of the hydrophilic airgel, that is, 0.5% of the hydrophilic airgel relative to the polyurethane foam.
  • the polyurethane foam of Example 3 contained 1.0 parts by weight of the hydrophilic airgel, that is, contained 1.0% of the hydrophilic airgel relative to the polyurethane foam.
  • the polyurethane foam of Example 4 contained 3.0 parts by weight of the hydrophilic airgel, that is, 3.0% of the hydrophilic airgel relative to the polyurethane foam. In Examples 1 to 4, other components are the same, and the content of the hydrophilic aerogel is changed.
  • the polyurethane foam of Comparative Example 1 contains 1.0 parts by weight of the hydrophobic airgel, that is, the polyurethane foam contains 1.0% of the hydrophobic airgel, and the polyurethane foam of Comparative Example 2 contains 3.0 parts by weight of the hydrophobic airgel.
  • the gel that is, contains 3.0% of hydrophobic airgel relative to the polyurethane foam.
  • hydrophobic aerogel is contained instead of hydrophilic aerogel.
  • Conventional polyurethane foam does not contain airgel.
  • Examples 1 to 4 in which the content of the hydrophilic airgel was 0.2% to 3% achieved a thermal conductivity of 20.5 mW/m ⁇ K or less. This is lower than the thermal conductivity 20.9 mW/m ⁇ K of the polyurethane foam of the conventional example. Therefore, Examples 1 to 4 have higher thermal insulation performance than the conventional example. In particular, Example 1 and Example 2 achieved a lower thermal conductivity of 20.3 mW/m ⁇ K. Therefore, by adjusting the content of the hydrophilic aerogel to 0.2% to 0.5% without changing other components, the thermal insulation performance is further improved.
  • the thermal conductivity of Comparative Example 1 was 21.0 mW/m ⁇ K.
  • the thermal conductivity of Comparative Example 2 was 21.6 mW/m ⁇ K. Both the thermal conductivity of Comparative Example 1 and Comparative Example 2 are higher than the thermal conductivity of 20.9 mW/m ⁇ K of the conventional polyurethane foam. Therefore, it can be seen that when the hydrophobic aerogel is contained instead of the hydrophilic aerogel, the thermal insulation performance is deteriorated.
  • Examples 1 to 4 have a lower foam density than the polyurethane foam of the conventional example, and the polyurethane foam can be made lighter.
  • the dimensional stability at low temperature (30°C ⁇ 48h (%)) and the dimensional stability at high temperature (70°C ⁇ 48h (%)) are not inferior to those of the conventional example.
  • the compressive strengths of Examples 1 to 4 were also 1.2 to 1.5 kgf ⁇ cm 2 , which was not inferior to the conventional examples.
  • FIG. 1 is a photograph of the pore size measurement of the polyurethane foam of Example 2.
  • FIG. 2 is a photograph of the pore size measurement of the polyurethane foam of Example 4.
  • FIG. 3 is a photograph of the pore size measurement of the polyurethane foam of Comparative Example 2.
  • FIG. Fig. 4 is a photo of the pore size measurement of the polyurethane foam of the conventional example.
  • the cell diameter (the size of the cells) of the polyurethane foam according to the embodiment of the present invention will be described with reference to FIGS. 1 to 4 .
  • the average cell diameter of the polyurethane foam of Example 2 was about 137 ⁇ m.
  • the average cell diameter of the polyurethane foam of Example 4 was about 142 ⁇ m. It can be seen that when the hydrophilic airgel of the polyurethane foam is reduced from 3% to 0.5%, the average cell diameter becomes smaller.
  • the average cell diameter of the polyurethane foam of Comparative Example 2 was 167 ⁇ m.
  • the average cell diameter of the polyurethane foam of the conventional example was 197 ⁇ m. From Figures 1 to 4, it can be seen that the average cell diameter of the polyurethane foam containing the hydrophobic airgel and the conventional polyurethane foam is larger than that of the polyurethane foam containing the hydrophilic airgel.
  • the average cell diameter can be reduced, that is, the cells can be made finer.
  • the average cell diameter can be further reduced by adjusting the content of the hydrophilic aerogel.
  • the urethane foam of the heat insulating material is a rigid urethane foam, which can be filled into the product roughly without unfilled parts and cells, has little deformation at low temperatures, and can be used in refrigerators, freezers, or freezers.
  • a heat insulating material with improved heat insulating performance can be provided. According to the present invention, it is possible to provide a heat insulating material having a smaller average cell diameter than conventional polyurethane foams. According to the present invention, by adjusting the content of the hydrophilic airgel in the polyurethane foam, it is possible to provide a heat insulating material with further improved heat insulating performance. According to the present invention, by adjusting the content of the hydrophilic airgel in the polyurethane foam, it is possible to provide a heat insulating material with a further reduced cell average diameter.
  • the present invention it is possible to provide a heat insulating material in which the polyurethane foam is composed of a polyol mixture of an amine polyol, a polyester polyol, and an aliphatic amine compound as a catalyst, a polyol mixture of diphenylmethane diisocyanate, Isocyanate, and a mixture of blowing agents such as cyclopentane are obtained, and the hydrophilic airgel is silica airgel.
  • the present invention it is possible to provide a heat insulating material using rigid polyurethane foam to improve the heat insulating performance of refrigerators, refrigerators, or freezers.
