CN113710715A - 一种基于整体有机气凝胶的模制品 - Google Patents

一种基于整体有机气凝胶的模制品 Download PDF

Info

Publication number
CN113710715A
CN113710715A CN202080028878.XA CN202080028878A CN113710715A CN 113710715 A CN113710715 A CN 113710715A CN 202080028878 A CN202080028878 A CN 202080028878A CN 113710715 A CN113710715 A CN 113710715A
Authority
CN
China
Prior art keywords
layer
aerogel
gel
monolithic
density
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202080028878.XA
Other languages
English (en)
Inventor
S·莫瓦海德
M·诺比斯
M·弗力可
W·勒尔斯贝格
D·温里克
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Elig Itt GmbH
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of CN113710715A publication Critical patent/CN113710715A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C08J9/283—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum a discontinuous liquid phase emulsified in a continuous macromolecular phase
    • 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
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/046—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
    • B32B19/04—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica next to another layer of the same or of a different material
    • B32B19/047—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B32B7/14—Interconnection of layers using interposed adhesives or interposed materials with bonding properties applied in spaced arrangements, e.g. in stripes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/046—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • 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
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
    • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • 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
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • 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
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/3243—Polyamines aromatic containing two or more aromatic rings
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • 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
    • F16L59/029—Shape or form of insulating materials, with or without coverings integral with the insulating materials layered
    • 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
    • F16L59/04—Arrangements using dry fillers, e.g. using slag wool which is added to the object to be insulated by pouring, spreading, spraying or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0058—Liquid or visquous
    • B29K2105/0061—Gel or sol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/12—Gel
    • B32B2266/126—Aerogel, i.e. a supercritically dried gel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2509/00—Household appliances
    • B32B2509/10—Refrigerators or refrigerating equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/18—Aircraft
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0091—Aerogels; Xerogels
    • 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
    • C08G2220/00—Compositions for preparing gels other than hydrogels, aerogels and xerogels
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

一种基于整体有机气凝胶的模制品，其密度为60至300kg/m3，热导率为12至17.8mW/m＊K，具有大于30体积％的直径小于150nm的孔，且具有大于20体积％的直径小于27nm的孔，基于总的孔体积计，以及通过压缩制备模制品的方法。

Description

一种基于整体有机气凝胶的模制品
本发明涉及一种密度为100至300kg/m3且热导率为12至17.8mW/m＊K的基于整体有机气凝胶的模制品，一种通过压缩基于整体有机气凝胶的模制品来制备所述模制品的方法，和一种包含片状形式的模制品的绝热材料。
软质聚氨酯泡沫和三聚氰胺-甲醛泡沫的热导率高于约30毫瓦/mk，与基于气凝胶的绝热板相比明显更高。由于较高的热导率，隔热性能较差。然而，刚性聚氨酯泡沫通常非常脆。
DE 10 2005 021 994公开了一种通过用气密膜包封包含开孔泡沫(优选硬质聚氨酯泡沫)的成型体以及随后对膜进行抽真空和气密焊接关闭来制备真空绝热板的方法，其中将包含开孔泡沫的成型体在固化之后和抽真空之前压缩。
可通过超临界和非超临界干燥获得的基于多异氰酸酯的气凝胶和干凝胶公开于WO 95/02009和WO 95/03358中。
WO 96/37539涉及基于多异氰酸酯的气凝胶及其制备方法。气凝胶通过在溶剂中混合有机多异氰酸酯、炭黑和催化剂而制备，并且能够制备密度低于不含填料的气凝胶的填充的多异氰酸酯基有机气凝胶。
US 2006/211840 A公开了聚脲气凝胶以及通过将多异氰酸酯与多胺在溶剂中混合并超临界干燥所得凝胶来制备聚脲气凝胶的方法。聚氧化烯胺是优选类型的多胺。
WO 2008/138978公开了干凝胶，其包含30至90重量％的至少一种多官能异氰酸酯和10至70重量％的至少一种多官能芳族胺，并且具有不超过5微米的体积平均孔径及其用于真空绝热板的用途。密度为170kg/m3的气凝胶材料在1004mbar压力下的热导率高于37mW/m＊K。
WO 2014/068105涉及包括型材和至少部分被型材包围的绝热芯的复合元件，其中绝热芯由有机多孔材料组成，其根据DIN 12667确定的热导率为13至30mW/m＊K，并且根据DIN 53421确定的抗压强度大于0.20N/mm′，涉及制备这种复合元件的方法和这种复合元件用于制备门窗、冷藏和/或冷冻装置和橱柜或立面结构元件的用途。实施例中的多孔材料的热导率为20至21mW/m＊K，密度为110至153g/l。
WO 2017/125414和WO 2017/125415涉及一种制备具有低密度、足够机械稳定性和环境压力下低热导率的基于异氰酸酯的气凝胶和干凝胶的方法及其作为绝热材料或用于真空绝热板的用途。
WO 2016/008726涉及一种制备多孔材料的方法，至少提供一种包含组合物(A)(包含适于形成有机凝胶的组分)的混合物(I)和溶剂(B)，使组合物(A)中的所述组分在溶剂(B)的存在下反应以形成凝胶，并将步骤b)中获得的凝胶干燥，其中组合物(A)包含选自具有4至8个碳原子的饱和或不饱和单羧酸的碱金属盐或碱土金属盐的催化剂(C)。
Lee等人在J Sol-gel Sci Technol(2009)49第209-220页中描述了通过溶胶-凝胶过程和超临界干燥获得的轻质聚脲基有机气凝胶。聚脲基气凝胶的收缩系数和热导率值(在37.8℃下确定)都随着目标和最终密度的增加而降低。
在Journal of Non-Crystalline Solids，2014，406，73-78中确定单轴压缩聚脲气凝胶基材的机械稳定性和热导率作为密度函数。固体热导率作为密度的函数而上升。
EP 2 615 132公开一种包含气凝胶颗粒和聚四氟乙烯(PTFE)粘合剂的材料，其在大气条件下的热导率小于或等于25mW/m K。该材料为可模制的或可成型的，具有很少或没有脱落或填料颗粒，并且可以例如通过将材料粘合在两个外层之间而形成诸如胶带或复合材料的结构。有利地，复合材料可以弯折、拉伸或弯曲而不会显著起尘或损失绝缘性能。
US 2014/0287641公开气凝胶材料和非气凝胶材料的层状复合材料，如纤维状片材或层压板，包括具有多功能特性的用于各种应用的机械强度复合材料，如用于服装的绝热、防弹材料、太空应用、飞机的轻质结构和汽车零件或运动器材。
WO 2016/053399公开了厚度小于10mm的高耐用、柔韧的纤维增强气凝胶的制备，其可用作热电池应用中的绝热材料。优选将无机二氧化硅气凝胶应用于非织造纤维增强材料。
因此，本发明的一个目的是避免上述缺点并提供基于整体有机气凝胶的模制品，其在高密度(尤其是密度大于100kg/m3)下具有低热导率。此外，模制品应具有足够的抗压强度、高柔韧性并且在处理过程中不应脆碎。此外，制备模制品的方法应该是容易的。
根据本发明，该目的通过基于整体有机气凝胶的模制品而实现，所述模制品的密度为60至300kg/m3，热导率为12至17.8mW/m＊K，且具有多于30体积％的直径小于150nm的孔，并且具有多于20体积％的直径小于27nm的孔，基于总的孔体积计。
本发明的基于整体有机气凝胶的模制品的密度为60至300kg/m3，优选为100至300kg/m3，更优选为140至240kg/m3。
热导率为12至17.8mW/m＊K，优选为15.5至17.0mW/m＊K，根据DIN EN 12667：2001-05在10℃和101325Pa下测量。
本发明的基于整体有机气凝胶的模制品具有多于30体积％的直径小于150nm的孔(中孔)和多于20体积％的直径小于27am的孔，基于总的孔体积计。直径150nm以上的孔(大孔)的比例为70体积％或更少。
优选地，本发明的基于整体有机气凝胶的模制品具有40至80体积％的直径小于150nm的孔(中孔)和21至75体积％的直径小于27nm的孔，基于总的孔体积计。直径150nm以上的孔(大孔)的比例优选为60至20体积％。
更优选地，本发明的基于整体有机气凝胶的模制品具有50至80体积％的直径小于150nm的孔(中孔)和40至75体积％的直径小于27nm的孔(中孔)，基于总的孔体积计。直径为150nm和更大的孔(大孔)的比例更优选为50至20体积％。
最优选地，本发明的模制品的密度为140至240kg/m3，热导率为15.5至17.0mW/m＊K，并且具有40至80体积％的直径小于150nm的孔，和21到75体积％的直径小于27nm的孔，基于总的孔体积计。
本发明的模制品优选具有平均孔径尺寸为1至150nm。
本发明的模制品的压缩强度优选为600-700kPa。根据DIN EN 12089：2013-06确定的弯曲强度优选为1000-5000KPa，更优选为1000-2500KPa。弯曲度优选为10-20mm。
根据所选择的成型工具，本发明的模制品可以具有各种尺寸和形状。模制品可以是块状或片状。模制品优选为厚度在100μm至10mm范围内，更优选在3至10mm范围内的片材形式。
根据所选择的模具，本发明的模制品可具有一定的表面纹理。
气凝胶为多孔材料，其可通过将溶胶倒入模具中，然后通过与超临界二氧化碳(scCO2)的溶剂交换进行干燥来获得。优选的气凝胶基于聚氨酯(PU)或聚脲(PUR)。有机气凝胶优选为基于聚氨酯(PU)、聚脲或聚异氰脲酸酯(PIR)或其混合物的整体气凝胶。优选地，有机气凝胶具有小于80％、更优选地小于50％的聚异氰脲酸酯(PIR)结构，基于PU-、PUR-和PIR-结构的总量计。PU-、PUR-和PIR-结构的量可以通过红外(IR)光谱测定。优选的气凝胶可以通过使包含至少一种多官能异氰酸酯(a1)、至少一种芳族胺(a2)和至少一种催化剂(a3)的混合物(A)在溶剂(B)的存在下反应以形成凝胶，并在超临界条件下干燥获得的凝胶来制备，如下文更详细描述的。