  • the polyurethane foam of the present invention has a low thermal conductivity and can be used as a heat insulating material for refrigerators, freezers, and refrigerators.
  • the polyurethane foam of the present invention can also be used for sandwich panels, building materials for panels, cooling pipes, and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Thermal Insulation (AREA)
  • Refrigerator Housings (AREA)

Abstract

A thermal insulation material, having a polyurethane foam that contains 0.2-3% of a hydrophilic aerogel. The polyurethane foam is obtained by mixing and foaming a polyol mixture of an amine polyol, a polyester polyol, and an aliphatic amine compound that serves as a catalyst, a polyisocyanate of diphenylmethane diisocyanate, a foaming agent such as cyclopentane, and a hydrophilic aerogel, wherein the hydrophilic aerogel is a silica aerogel. The polyurethane foam of the thermal insulation material has fine bubbles and a high thermal insulation performance.

Description

隔热材料及使用该隔热材料的冰箱、冷藏库或冷冻库Insulation material and refrigerator, freezer or freezer using same 技术领域technical field
本发明涉及具备聚氨酯泡沫的隔热材料及使用该隔热材料的冰箱、冷藏库或冷冻库。The present invention relates to a heat insulating material provided with polyurethane foam, and a refrigerator, a freezer, or a freezer using the heat insulating material.
背景技术Background technique
硬质聚氨酯发泡树脂广泛用于冰箱、冷藏库、冷冻库的隔热材料。需要对这种聚氨酯泡沫进行改良，开发新一代高性能隔热材料。Rigid polyurethane foam resins are widely used as insulation materials for refrigerators, refrigerators, and freezers. Improvements to this polyurethane foam are needed to develop a new generation of high-performance insulation materials.
多元醇与多异氰酸酯反应的树脂化时间称为凝胶时间。聚氨酯泡沫通过微细气泡能够提高绝热性。通常，当抑制凝胶时间时，聚氨酯泡沫膨胀的时间会缩短，因此聚氨酯泡沫的气泡变得微细。The resinification time of polyol and polyisocyanate reaction is called gel time. Urethane foam can improve thermal insulation with fine air cells. In general, when the gel time is suppressed, the expansion time of the polyurethane foam is shortened, so the cells of the polyurethane foam become finer.
但是，若缩短凝胶时间，则聚氨酯泡沫在未填充满制品的整个区域之前就会发泡，从而形成未填充部分。However, if the gel time is shortened, the polyurethane foam will foam before it fills the entire area of the product, resulting in an unfilled portion.
另外，作为高性能隔热材料，在专利文献1日本特表2020-515685号公报中记载了一种隔热材料，其含有聚合物基体、气凝胶颗粒及膨胀微球，其中，基于聚合物基体、气凝胶颗粒及膨胀微球的总质量，气凝胶颗粒的质量分数不低于30％，聚合物基体的质量分数不低于20％，膨胀微球的质量分数介于0.5％～15％之间。另外，隔热材料的导热系数在大气条件下小于40mW/m·K。In addition, as a high-performance heat-insulating material, a heat-insulating material is described in Patent Document 1, Japanese National Publication No. 2020-515685, which contains a polymer matrix, airgel particles, and expanded microspheres. The total mass of matrix, airgel particles and expanded microspheres, the mass fraction of airgel particles is not less than 30%, the mass fraction of polymer matrix is not less than 20%, and the mass fraction of expanded microspheres is between 0.5% and Between 15%. In addition, the thermal conductivity of the insulating material is less than 40mW/m·K under atmospheric conditions.
因此，无法使聚氨酯泡沫的气泡变得微细而消除制品的未填充部分。另外，在专利文献1的实施例中，没有在聚合物基体中使用聚氨酯泡沫。另外，专利文献1中制造的隔热材料多使用气凝胶，价格昂贵。Therefore, the unfilled portion of the product cannot be eliminated by making the cells of the polyurethane foam finer. In addition, in the examples of Patent Document 1, no polyurethane foam is used in the polymer matrix. In addition, the heat insulating material produced in Patent Document 1 often uses aerogel, which is expensive.
发明内容Contents of the invention
因此，本发明的目的之一在于提供一种隔热材料，该隔热材料凝胶时间较长、消除未填充部分，同时可以抑制气泡的膨胀，使聚氨酯泡沫的气泡微细化。另外，本发明的目的之一是提供一种聚氨酯发泡形成的隔热材料，其气凝胶的含量得到了优化，并提高了绝热性能。Therefore, one object of the present invention is to provide a heat insulating material that has a long gel time, eliminates unfilled parts, suppresses the expansion of air cells, and makes the air cells of polyurethane foam micronized. In addition, one of the objects of the present invention is to provide a thermal insulation material formed by foaming polyurethane, the airgel content of which is optimized, and the thermal insulation performance is improved.
本发明通过在聚氨酯泡沫的原料中混合隔热性能高的亲水性气凝胶来提高材料的粘度，从而解决上述课题之一。另外，本发明通过提供一种优化了亲水性气凝胶的含量的聚氨酯泡沫来解决上述问题之一。The present invention solves one of the above-mentioned problems by mixing a hydrophilic aerogel having high thermal insulation performance with a polyurethane foam raw material to increase the viscosity of the material. In addition, the present invention solves one of the above-mentioned problems by providing a polyurethane foam with an optimized content of hydrophilic aerogel.