高度交联的有机气凝胶和干凝胶的片材或模制品通常是非柔性的。它们可以通过非破坏性压缩转换成更薄的片材或模制品，而没有在液压机或气动压力机中进行的横向变形。由于更高的密度，压缩片材或模制品显示出更好的机械性能。令人惊讶的是，与未压缩的具有可比密度的片材或模制品相比，导热性另外显著降低。压缩片材或模制品在脆碎性测试中表现出较低的材料损失。
本发明还涉及一种制备上述模制品的方法，该方法包括压缩一种密度为50至140kg/m3，优选为80至140kg/m3，压缩因子(compressing factor)为5至70体积％的基于有机气凝胶的模制品以获得基于整体有机气凝胶的模制品，该整体有机气凝胶的密度为60至300kg/m3，优选为100到300kg/m3，更优选为140至240kg/m3。压缩因子优选为30至50体积％。
优选的方法包括在片材的厚度方向上单向压缩片材形式的基于有机气凝胶的模制品。
压缩可以在液压机或气动压力机中进行。优选地，模制品的温度为10至80℃。施加的压力优选为0.12-10MPa/1000cm2。在压缩过程中，可以使用工具，即带有标志的工具，将标志压印在片材的表面上。
在压缩之前，有机气凝胶片材或模制品具有均匀的纳米多孔结构，平均孔径尺寸为10至1000nm，并显示出热导率为18到20mW/m＊K和密度为80至140kg/m3。这样的气凝胶片材或模制品可以即如WO 2017/125414中所述来制备。
在压缩之后，气凝胶片材或模制品更柔韧并且具有更低的热导率。片材或模制品的热导率优选为17.8mW/m＊K或更低，更优选在15.5至17.0mW/m＊K，密度为100-300kg/m3，优选为140和240kg/m3。压缩后的平均孔径尺寸优选为1至100nm。
制备如上所述的模制品的另一优选方法包括以下步骤：
a)使包含至少一种多官能异氰酸酯(a1)、至少一种芳族胺(a2)和至少一种催化剂(a3)的混合物(A)在溶剂(B)存在下反应以形成凝胶，
b)在超临界条件下干燥步骤b)中获得的凝胶，
c)任选地将干燥的凝胶切成厚度为0.1至10mm的片，和
d)将干燥的凝胶压缩至密度为100至300kg/m3。
可能的多官能异氰酸酯是每分子具有两个或更多个异氰酸酯基团的芳族、脂族、脂环族和/或芳脂族异氰酸酯。
作为多官能异氰酸酯(a1)，优选芳族异氰酸酯。特别优选的组分(a1)的多官能异氰酸酯为以下实施方案：
(i)基于甲苯二异氰酸酯(TDI)的多官能异氰酸酯，特别是2，4-TDI或2，6-TDI或2，4-和2，6-TDI的混合物；
(ii)基于二苯基甲烷二异氰酸酯(MDI)的多官能异氰酸酯，特别是2，2′-MDI或2，4′-MDI或4，4′-MDI或低聚MDI，也称为聚苯基聚亚甲基异氰酸酯，或两种或三种上述二苯基甲烷二异氰酸酯或粗制MDI的混合物，所述粗制MDI在MDI或至少一种MDI低聚物的混合物和至少一种上述低分子量MDI衍生物的制备中获得；
(iii)至少一种实施方案i)的芳族异氰酸酯和至少一种实施方式ii)的芳族异氰酸酯的混合物。
优选地，芳族胺(a2)为多官能芳族胺。
所述胺(a2)优选选自3，3′，5，5′-四烷基-4，4′-二氨基二苯基甲烷、3，3′，5，5′-四烷基-2，2′-二氨基二苯基甲烷和3，3′，5，5′-四烷基-2，4′-二氨基二苯基甲烷，其中3、3′、5和5′位置的烷基可以相同或不同并且各自独立地选自具有1至12个碳原子并可带有其它官能团的直链或支链烷基。上述烷基优选为甲基、乙基、正丙基、异丙基、正丁基、仲丁基或叔丁基(各自未取代)。
组合物(A)优选进一步包含至少一种一元醇(am)。原则上，在本发明的上下文中可以使用任何一元醇。根据本发明，组合物(A)还可能含两种或更多种一元醇。一元醇可以是支化的或直链的。根据本发明，伯醇、仲醇或叔醇是合适的。优选地，一元醇(am)是直链醇，更优选直链伯醇。在本发明的上下文中，一元醇可以是脂族一元醇或芳族一元醇。此外，一元醇还可以含有其他官能团，只要这些官能团在本发明方法的条件下不与其他组分反应。一元醇可以例如包含C-C双键或C-C三键。一元醇可以例如是卤化一元醇，特别是氟化一元醇，例如多氟化一元醇或全氟化一元醇。
根据另一个实施方案，本发明因此涉及制备如上文公开的多孔材料的方法，其中组合物(A)包含至少一种一元醇(am)。
催化剂(a3)优选选自二甲基环己胺、双(2-二甲基氨基乙基)醚、N，N，N，N，N-五甲基二亚乙基三胺、甲基咪唑、二甲基咪唑、氨基丙基咪唑、二甲基苄基胺、1，6-二氮杂双环[5.4.0]-7-十一烯、三二甲氨基丙基六氢三嗪、三乙胺、三(二甲氨基甲基)苯酚、三乙二胺(二氮杂双环[2.2.2]辛烷)、二甲氨基乙醇胺、二甲氨基丙胺、N，N-二甲氨基乙氧基乙醇、N，N，N-三甲氨基乙基乙醇胺、三乙醇胺、二乙醇胺、三异丙醇胺、二异丙醇胺、甲基二乙醇胺、丁基二乙醇胺、乙酰丙酮金属盐、羧酸铵和羧酸金属盐如乙酸盐、丙酸盐、山梨酸盐、乙基己酸盐、辛酸盐、苯甲酸盐和柠檬酸盐、磷酸铵和磷酸金属盐。
组合物(A)还可包含至少一种阻燃剂(af)。根据本发明，化合物(af)包含磷和至少一种对异氰酸酯呈反应性的官能团。根据本发明，磷可以以包含磷的官能团的形式存在于化合物(af)中或存在于分子的任何其他部分中，例如存在于分子的主链中。化合物(af)进一步包含至少一种对异氰酸酯呈反应性的官能团。化合物(af)还可包含两种或更多种对异氰酸酯呈反应性的官能团，特别是对异氰酸酯呈反应性的两种基团。通常，根据本发明，化合物(af)以使得多孔材料中磷含量为1至5重量％的量使用。
对异氰酸酯呈反应性的合适的官能团为例如羟基或胺基。在本发明的上下文中，组合物(A)也可能包含两种或更多种不同的化合物(af)。组合物(A)可以例如包含一种包含磷和至少一种对异氰酸酯呈反应性的官能团的化合物(af)和包含磷和至少两个对异氰酸酯呈反应性的官能团的第二化合物(af)。
合适的包含磷的官能团是本领域技术人员已知的。包含磷的官能团可例如选自磷酸盐、膦酸盐、次膦酸盐、亚磷酸盐、亚膦酸盐、次膦酸盐和氧化膦。因此，根据进一步的实施方案，本发明涉及制备如上公开的多孔材料的方法，其中化合物(af)包含至少一种包含磷的官能团，所述磷选自磷酸盐、膦酸盐、次膦酸盐、亚磷酸盐、亚膦酸盐、次膦酸盐和氧化膦。
组合物(A)优选进一步包含至少一种多元醇(ap)。原则上，在本发明的上下文中可以使用任何多元醇。根据本发明，组合物(A)还可以包含两种或更多种多元醇。多元醇可以是支化的或直链的。根据本发明，伯醇、仲醇或叔醇是合适的。优选地，多元醇(ap)是线性二醇，更优选线性伯二醇。在本发明的上下文中，多元醇可以是脂族多元醇或芳族多元醇。此外，多元醇还可以包含其他官能团，只要这些官能团在本发明方法的条件下不与其他组分反应即可。多元醇可以例如包含C-C-双键或C-C三键。多元醇可以是例如卤化多元醇，特别是氟化多元醇，例如多氟化多元醇。
在本发明的上下文中，多元醇还可选自烯丙醇、烷基酚或炔丙醇。此外，烷氧基化物可用于本发明的上下文中，例如脂肪醇烷氧基化物、氧代醇烷氧基化物或烷基酚烷氧基化物。
根据进一步优选的实施方案，多元醇选自具有1至20个碳原子的脂族或芳族多元醇。合适的伯多元醇是例如直链醇如乙二醇、二甘醇、三甘醇、四甘醇、丙二醇、丁二醇、戊二醇、己二醇、庚二醇或辛二醇。其他的实例为聚氧化烯、聚氧化烯基、聚酯二醇、聚酯醇、聚醚二醇，尤其是聚丙二醇、聚乙二醇、聚丙二醇、聚亚丙基乙二醇。
合适的支化伯多元醇是例如甘油和三羟甲基丙烷。
可以使用多元醇的混合物。混合物可以理解为例如共聚物，但也可以理解为聚合多元醇或非聚合多元醇的混合物。
通常，存在于组合物(A)中的多元醇的量可在宽范围内变化。优选地，多元醇以基于组合物(A)计的0.1至30重量％的量，更优选地以基于组合物(A)计的0.5至25重量％的量，特别是以基于组合物(A)计的1.0至22重量％的量，例如基于组合物(A)计的1.5至20重量％的量存在于组合物(A)中。
可能的溶剂(B)是例如酮、醛、链烷酸烷基酯、酰胺如甲酰胺、N-甲基吡咯烷酮、N-乙基吡咯烷酮、亚砜如二甲亚砜、脂族和脂环族卤代烃、卤代芳族化合物和含氟醚。两种以上上述化合物的混合物同样是可能的。特别优选醛和/或酮作为溶剂(B)。合适的醛或酮特别是乙醛、丙醛、正丁醛、异丁醛、2-乙基丁醛、戊醛、异戊醛、2-甲基戊醛、2-乙基己醛、丙烯醛、甲基丙烯醛、巴豆醛、糠醛、丙烯醛二聚体、甲基丙烯醛二聚体、1，2，3，6-四氢苯甲醛、6-甲基-3-环己烯醛、氰基乙醛、乙醛酸乙酯、苯甲醛、丙酮、二乙酮、甲乙酮、甲基异丁基酮、甲基正丁基酮、甲基戊酮、二丙基酮、乙基异丙基酮、乙基丁基酮、二异丁基酮、5-甲基-2-乙酰基呋喃、2-乙酰基呋喃、2-甲氧基-4-甲基戊-2-酮、5-甲基庚烷-3-酮、2-庚酮、辛酮、环己酮、环戊酮和苯乙酮。上述醛和酮也可以混合物的形式使用。优选具有每个取代基具有至多达3个碳原子的烷基的酮和醛作为溶剂(B)。
混合物(A)的组分，例如组分(a1)和(a2)优选彼此分开提供，各自在合适的部分量的溶剂(B)中。单独提供使得在混合之前和混合过程中对胶凝反应进行最佳监测或控制成为可能。
步骤a)中的胶凝形成是加聚反应，特别是异氰酸酯基团和氨基的加聚反应。为了本发明的目的，凝胶是基于聚合物(其与液体接触存在)的交联系统(称为溶剂凝胶或液凝胶，或与水作为液体：水凝胶(aquagel)或水凝胶(hydrogel))。此处，聚合物相形成连续的三维网络。
步骤b)中凝胶的干燥在超临界条件下进行，优选在用CO2或适用于超临界干燥目的的其他溶剂替代溶剂之后进行。这种干燥本身是本领域技术人员已知的。超临界条件表征CO2或用于去除胶凝溶剂的任何溶剂以超临界状态存在的温度和压力。以此方式，可以减少去除溶剂时凝胶体的收缩。
步骤c)中的压缩可以在液压机或气动压力机中进行。优选地，模制品的温度为10和80℃。施加的压力优选在0.12-10MPa/1000cm2。
本发明的方法允许通过使用不同的工具和/或压力来制备具有不同形状和厚度(即楔形的)的有机气凝胶的模制品或片材。
可以在压缩之前或之后将涂料或层压材料施用至片材或模制品上。片材或模制品可以在压缩过程中通过使用压花工具进行压花。标志、或装饰物或图案因此可施加至片材或模制品的表面。
可通过将涂层或柔性层施加至如上所述的基于整体有机气凝胶的模制品上获得柔性产品。柔性层可以是热塑性聚合物，或用有机纤维或无机纤维或机织织物(wovenfabrics)或非机织织物(non-woven fabrics)增强的热塑性聚合物。涂层或柔性层可以用添加剂改性以赋予功能，例如导电性或阻燃性。优选覆盖层C)是聚合物膜，更优选透明聚丙烯膜。
因此，本发明的另一主题是一种绝热材料，其包含片材形式的基于整体有机气凝胶的模制品作为层A)和至少一个涂层或覆盖层C)。优选地，层A)的厚度为0.99至1.99mm，更优选为0.25至1.45mm。所述至少一个涂层或覆盖层C)的厚度为0.01至1mm，更优选为0.05至0.5mm。
另外的功能层F)可包含在层A)之间以及层A)和C)之间。功能层F)优选选自电绝缘或导电层、阻燃层或散热器层。可以将多个功能集成为一层F)。
这些层可以通过热、压力或化学键合彼此连接。优选地，这些层通过粘合剂连接。粘合剂可以以斑点、条纹或其他图案或以单独的粘合剂层(B)施用。优选地，绝热材料由一层A)和一层或两层C)组成，它们通过粘合剂层B)连接，从而分别产生层结构A-B-C和C-B-A-B-C。
为了促进隔热材料的施用，可以将另外的粘合剂层B)施加至覆盖层C)的外侧，从而产生结构A-B-C-B和C-B-A-B-C-B。
在绝热材料中，每一层A)、B)、C)和F)具有不同的化学组成，但可具有相似的功能，例如除了它们的主要功能之外，还具有阻燃性。
优选地，绝热材料的厚度为0.3至2.5mm。对于需要胶带或箔形式的非常薄的绝热材料的应用，优选仅存在层A)、B)和C)。对于非常薄的绝热胶带或箔特别优选由一层A)、一层B)和一层覆盖层C)组成的绝热材料。
如果具有较高柔韧性的绝热胶带是有利的，则优选由具有层结构C-B-A-B-C的通过粘合剂层B)连接的由一层A)和两层覆盖层C)组成的绝热材料。
优选地，至少一个层A的厚度为0.09至4.49mm，更优选为0.25至2.45mm。
至少一个覆盖层C)的厚度优选为0.01至2.5mm，更优选0.05至1.0mm，最优选0.05至0.5mm。
优选地，所有层A)的总厚度为绝热材料总厚度的50％至99.9％，更优选地90％至99％。
层B)
对于粘合剂层，可以使用任何合适的粘合剂，例如聚氨酯、丙烯酸酯、环氧树脂、硅酸酯或硅氧烷。粘合剂层B)可包含添加剂，例如碳粉、玻璃纤维或粉末或阻燃剂。
粘合剂层可以直接施加到任何层的一侧或两侧，优选施加到覆盖层C)或功能层F)。优选地，层C)以由覆盖层C)和粘合剂层B)组成的混合胶带CB)或由覆盖层C)、功能层F)和粘合剂层B组成的混合胶带CFB的形式使用。然后可以将混合层固定到气凝胶层A)的一侧或两侧以构建绝热材料。
层C)
层C)在化学上不同于层A)和/或具有不同的机械性能。与气凝胶层A)相比，层C)优选具有更高的机械柔韧性。柔性产品可以通过在基于如上所述的整体有机气凝胶的模制品的表面上施用涂层或柔性覆盖层C)来获得。柔性覆盖层C)可以是热塑性聚合物，或用有机纤维或无机纤维或织机织物或非织机织物增强的热塑性聚合物。适合作为柔性覆盖层的其他材料是石墨或石墨烯膜、金属膜或陶瓷膜，例如羟基磷灰石(hydroxyapatite)膜或玻璃纤维纸。涂层或柔性层C)可以用添加剂改性以赋予功能性，例如导电性或绝缘性或阻燃性。优选地，覆盖层C)是聚合物膜、石墨或石墨烯膜、金属膜或陶瓷膜，例如羟基磷灰石膜或矿物绒(mineral fleece)。更优选热塑性聚合物膜，例如透明聚乙烯膜、聚丙烯膜或聚对苯二甲酸酯膜或矿物绒。
层F)
功能层F)任选地用于绝热材料中并且优选为导电或绝缘层、阻燃层、散热器层。功能层F)可以作为单独层施用，优选在层A)和C)之间施用或作为混合胶带CF或CBF施用，该混合胶带CF或CBF包括任选地通过粘合剂层B)连接至功能层F)的层C)。
因此，本发明的另一主题是一种绝热材料，其包含片材形式的基于整体有机气凝胶的模制品作为层A)和至少一个涂层或覆盖层C)。优选地，层A)的厚度为0.09至4.49mm，更优选为0.25至2.45mm。至少一个涂层或覆盖层C)的厚度为0.01至2.5mm，更优选为0.05至1.0mm。
优选地，层压片材包括附着在基于聚氨酯(PU)、聚脲(PUR)、聚异氰脲酸酯(PIR)或其混合物的整体气凝胶的层A)的全部或部分表面上的胶黏带。优选地，层C包括面向外侧的粘合剂层，以方便地附接到其他部件。
绝热材料可通过热成型或滚压成直径低至3mm的圆柱体以适用于各种形式。绝热材料可以很容易地用剪刀或锯等常用工具切割成所需的形状。