即，本发明的隔热材料的特点是，具备含有0.2％～3％的亲水性气凝胶的聚氨酯泡沫。That is, the heat insulating material of the present invention is characterized by comprising polyurethane foam containing 0.2% to 3% of hydrophilic airgel.
本发明的隔热材料通过在聚氨酯泡沫的原料中混合隔热性能高的亲水性的气凝胶来提高材料的粘度，从而抑制气泡的膨胀。另外，本发明的隔热材料能够延长凝胶时间，消除制品的未填充部分。另外，本发明的隔热材料由于优化了亲水性气凝胶的含量，因此隔热性能得到改善。In the heat insulating material of the present invention, the viscosity of the material is increased by mixing hydrophilic airgel having high heat insulating performance into the raw material of polyurethane foam, thereby suppressing the expansion of air cells. In addition, the insulating material of the present invention can extend the gel time, eliminating unfilled parts of the article. In addition, since the heat insulating material of the present invention optimizes the content of the hydrophilic aerogel, the heat insulating performance is improved.
另外，本发明的特点是，所述聚氨酯泡沫的泡孔平均直径为142μm以下。In addition, the present invention is characterized in that the polyurethane foam has an average cell diameter of 142 μm or less.
本发明能够使泡孔平均直径(气泡的大小)比以往的聚氨酯泡沫小。The present invention can make the average cell diameter (the size of the cells) smaller than that of the conventional polyurethane foam.
另外，本发明的隔热材料的特点是，含有0.2％～0.5％的亲水性气凝胶。In addition, the heat insulating material of the present invention is characterized by containing 0.2% to 0.5% of hydrophilic airgel.
本发明的隔热材料通过调整聚氨酯泡沫中亲水性气凝胶的含量，能够进一步改善隔热性能。The thermal insulation material of the present invention can further improve the thermal insulation performance by adjusting the content of the hydrophilic airgel in the polyurethane foam.
此外，本发明的特点是，所述聚氨酯泡沫的泡孔平均直径为137μm以下。In addition, the present invention is characterized in that the polyurethane foam has an average cell diameter of 137 μm or less.
本发明的隔热材料通过调整聚氨酯泡沫中亲水性气凝胶的含量，能够进一步减小泡孔平均直径。The thermal insulating material of the present invention can further reduce the average cell diameter by adjusting the content of the hydrophilic airgel in the polyurethane foam.
此外，本发明的特点是，所述聚氨酯泡沫由胺系多元醇、聚酯系多元醇和作为催化剂的脂肪族胺化合物的多元醇混合物，二苯基甲烷二异氰酸酯的多异氰酸酯，以及环戊烷等发泡剂，亲水性气凝胶混合获得，其中，亲水性气凝胶是二氧化硅气凝胶。In addition, the present invention is characterized in that the polyurethane foam is composed of polyol mixture of amine polyol, polyester polyol and aliphatic amine compound as a catalyst, polyisocyanate of diphenylmethane diisocyanate, and cyclopentane, etc. The foaming agent is obtained by mixing hydrophilic airgel, wherein the hydrophilic airgel is silica airgel.
另外，本发明的冰箱、冷藏库或冷冻库的特点是，使用所述硬质聚氨酯泡沫作为隔热材料。Moreover, the refrigerator, refrigerator, or freezer of this invention is characterized by using the said rigid polyurethane foam as a heat insulating material.
本发明的冰箱、冷藏库或冷冻库，通过使用硬质聚氨酯泡沫来改善隔热性能。In the refrigerator, refrigerator or freezer of the present invention, the thermal insulation performance is improved by using rigid polyurethane foam.
发明效果Invention effect
本发明提供一种隔热性能得到改善的隔热材料。本发明提供一种泡孔平均直径比以往的聚氨酯泡沫小的隔热材料。根据本发明，通过调整聚氨酯泡沫中亲水性气凝胶的含量，进一步改善隔热性能。本发明通过调整聚氨酯泡沫中亲水性气凝胶的含量，能够提供进一步减小了泡孔平均直径的隔热材料。The present invention provides a heat insulating material with improved heat insulating properties. The present invention provides a heat insulating material having a smaller average cell diameter than conventional polyurethane foam. According to the present invention, the thermal insulation performance is further improved by adjusting the content of the hydrophilic airgel in the polyurethane foam. The present invention can provide a thermal insulation material with further reduced cell average diameter by adjusting the content of the hydrophilic airgel in the polyurethane foam.
另外，采用本发明，可以提供一种隔热材料，其中，聚氨酯泡沫由胺系多元醇、聚酯系多元醇和作为催化剂的脂肪族胺化合物的多元醇混合物，二苯基甲烷二异氰酸酯的多异氰酸酯，以及环戊烷等发泡剂混合获得，亲水性气凝胶是二氧化硅气凝胶。本发明，提供一种使用上述硬质聚氨酯泡沫作为所述隔热材料来改善绝热性能的冰箱、冷藏库或冷冻库。In addition, according to the present invention, it is possible to provide a heat insulating material in which the polyurethane foam is composed of a polyol mixture of an amine polyol, a polyester polyol and an aliphatic amine compound as a catalyst, a polyisocyanate of diphenylmethane diisocyanate , and cyclopentane and other foaming agents are mixed to obtain, and the hydrophilic airgel is silica airgel. The present invention provides a refrigerator, refrigerator, or freezer that uses the rigid polyurethane foam as the heat insulating material to improve heat insulation performance.