优选地，绝热材料包括作为层C)的胶黏带，其附着在基于聚氨酯(PU)、聚脲(PUR)、聚异氰脲酸酯(PIR)或其混合物的整体气凝胶的层A)的全部或部分表面上.
绝热材料可通过热成型或滚压成直径低至10mm的圆柱体以适用于各种形式。
本发明的另一个主题是一种制备绝热材料的方法，包括以下步骤：
a)使包含至少一种多官能异氰酸酯(a1)、至少一种芳族胺(a2)和至少一种催化剂(a3)的混合物(A)在溶剂(B)存在下反应形成凝胶，
b)在超临界条件下干燥步骤b)中获得的凝胶以形成整体气凝胶)，
c)任选地将干燥的凝胶切成厚度为0.99至1.99mm的片材，
d)将来自步骤b)的整体气凝胶压缩至密度为100至300kg/m3以获得层A)，
e)任选地通过粘合剂层B)将至少一个覆盖层C)施加至在步骤c)中获得的层A)上。
本发明的模制品在高密度下显示出低导热性并因此显示出良好的绝热性能。同时，该模制品在机械上是稳定的并显示出高压缩强度和弯曲强度。在处理过程中不脆碎。本发明方法的压缩步骤将整体有机气凝胶模制品的孔结构改变为具有更高体积分数的孔径小于150nm和小于27nm的中孔(mesopore)的孔结构。
本发明的模塑制品和隔热材料适合用于建筑和制冷器具行业或用于电子设备和电池，优选作为绝热材料用于内保温、百叶窗、扇窗、冰箱、电子设备、智能手机、平板电脑、笔记本电脑或可充电电池。
实施例
方法：
根据DIN EN 12667：2001-05使用来自Hesto的热流计(Lambda Control A50)在10℃下测量热导率。对于厚度为1-2mm的层压片材和非层压片材，最多可测量9片(15厘米＊15厘米)的堆叠。
抗压强度根据DIN EN ISO 844：2014-11以6％的应变测定。
弯曲强度根据DIN EN 12089：2013-06通过三点弯曲试验测定。固定点间隔50mm。最大弯曲半径为90°。样品尺寸约为100x20mm。一侧层压的样品在层压侧进行按压。
脆碎性是根据ASTM C 421-77使用长宽25x25mm以及表4中报告的厚度的样品通过滚动脆碎性测试确定的。
使用来自Quantachrome Instruments的Nova 4000e孔径尺寸分析仪根据DIN66134：1998-02测量孔体积。从原始样品上取下约15-20mg的样品并放入测量玻璃池中。样品在50mm Hg真空和60℃下脱气15小时，以去除样品上的任何吸附成分。在表面积和孔径尺寸分析之前再次称重样品。
表面积测量：比表面积通过Brunauer-Emmet-Teller(BET)方法使用IUPAC推荐的P/P0(0.05-0.30)范围内的低温氮吸附分析(在氮的沸点，77K下)确定。1/((w.(P0/P-1)))与P/P0图产生线性图，相关系数(r)高于0.999。
孔径分布：在P/P0(0.05-0.99)范围内确定了低温氮气吸附-解吸曲线。使用Barret-Joyner-Halenda(BJH方法)确定孔径分布，该方法使用给定孔径的孔填充开尔文模型。通过该方法可测量的理论最大孔径为190nm。
孔体积(小于190nm的孔所占的)：总中孔体积由在P/P0＝0.99时吸附在孔上(在S.T.P条件下)的氮的总体积(vads)然后将该值乘上一个提供填充在孔隙内的液氮值的转换因子而确定。
整体有机气凝胶样品的总孔体积计算为样品的比体积与固体聚合物的比体积(骨架体积)的差。固体聚合物的比体积可以根据ISO12154：2014-04通过比重瓶测定。在实施例中，异氰酸酯基聚合物的比体积为0.65cm3/g。
材料：
M200 低聚MDI(Lupranat M200)，根据ASTMD-5155-96 A的NCO含量为30.9g/100g，官能度为3左右，根据DIN 53018的在25℃下粘度为2100mPa·s。
MDEA 3，3′，5，5′-四乙基-4，4′-二氨基二苯基甲烷
MEK 甲乙酮
Ksorbate溶液 山梨酸钾溶于单乙二醇中(5％)
TBA柠檬酸盐 四丁基柠檬酸铵(25重量％在MEG中)
Exolit OP560 磷多元醇
透明胶带(CB1)：
约0.06mm厚的透明PP胶带(宽5cm)，具有接触型粘合剂(
Figure BDA0003303938770000121
e-胶带)
织物增强胶带(CB2)：
约0.3mm厚的聚合物胶带(宽5cm)，具有织物增强和接触型粘合剂(
Figure BDA0003303938770000131
4651白色)
纸(CB3)：
办公用纸80g/m2，具有手工施加的固体胶粘合剂层(
Figure BDA0003303938770000133
原装固体胶)
石墨箔(CFB4)：
约25μm厚的石墨箔，具有10μm的电绝缘聚合物层和接触型粘合剂(ProGraphite的散热箔)
铝涂布纸(CFB5)：
约0.3mm厚的铝涂布纸，具有接触型粘合剂
矿物绒(CFB6)：
约0.6mm厚的防火矿物绒(Innobra MIV 520 P)，具有手工施加的固体胶粘合剂层(
Figure BDA0003303938770000132
原装固体胶)
实施例1
在聚丙烯容器中，将48g M200在220g MEK中在20℃下搅拌产生澄清溶液。类似地，将8g MDEA、2g Ksorbate溶液(5％在MEG中)、2g Exolit OP560和4g丁醇溶解在220g MEK中以获得第二溶液。通过将一种溶液倒入另一种溶液中，在矩形容器(20x20cm x5cm高)中合并溶液，从而形成低粘度的均匀混合物。容器盖上盖子，混合物在室温下凝胶化24小时。所得的整体凝胶板在25l高压釜中用scCO2通过溶剂萃取干燥，得到多孔材料。
使用带有压板(30x30cm)的液压机(Schmidt Maschinentechnik)在25℃下以30-60kN/900cm2的压力和22.8cm/min的按压速度将得到的孔状板压缩2秒(实施例1-1、1-2)。
将扳手置于实施例1-C的多孔板顶部并压缩。之后，扳手在板的表面上压印了它的标志。
实施例2
在聚丙烯容器中，将25.6g M200在146.67g MEK中在20℃下搅拌产生澄清溶液。类似地，将5.33g MDEA、1.33g Ksorbate溶液(5％在MEG中)、1.33g Exolit OP560和2.67g丁醇溶解在146.67g MEK中以获得第二溶液。通过将一种溶液倒入另一种溶液中，在矩形容器(16x 16cm x3cm高)中合并溶液，从而形成低粘度的均匀混合物。容器盖上盖子，混合物在室温下凝胶化24小时。所得的整体凝胶板在25l高压釜中用scCO2通过溶剂萃取干燥，得到多孔材料。
使用带有压板(30x30cm)的液压机(Schmidt Maschinentechnik)在25℃下以30-60kN/900cm2的压力和22.8cm/min的按压速度将得到的孔状板压缩2秒(实施例2-1、2-2、2-3、2-4)。
实施例3-C
在聚丙烯容器中，将22.4g M200在121.6g MEK中在20℃下搅拌产生澄清溶液。类似地，将5.33g MDEA、1.33g Ksorbate溶液(5％在MEG中)、1.33g Exolit OP560和2.67g丁醇溶解在121.6g MEK中以获得第二溶液。通过将一种溶液倒入另一种溶液中，在矩形容器(16x16cm x3cm高)中合并溶液，从而形成低粘度的均匀混合物。容器盖上盖子，混合物在室温下凝胶化24小时。所得的整体凝胶板在25l高压釜中用scCO2通过溶剂萃取干燥，得到多孔材料。
实施例4-C
在聚丙烯容器中，将22.4g M200在96.8gMEK中在20℃下搅拌产生澄清溶液。类似地，将5.33g MDEA、1.33g Ksorbate溶液(5％在MEG中)、1.33g Exolit OP560和2.67g丁醇溶解在96.8g MEK中以获得第二溶液。通过将一种溶液倒入另一种溶液中，在矩形容器(16x16cm x3cm高)中合并溶液，从而形成低粘度的均匀混合物。容器盖上盖子，混合物在室温下凝胶化24小时。将所得的整体凝胶板在25l高压釜中用scCO2通过溶剂萃取干燥，得到多孔材料。
实施例5-C
在聚丙烯容器中，将22.4g M200在54.3g MEK中在20℃下搅拌产生澄清溶液。类似地，将5.33g MDEA、1.33g Ksorbate溶液(5％在MEG中)、1.33g Exolit OP560和2.67g丁醇溶解在54.3g MEK中以获得第二溶液。通过将一种溶液倒入另一种溶液中，在矩形容器(16x16cm x3cm高)中合并溶液，从而形成低粘度的均匀混合物。容器盖上盖子，混合物在室温下凝胶化24小时。所得的整体凝胶板在25l高压釜中用scCO2通过溶剂萃取干燥，得到多孔材料。
结果总结在表1中。压缩的多孔板在较高密度下显示出显著较低的热导率和较高的弯曲强度。
实施例6：
制备压缩整体气凝胶层A1：
在聚丙烯容器中，将48g M200在220g MEK中在20℃下搅拌产生澄清溶液。类似地，将6g MDEA、2g Ksorbate溶液、2g Exolit OP560和6g丁醇溶解在220g MEK中以获得第二溶液。通过将一种溶液倒入另一种溶液中，在矩形容器(20cm x20cm x5cm高)中合并溶液，从而形成低粘度的均匀混合物。容器盖上盖子，混合物在室温下凝胶化24小时。所得的整体凝胶板在25l高压釜中用scCO2通过溶剂萃取干燥，得到多孔材料。
使用带锯将15x15x1.5cm的多孔材料板切割成15x15cm和1-3mm厚的片材。
制备压缩整体气凝胶层A2：
使用具有压板(30x30cm)的液压机(Schmidt Maschinentechnik)在25℃下以30-60kN/900cm2的压力和20-25cm/min的按压速度将如上所述获得的用于整体气凝胶层A1的多孔板压缩2秒。在表1中，厚度减少量以压缩％形式列出。
实施例6-1至6-11
将预先切割的胶黏带(CB1)、织物胶带(CB2)、具有一层固体胶胶粘剂的纸(CB3)、石墨箔(CFB4)、铝涂布纸(CFB5)或具有一层固体胶胶粘剂(CFB6)的矿物绒的条与粘合剂层一起手动按压在整体气凝胶层A1和A2上。在CB1和CB2的情况下，对于宽度为5cm或更小的样品，每面使用一层胶带。对于宽度超过5cm的样品，胶带层以在层之间形成约5-10mm的重叠的方式施加。绝热材料的层压结构、厚度和机械性能总结于表1中。
实施例6-3至6-7、6-8、6-10和6-11在三点弯曲试验中未显示分层，当在外侧胶带层弯曲时不发生分层。最小直径是弯曲或卷曲时没有明显损坏的直径。在片材在一侧具有层压的情况下，片材在没有覆盖层的一侧之上弯曲。如果材料在弯曲到最小轧制直径后发生断裂和/或部分分层，则认为板材不可重复使用。
结果总结在表2中。
实施例7
在聚丙烯容器中，将48g M200在220g MEK中在20℃下搅拌产生澄清溶液。类似地，将8g MDEA、2g Ksorbate溶液(5％在MEG中)、2g Exolit OP560和4g 1-丁醇溶解在220gMEK中以获得第二溶液。通过将一种溶液倒入另一种溶液中，将所述溶液合并在矩形容器(20x20cm x5cm高)中，从而形成低粘度的均匀混合物。容器盖上盖子，混合物在室温下凝胶化24小时。所得的整体凝胶板在25l高压釜中用scCO2通过溶剂萃取干燥产生多孔材料。
使用具有压板(30x30cm)的液压机(Schmidt Maschinentechnik)在25℃下以30-60kN/900cm2的压力和22.8cm/min的按压速度将获得的多孔板压缩2秒(实施例7-C至7.4)。结果总结在表3中。
实施例8
在聚丙烯容器中，在20℃下将25.6g M200在220g MEK中搅拌产生澄清溶液。类似地，将5.44g MDEA、0.67g TBA-Citrat溶液(25％在MEG中)、1g Exolit OP560和2.67g 1-丁醇溶解在220g MEK中以获得第二溶液。通过将一种溶液倒入另一种溶液中，将所述溶液合并在矩形容器(20x20cm x5cm高)中，从而形成低粘度的均匀混合物。容器盖上盖子，混合物在室温下凝胶化24小时。所得的整体凝胶板在25l高压釜中用scCO2通过溶剂萃取干燥，得到多孔材料。
使用带有压板(30x30cm)的液压机(Schmidt Maschinentechnik)在25℃下以30-60kN/900cm2的压力和22.8cm/min的按压速度将获得的多孔板压缩2秒(实施例8-C至8.4)。结果总结在表3中。
实施例9-12
使用表5所示的不同量和浓度的原材料重复实施例9，以获得具有不同密度和厚度的整体气凝胶样品。
使用带有压板(30x30cm)的液压机(Schmidt Maschinentechnik)在25℃下以30-60kN/900cm2的压力和22.8cm/min的按压速度将得到的多孔板压缩2秒以获得厚度约8mm的压缩板。结果总结在表4中。
实施例11-4在脆碎性测试中显示了0.3重量％的质量损失，这远低于对比实施例10-C的1.7重量％的质量损失。
实施例13和14
所有步骤均在20℃下进行。实施例13(1重量％藻酸盐)和14(2重量％藻酸盐)通过将28g(13)或56g(14)的藻酸钠加入烧杯中的2500g水中并用实验室的搅拌器搅拌过夜进行。然后，使用转子-定子混合器将8.2g(13)或16.3g(14)碳酸钙粉末分散在水中，并且在搅拌的同时将得到的分散体立即加入至藻酸盐溶液中。将6.8g(13)或13.6g(14)D-葡萄糖酸-δ-内酯(GDL)通过剧烈搅拌10s溶解在66.7g水中，然后将所得溶液加入至750g藻酸盐/碳酸钙的混合物中，然后将所得混合物搅拌30s。立即将混合物倒入20x20cm的聚合物模具中，使其高度为10-15mm，并将填充的模具放置过夜，使混合物凝胶化。每2-6小时去除一次在凝胶化过程中从凝胶中排出的液体。将获得的凝胶板在750g预先制备的氯化钙溶液(15g氯化钙在2975g的水中)中老化24h。通过将凝胶板在每一个750g20体积％、40体积％、60体积％、80体积％的乙醇的水溶液中放置24h和最后在纯乙醇中放置24h将凝胶液体从水溶液转换为乙醇。使用超临界二氧化碳干燥凝胶板以获得藻酸盐多孔板。
使用带有压板(30x30cm)的液压机(Schmidt Maschinentechnik)在25℃下以30-60kN/900cm2的压力和22.8cm/min的按压速度将获得的多孔板压缩2秒以得到厚度约8mm的压缩板。结果总结在表4中。
Figure BDA0003303938770000181
Figure BDA0003303938770000191
Figure BDA0003303938770000201
Figure BDA0003303938770000211
Figure BDA0003303938770000221