附图说明Description of drawings
图1是实施例2的聚氨酯泡沫的泡孔直径测量照片。FIG. 1 is a photograph of the cell diameter measurement of the polyurethane foam of Example 2. FIG.
图2是实施例4的聚氨酯泡沫的泡孔直径测量照片。FIG. 2 is a photograph of the cell diameter measurement of the polyurethane foam of Example 4. FIG.
图3是比较例2的聚氨酯泡沫的泡孔直径测量照片。FIG. 3 is a photograph of the cell diameter measurement of the polyurethane foam of Comparative Example 2. FIG.
图4是传统例的聚氨酯泡沫的泡孔直径测量照片。Fig. 4 is a photo of cell diameter measurement of a polyurethane foam of a conventional example.
具体实施方式Detailed ways
对本发明的聚氨酯泡沫的实施方式进行说明。Embodiments of the polyurethane foam of the present invention will be described.
本发明的聚氨酯泡沫是多元醇化合物、作为催化剂的多元醇混合物以及异氰酸酯化合物的多异氰酸酯，在存在发泡剂、亲水性气凝胶的情况下反应而得到的。反应后的聚氨酯泡沫的结构复杂，一般情况下无法确定。The polyurethane foam of the present invention is obtained by reacting a polyol compound, a polyol mixture as a catalyst, and polyisocyanate as an isocyanate compound in the presence of a foaming agent and a hydrophilic airgel. The structure of the reacted polyurethane foam is complex and generally cannot be determined.
本发明的实施方式中，多元醇混合物的多元醇化合物含有胺系多元醇。胺系多元醇包含三乙醇胺、乙二胺、芳香族二胺、二亚乙基三胺中的一种或多种。In an embodiment of the present invention, the polyol compound of the polyol mixture contains an amine-based polyol. The amine polyol contains one or more of triethanolamine, ethylenediamine, aromatic diamine, and diethylenetriamine.
另外，本发明的实施方式中，多元醇混合物的多元醇化合物含有聚酯系多元醇。聚酯系多元醇是将数种羧酸和多元醇脱水缩合而生产的。作为羧酸，可以使用己二酸、邻苯二甲酸等，作为多元醇，可以使用乙二醇、1，4-丁二醇、1，6-己二醇等。硬质聚氨酯泡沫主要使用邻苯二甲酸系的聚酯系多元醇。Moreover, in embodiment of this invention, the polyol compound of a polyol mixture contains a polyester type polyol. Polyester-based polyols are produced by dehydrating and condensing several types of carboxylic acids and polyols. As the carboxylic acid, adipic acid, phthalic acid, etc. can be used, and as the polyhydric alcohol, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, etc. can be used. Rigid polyurethane foam mainly uses phthalic acid-based polyester-based polyols.
本发明的实施方式中，多元醇混合物的催化剂用于调节聚氨酯泡沫的合成反应。本发明的实施方式的多元醇混合物的催化剂含有脂肪族胺。脂肪族胺能够使用甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺，乙二胺、三乙醇胺、N，N-二异丙基乙胺、四甲基乙二胺、己二胺、亚精胺、精胺、金刚烷胺、四甲基己二胺、五甲基二乙烯三胺中的一种或多种。In an embodiment of the invention, the catalyst of the polyol mixture is used to regulate the synthesis reaction of the polyurethane foam. The catalyst of the polyol mixture according to the embodiment of the present invention contains an aliphatic amine. Aliphatic amines can use methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, triethanolamine, N,N-diisopropylethylamine, tetramethylethylenediamine , Hexamethylenediamine, spermidine, spermine, amantadine, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, one or more.
本发明的实施方式的多元醇混合物优选使用100重量份。It is preferable to use 100 weight part of the polyol mixture of embodiment of this invention.
作为本发明的实施方式的多异氰酸酯的异氰酸酯化合物，可以使用甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、间苯二甲基异氰酸酯中的一种或多种。As the isocyanate compound of the polyisocyanate according to the embodiment of the present invention, one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and m-xylylene diisocyanate can be used. or more.
在本发明的实施方式中，作为异氰酸酯化合物，优选使用二苯基甲烷二异氰酸酯。另外，本发明的实施方式的多异氰酸酯优选使用124重量份。In an embodiment of the present invention, diphenylmethane diisocyanate is preferably used as the isocyanate compound. Moreover, it is preferable to use 124 weight part of the polyisocyanate which concerns on embodiment of this invention.
本发明的实施方式的聚氨酯泡沫通过发泡剂发泡。本发明的实施方式的发泡剂能够使用环戊烷、三氯氟甲烷、1,1-二氯-1-氟甲烷、1,1,1,3,3-五氟丙烷、1,1,1,3,3-五氟丁烷、二氧化碳中的一种或多种。本发明的实施方式的发泡剂优选使用环戊烷。 另外，本发明的实施方式的发泡剂优选使用14重量份。The polyurethane foam according to the embodiment of the present invention is foamed by a blowing agent. Cyclopentane, trichlorofluoromethane, 1,1-dichloro-1-fluoromethane, 1,1,1,3,3-pentafluoropropane, 1,1, One or more of 1,3,3-pentafluorobutane and carbon dioxide. Cyclopentane is preferably used as the blowing agent in the embodiment of the present invention. In addition, it is preferable to use 14 parts by weight of the foaming agent according to the embodiment of the present invention.