Claims (13)

1.一种基于整体有机气凝胶的模制品，其密度为60至300kg/m3，热导率为12至17.8mW/m＊K，且具有多于30体积％的直径小于150nm的孔，并且具有多于20体积％的直径小于27nm的孔，基于总的孔体积计。
2.如权利要求1所述的模制品，其压缩强度为600-700kPa。
3.如权利要求1或2所述的模制品，其弯曲强度为1000-5000KPa。
4.如权利要求1至3中任一项所述的模制品，其中所述有机气凝胶为聚异氰脲酸酯(PIR)结构少于80％的基于聚氨酯(PU)和/或聚脲(PUR)的整体气凝胶。
5.如权利要求1至4中任一项所述的模制品，其为厚度在100μm至10mm范围内的片材形式。
6.一种制备密度为60至300kg/m3的基于整体有机气凝胶的模制品的方法，其包括将密度为50至140kg/m3的基于有机气凝胶的模制品压缩，压缩因子为5到70体积％。
7.根据权利要求6的方法，用于制备如权利要求1至5中任一项所述的模制品。
8.如权利要求6或7所述的方法，其包括在片材的厚度方向上单向压缩片材形式的基于有机气凝胶的模制品。
9.如权利要求6至8所述的方法，其中压缩在液压机或气动压力机中在10至80℃的模制温度和0.12至10MPa/1000em2的压力下进行。
10.一种制备如权利要求1至5中任一项所述的模制品的方法，包括以下步骤
a)使包含至少一种多官能异氰酸酯(a1)、至少一种芳族胺(a2)和至少一种催化剂(a3)的混合物(A)在溶剂(B)的存在下反应以形成凝胶，
b)在超临界条件下干燥步骤b)中获得的凝胶，
c)任选地将干燥的凝胶切成厚度为0.1至10mm的片材，和
d)将干燥的凝胶压缩至密度为100至300kg/m3。
11.一种绝热材料，其包括根据权利要求5的片材形式的模制品作为气凝胶层A)和至少一个厚度为10μm至1mm的覆盖层C)。
12.一种制备根据权利要求11的绝热材料的方法，其包括以下步骤：
a)使包含至少一种多官能异氰酸酯(a1)、至少一种芳族胺(a2)和至少一种催化剂(a3)的混合物(A)在溶剂(B)存在下反应以形成凝胶，
b)在超临界条件下干燥步骤b)中获得的凝胶以形成整体气凝胶)，
c)任选地将干燥的凝胶切成厚度为0.1至10mm的片材，
d)将步骤b)的整体气凝胶压缩至密度为100至300kg/m3以获得气凝胶层A)，
e)将至少一个覆盖层C)任选地通过粘合剂层B)施加至在步骤c)中获得的层A)上。
13.如权利要求1至5中任一项所述的模制品或如权利要求11所述的绝热材料在建筑和构造、制冷设备、电子设备、航空航天和电池中作为绝热材料的用途。
CN202080028878.XA 2019-04-15 2020-04-09 一种基于整体有机气凝胶的模制品 Pending CN113710715A (zh)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP19169258 2019-04-15
EP19169258.1 2019-04-15
EP20163623 2020-03-17
EP20163623.0 2020-03-17
PCT/EP2020/060129 WO2020212241A1 (en) 2019-04-15 2020-04-09 A molding based on a monolithic organic aerogel