当使多元醇化合物、作为催化剂的100重量份的多元醇混合物,以及124重量份的异氰酸酯化合物的多异氰酸酯,在存在14重量份的发泡剂的情况下反应时，本发明的聚氨酯泡沫优选形成100重量份。When the polyol compound, 100 parts by weight of the polyol mixture as a catalyst, and the polyisocyanate of 124 parts by weight of the isocyanate compound are reacted in the presence of 14 parts by weight of a blowing agent, the polyurethane foam of the present invention is preferably formed 100 parts by weight.
本发明的实施方式的聚氨酯泡沫通过亲水性气凝胶来控制发泡。本发明的实施方式的亲水性气凝胶能够使用二氧化硅气凝胶、碳气凝胶、金属气凝胶、聚合物气凝胶。The foaming of the polyurethane foam according to the embodiment of the present invention is controlled by the hydrophilic aerogel. As the hydrophilic aerogel according to the embodiment of the present invention, silica aerogel, carbon aerogel, metal aerogel, and polymer aerogel can be used.
本发明的实施方式的亲水性气凝胶优选使用二氧化硅气凝胶。亲水性的二氧化硅气凝胶由于表面的羟基而亲水性高。本发明的实施方式的亲水性气凝胶优选为粒径为200μm～400μm的粒状。本发明的实施方式的亲水性气凝胶优选使用0.2重量份～3重量份。Silica aerogel is preferably used as the hydrophilic aerogel according to the embodiment of the present invention. Hydrophilic silica airgel has high hydrophilicity due to the hydroxyl groups on the surface. The hydrophilic airgel according to the embodiment of the present invention is preferably in a granular form with a particle diameter of 200 μm to 400 μm. The hydrophilic aerogel according to the embodiment of the present invention is preferably used in an amount of 0.2 to 3 parts by weight.
根据上述实施方式，通过在聚氨酯泡沫的原料中掺入隔热性能高的亲水性的气凝胶来提高材料的粘度，从而抑制气泡的膨胀。另外，根据上述实施方式，能够延长凝胶时间，消除制品的未填充部分。另外，根据上述实施方式，由于使用优化了含量的亲水性气凝胶的聚氨酯泡沫，因此隔热性得到改善。According to the above-mentioned embodiment, the expansion of the air cells is suppressed by adding a hydrophilic airgel having high thermal insulation performance to the raw material of the polyurethane foam to increase the viscosity of the material. In addition, according to the above-mentioned embodiment, the gel time can be extended, and the unfilled portion of the product can be eliminated. In addition, according to the above-described embodiment, since the urethane foam with the optimized content of the hydrophilic airgel is used, thermal insulation is improved.
实施例1Example 1
本实施例使用表1的原料，按照实施例1～4、比较例1，2及传统例的原料生产聚氨酯泡沫。实施例1～4的聚氨酯泡沫，是多元醇混合物与多异氰酸酯在存在发泡剂、亲水性气凝胶的情况下反应获得的。比较例1、2的聚氨酯泡沫，是多元醇混合物与多异氰酸酯在存在发泡剂、疏水性气凝胶的情况下反应获得的。多元醇混合物与多异氰酸酯在存在发泡剂的情况下反应得到传统例的聚氨酯泡沫。In this embodiment, the raw materials in Table 1 are used to produce polyurethane foam according to the raw materials in Examples 1-4, Comparative Examples 1, 2 and the conventional example. The polyurethane foams of Examples 1-4 are obtained by reacting polyol mixtures with polyisocyanates in the presence of blowing agents and hydrophilic aerogels. The polyurethane foams of Comparative Examples 1 and 2 are obtained by reacting polyol mixtures and polyisocyanates in the presence of blowing agents and hydrophobic aerogels. The polyol mixture is reacted with polyisocyanate in the presence of a blowing agent to obtain a polyurethane foam of the conventional example.
多元醇混合物和气凝胶如下。Polyol mixtures and aerogels are as follows.
多元醇：住化科思创聚氨酯株式会社(Sumika Covestro Urethane Co.,Ltd)制造。Polyol: manufactured by Sumika Covestro Urethane Co., Ltd.
气凝胶：广东埃力生高新科技有限公司制造。Airgel: Manufactured by Guangdong Allison High-tech Co., Ltd.
导热系数用英弘精机公司制造的FOX200测定。The thermal conductivity was measured with FOX200 manufactured by Hideo Seiki Co., Ltd.
所有的聚氨酯泡沫都是100重量份的多元醇混合物、14重量份的发泡剂、124重量份的多异氰酸酯反应而形成了100重量份的聚氨酯泡沫。For all polyurethane foams, 100 parts by weight of polyol mixture, 14 parts by weight of blowing agent, and 124 parts by weight of polyisocyanate were reacted to form 100 parts by weight of polyurethane foam.
实施例1的聚氨酯泡沫含有0.2重量份的亲水性气凝胶，即相对于聚氨酯泡沫含有0.2％的亲水性气凝胶。实施例2的聚氨酯泡沫含有0.5重量份的亲水性气凝胶，即相对于聚氨酯泡沫含有0.5％的亲水性气凝胶。实施例3的聚氨酯泡沫含有1.0重量份的亲水性气凝胶，即相对于聚氨酯泡沫含有1.0％的亲水性气凝胶。实施例4的 聚氨酯泡沫含有3.0重量份的亲水性气凝胶，即相对于聚氨酯泡沫含有3.0％的亲水性气凝胶。实施例1～4中，其它成分相同，改变亲水性气凝胶的含量。The polyurethane foam of Example 1 contains 0.2 parts by weight of the hydrophilic airgel, that is, 0.2% of the hydrophilic airgel relative to the polyurethane foam. The polyurethane foam of Example 2 contains 0.5 parts by weight of the hydrophilic airgel, that is, 0.5% of the hydrophilic airgel relative to the polyurethane foam. The polyurethane foam of Example 3 contained 1.0 parts by weight of the hydrophilic airgel, that is, contained 1.0% of the hydrophilic airgel relative to the polyurethane foam. The polyurethane foam of Example 4 contained 3.0 parts by weight of the hydrophilic airgel, that is, 3.0% of the hydrophilic airgel relative to the polyurethane foam. In Examples 1 to 4, other components are the same, and the content of the hydrophilic aerogel is changed.
另一方面，比较例1的聚氨酯泡沫含有1.0重量份的疏水性气凝胶，即相对于聚氨酯泡沫含有1.0％的疏水性气凝胶，比较例2的聚氨酯泡沫含有3.0重量份的疏水性气凝胶，即相对于聚氨酯泡沫含有3.0％的疏水性气凝胶。比较例1、2与实施例的不同点在于含有疏水性气凝胶来代替亲水性气凝胶。传统例的聚氨酯泡沫不含气凝胶。On the other hand, the polyurethane foam of Comparative Example 1 contains 1.0 parts by weight of the hydrophobic airgel, that is, the polyurethane foam contains 1.0% of the hydrophobic airgel, and the polyurethane foam of Comparative Example 2 contains 3.0 parts by weight of the hydrophobic airgel. The gel, that is, contains 3.0% of hydrophobic airgel relative to the polyurethane foam. The difference between Comparative Examples 1 and 2 and Examples is that hydrophobic aerogel is contained instead of hydrophilic aerogel. Conventional polyurethane foam does not contain airgel.
亲水性气凝胶的含量为0.2％～3％的实施例1～4实现了20.5mW/m·K以下的导热系数。这比传统例的聚氨酯泡沫的导热系数20.9mW/m·K低。因此，实施例1～4与传统例相比隔热性能较高。特别是实施例1和实施例2实现了更低的20.3mW/m·K的导热系数。因此，通过不改变其它成分而将亲水性气凝胶的含量调整为0.2％～0.5％，进一步改善了隔热性能。Examples 1 to 4 in which the content of the hydrophilic airgel was 0.2% to 3% achieved a thermal conductivity of 20.5 mW/m·K or less. This is lower than the thermal conductivity 20.9 mW/m·K of the polyurethane foam of the conventional example. Therefore, Examples 1 to 4 have higher thermal insulation performance than the conventional example. In particular, Example 1 and Example 2 achieved a lower thermal conductivity of 20.3 mW/m·K. Therefore, by adjusting the content of the hydrophilic aerogel to 0.2% to 0.5% without changing other components, the thermal insulation performance is further improved.
相对于此，比较例1的导热系数为21.0mW/m·K。另外，比较例2的导热系数为21.6mW/m·K。比较例1和比较例2的导热系数均高于以往的聚氨酯泡沫的导热系数20.9mW/m·K。因此可知，如果含有疏水性气凝胶来代替亲水性气凝胶，则隔热性能变差。On the other hand, the thermal conductivity of Comparative Example 1 was 21.0 mW/m·K. In addition, the thermal conductivity of Comparative Example 2 was 21.6 mW/m·K. Both the thermal conductivity of Comparative Example 1 and Comparative Example 2 are higher than the thermal conductivity of 20.9 mW/m·K of the conventional polyurethane foam. Therefore, it can be seen that when the hydrophobic aerogel is contained instead of the hydrophilic aerogel, the thermal insulation performance is deteriorated.
另外，实施例1～4与传统例的聚氨酯泡沫相比，发泡密度低，能够使聚氨酯泡沫变轻了。另外，实施例1～4中，低温尺寸稳定性(30℃×48h(％))、高温尺寸稳定性(70℃×48h(％))与传统例相比并不逊色。而且，实施例1～4的压缩强度也为1.2～1.5kgf·cm 2，与传统例相比并不逊色。 In addition, Examples 1 to 4 have a lower foam density than the polyurethane foam of the conventional example, and the polyurethane foam can be made lighter. In addition, in Examples 1 to 4, the dimensional stability at low temperature (30°C×48h (%)) and the dimensional stability at high temperature (70°C×48h (%)) are not inferior to those of the conventional example. Furthermore, the compressive strengths of Examples 1 to 4 were also 1.2 to 1.5 kgf·cm 2 , which was not inferior to the conventional examples.
另外，实施例1～4的泡沫状态也没有泡孔粗糙。In addition, the foam states of Examples 1 to 4 did not have rough cells.
图1是实施例2的聚氨酯泡沫的孔径测量照片。图2是实施例4的聚氨酯泡沫的孔径测量照片。图3是比较例2的聚氨酯泡沫的孔径测量照片。图4是传统例的聚氨酯泡沫的孔径测量照片。参照图1至图4，对本发明的实施方式的聚氨酯泡沫的泡孔直径(气泡的大小)进行说明。FIG. 1 is a photograph of the pore size measurement of the polyurethane foam of Example 2. FIG. FIG. 2 is a photograph of the pore size measurement of the polyurethane foam of Example 4. FIG. FIG. 3 is a photograph of the pore size measurement of the polyurethane foam of Comparative Example 2. FIG. Fig. 4 is a photo of the pore size measurement of the polyurethane foam of the conventional example. The cell diameter (the size of the cells) of the polyurethane foam according to the embodiment of the present invention will be described with reference to FIGS. 1 to 4 .
参照图1，实施例2的聚氨酯泡沫的泡孔平均直径为约137μm。参照图2，实施例4的聚氨酯泡沫的泡孔平均直径为约142μm。由此可知，当将聚氨酯泡沫的亲水性气凝胶从3％降低到0.5％时，泡孔平均直径变小。Referring to FIG. 1 , the average cell diameter of the polyurethane foam of Example 2 was about 137 μm. Referring to FIG. 2 , the average cell diameter of the polyurethane foam of Example 4 was about 142 μm. It can be seen that when the hydrophilic airgel of the polyurethane foam is reduced from 3% to 0.5%, the average cell diameter becomes smaller.
参照图3，比较例2的聚氨酯泡沫的泡孔平均直径为167μm。参照图4，传统例的聚氨酯泡沫的泡孔平均直径为197μm。由图1～4可知，含有疏水性气凝胶的聚氨酯泡沫和以往的聚氨酯泡沫的泡孔平均直径均大于含有亲水性气凝胶的聚氨酯泡 沫。Referring to FIG. 3 , the average cell diameter of the polyurethane foam of Comparative Example 2 was 167 μm. Referring to FIG. 4 , the average cell diameter of the polyurethane foam of the conventional example was 197 μm. From Figures 1 to 4, it can be seen that the average cell diameter of the polyurethane foam containing the hydrophobic airgel and the conventional polyurethane foam is larger than that of the polyurethane foam containing the hydrophilic airgel.
因此，实施例1～4与比较例1、2和传统例相比，能够减小泡孔平均直径，即能够使气泡微细。另外，实施例1～4通过调整亲水性气凝胶的含量，能够进一步减小了泡孔平均直径。Therefore, in Examples 1 to 4, compared with Comparative Examples 1 and 2 and the conventional example, the average cell diameter can be reduced, that is, the cells can be made finer. In addition, in Examples 1 to 4, the average cell diameter can be further reduced by adjusting the content of the hydrophilic aerogel.
[表1][Table 1]
Figure PCTCN2022139036-appb-000001
Figure PCTCN2022139036-appb-000001
隔热材料的聚氨酯泡沫为硬质聚氨酯泡沫，能够没有未填充部分和泡孔粗糙地填充到制品中，低温变形性小，能够用于冰箱、冷冻库或冷藏库。The urethane foam of the heat insulating material is a rigid urethane foam, which can be filled into the product roughly without unfilled parts and cells, has little deformation at low temperatures, and can be used in refrigerators, freezers, or freezers.
根据本发明，能够提供隔热性能得到改善的隔热材料。采用本发明，能够提供泡孔平均直径比以往的聚氨酯泡沫小的隔热材料。采用本发明，通过调整聚氨酯泡沫中亲水性气凝胶的含量，能够提供隔热性能进一步改善的隔热材料。采用本发明，通过调整聚氨酯泡沫中亲水性气凝胶的含量，能够提供进一步减小泡孔平均直径的 隔热材料。According to the present invention, a heat insulating material with improved heat insulating performance can be provided. According to the present invention, it is possible to provide a heat insulating material having a smaller average cell diameter than conventional polyurethane foams. According to the present invention, by adjusting the content of the hydrophilic airgel in the polyurethane foam, it is possible to provide a heat insulating material with further improved heat insulating performance. According to the present invention, by adjusting the content of the hydrophilic airgel in the polyurethane foam, it is possible to provide a heat insulating material with a further reduced cell average diameter.
另外，采用本发明，能够提供一种隔热材料，其中，聚氨酯泡沫由胺系多元醇、聚酯系多元醇及作为催化剂的脂肪族胺化合物的多元醇混合物，二苯基甲烷二异氰酸酯的多异氰酸酯，以及环戊烷等发泡剂的混合物得到，亲水性气凝胶是二氧化硅气凝胶。采用本发明，能够提供使用聚氨酯泡沫为硬质聚氨酯泡沫的隔热材料来改善冰箱、冷藏库或冷冻库的隔热性能。In addition, according to the present invention, it is possible to provide a heat insulating material in which the polyurethane foam is composed of a polyol mixture of an amine polyol, a polyester polyol, and an aliphatic amine compound as a catalyst, a polyol mixture of diphenylmethane diisocyanate, Isocyanate, and a mixture of blowing agents such as cyclopentane are obtained, and the hydrophilic airgel is silica airgel. According to the present invention, it is possible to provide a heat insulating material using rigid polyurethane foam to improve the heat insulating performance of refrigerators, refrigerators, or freezers.
产业上的可利用性Industrial availability
本发明的聚氨酯泡沫的导热系数低，能够用作冰箱、冷冻库、冷藏库的隔热材料。另外，本发明的聚氨酯泡沫还能够用于夹芯板、板用建材、保冷管等。The polyurethane foam of the present invention has a low thermal conductivity and can be used as a heat insulating material for refrigerators, freezers, and refrigerators. In addition, the polyurethane foam of the present invention can also be used for sandwich panels, building materials for panels, cooling pipes, and the like.

Claims (10)

  1. 一种隔热材料，其特征在于，包含含有0.2％～3％的亲水性气凝胶的聚氨酯泡沫。A heat insulating material characterized by comprising polyurethane foam containing 0.2% to 3% of hydrophilic airgel.
  2. 根据权利要求1所述的隔热材料，其特征在于，所述聚氨酯泡沫的泡孔平均直径为142μm以下。The heat insulating material according to claim 1, wherein the polyurethane foam has an average cell diameter of 142 μm or less.
  3. 根据权利要求1所述的隔热材料，其特征在于,聚氨酯泡沫含有0.2％～0.5％的亲水性气凝胶。The heat insulating material according to claim 1, wherein the polyurethane foam contains 0.2% to 0.5% of hydrophilic airgel.
  4. 根据权利要求3所述的隔热材料，其特征在于，The heat insulating material according to claim 3, characterized in that,
    所述聚氨酯泡沫的泡孔平均直径为137μm以下。The polyurethane foam has an average cell diameter of 137 μm or less.
  5. 根据权利要求1所述的隔热材料，其特征在于，The heat insulating material according to claim 1, characterized in that,
    所述聚氨酯泡沫由The polyurethane foam consists of
    胺系多元醇、聚酯系多元醇和作为催化剂的脂肪族胺化合物的多元醇混合物，二苯基甲烷二异氰酸酯的多异氰酸酯，Polyol mixtures of amine polyols, polyester polyols and aliphatic amine compounds as catalysts, polyisocyanates of diphenylmethane diisocyanate,
    以及发泡剂、亲水性气凝胶的混合物获得，And the mixture of foaming agent and hydrophilic airgel is obtained,
    亲水性气凝胶是二氧化硅气凝胶。Hydrophilic aerogels are silica aerogels.
  6. 根据权利要求5中任一项所述的隔热材料，其特征在于，The insulating material according to any one of claims 5, characterized in that,
    胺系多元醇包含三乙醇胺、乙二胺、芳香族二胺、二亚乙基三胺中的1种或多种；Amine polyols contain one or more of triethanolamine, ethylenediamine, aromatic diamine, and diethylenetriamine;
    聚酯系多元醇由羧酸和多元醇脱水缩合获得，所述羧酸为己二酸或邻苯二甲酸；所述多元醇为乙二醇、或1，4-丁二醇、或1，6-己二醇；Polyester polyol is obtained by dehydration condensation of carboxylic acid and polyol, the carboxylic acid is adipic acid or phthalic acid; the polyol is ethylene glycol, or 1,4-butanediol, or 1, 6-hexanediol;
    脂肪族胺化合物包括甲胺、二甲胺，三甲胺、乙胺、二乙胺、三乙胺，乙二胺、三乙醇胺、N，N-二异丙基乙胺、四甲基乙二胺、己二胺、亚精胺、精胺、金刚烷胺、四甲基己二胺、五甲基二乙烯三胺中的一种或多种；Aliphatic amine compounds include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, triethanolamine, N,N-diisopropylethylamine, tetramethylethylenediamine , one or more of hexamethylenediamine, spermidine, spermine, amantadine, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine;
    多异氰酸酯包括甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、间苯二甲基异氰酸酯中的一种或多种；Polyisocyanates include one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate;
    发泡剂包括环戊烷、三氯氟甲烷、1，1-二氯-1-氟甲烷、1，1，1，3，3-五氟丙烷、1，1，1，3，3-五氟丁烷、二氧化碳中的一种或多种。Blowing agents include cyclopentane, trichlorofluoromethane, 1,1-dichloro-1-fluoromethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-penta One or more of fluorobutane and carbon dioxide.
  7. 根据权利要求6中任一项所述的隔热材料，其特征在于，由100重量份多元醇混合物、124重量份的异氰酸酯化合物的多异氰酸酯、14重量份的发泡剂、0.2～3 重量份的亲水性凝胶混合得到100重量份的聚氨酯泡沫。The heat insulating material according to any one of claim 6, characterized in that 100 parts by weight of polyol mixture, 124 parts by weight of polyisocyanate of isocyanate compound, 14 parts by weight of blowing agent, 0.2 to 3 parts by weight The hydrophilic gel was mixed to obtain 100 parts by weight of polyurethane foam.
  8. 根据权利要求6所述的隔热材料，其特征在于，亲水性气凝胶为200μm～400μm的粒状，亲水性气凝胶相较聚氨酯泡沫的质量分数为0.2％～3％。The heat insulating material according to claim 6, characterized in that the hydrophilic airgel is in the granular shape of 200 μm-400 μm, and the mass fraction of the hydrophilic airgel relative to the polyurethane foam is 0.2%-3%.
  9. 根据权利要求1所述的隔热材料，其特征在于，导热系数介于20.3mW/m·K～20.5mW/m·K。The heat insulating material according to claim 1, characterized in that the thermal conductivity is between 20.3mW/m·K～20.5mW/m·K.
  10. 一种冰箱、冷藏库或冷冻库，使用权利要求1到9中任一项所述的使用隔热材料。A refrigerator, refrigerator or freezer using the heat insulating material described in any one of claims 1 to 9.
PCT/CN2022/139036 2021-12-17 2022-12-14 Thermal insulation material, and refrigerator, refrigerated storage, or freezer using same WO2023109869A1 (en)

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