Publications (1)

Publication Number Publication Date
CN113710715A true CN113710715A (zh) 2021-11-26

Family

ID=70482593

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080028878.XA Pending CN113710715A (zh) 2019-04-15 2020-04-09 一种基于整体有机气凝胶的模制品

Country Status (6)

Country Link
US (1) US20220195137A1 (zh)
EP (1) EP3956375A1 (zh)
JP (1) JP2022529347A (zh)
KR (1) KR20210155016A (zh)
CN (1) CN113710715A (zh)
WO (1) WO2020212241A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022221687A1 (en) * 2021-04-15 2022-10-20 Patel Dishank Systems and methods for manufacturing an aerogel
CN114180984B (zh) * 2021-11-10 2022-10-11 安徽壹石通材料科学研究院有限公司 一种羟基磷灰石/氧化硅复合气凝胶及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5942553A (en) * 1995-05-22 1999-08-24 Imperial Chemical Industries Plc Organic aerogels
US20070259979A1 (en) * 2006-05-03 2007-11-08 Aspen Aerogels, Inc. Organic aerogels reinforced with inorganic aerogel fillers
US20160380244A1 (en) * 2014-06-23 2016-12-29 Aspen Aerogels, Inc. Thin aerogel materials
US20170210108A1 (en) * 2016-01-27 2017-07-27 Aspen Aerogels,Inc. Laminates comprising reinforced aerogel composites

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5478867A (en) 1993-07-07 1995-12-26 The Dow Chemical Company Microporous isocyanate-based polymer compositions and method of preparation
AU676109B2 (en) 1993-07-22 1997-02-27 Huntsman Ici Chemicals Llc Organic aerogels
US7118801B2 (en) 2003-11-10 2006-10-10 Gore Enterprise Holdings, Inc. Aerogel/PTFE composite insulating material
US20060211840A1 (en) 2005-03-20 2006-09-21 Aspen Aerogels Inc. Polyurea aerogels
DE102005021994A1 (de) 2005-05-09 2006-11-23 Basf Ag Verfahren zur Herstellung von Vakuumisolations-Paneelen
JP5383663B2 (ja) 2007-05-16 2014-01-08 ビーエーエスエフ ソシエタス・ヨーロピア 芳香族ポリ尿素ベースのキセロゲル
EP2914795B1 (de) 2012-11-05 2017-02-22 Basf Se Verfahren zur herstellung von profilierten elementen
US20140287641A1 (en) 2013-03-15 2014-09-25 Aerogel Technologies, Llc Layered aerogel composites, related aerogel materials, and methods of manufacture
EP3169724B1 (en) 2014-07-18 2021-05-26 Basf Se Process for producing porous materials
CN108473659A (zh) 2016-01-18 2018-08-31 巴斯夫欧洲公司 制备多孔材料的方法
WO2017125414A1 (en) 2016-01-18 2017-07-27 Basf Se Process for producing porous materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5942553A (en) * 1995-05-22 1999-08-24 Imperial Chemical Industries Plc Organic aerogels
US20070259979A1 (en) * 2006-05-03 2007-11-08 Aspen Aerogels, Inc. Organic aerogels reinforced with inorganic aerogel fillers
US20160380244A1 (en) * 2014-06-23 2016-12-29 Aspen Aerogels, Inc. Thin aerogel materials
US20170210108A1 (en) * 2016-01-27 2017-07-27 Aspen Aerogels,Inc. Laminates comprising reinforced aerogel composites

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JE KYUN LEE等: ""Polydicyclopentadiene based aerogel: a new insulation material"", 《J SOL-GEL SCI TECHNOL》 *

Also Published As

Publication number Publication date
JP2022529347A (ja) 2022-06-21
KR20210155016A (ko) 2021-12-21
EP3956375A1 (en) 2022-02-23
US20220195137A1 (en) 2022-06-23
WO2020212241A1 (en) 2020-10-22

Similar Documents

Publication Publication Date Title
US20210354420A1 (en) Laminates comprising reinforced aerogel composites
US20130071602A1 (en) Composite materials comprising an open-cell polymer matrix and granules embedded therein
JP7391856B2 (ja) 熱絶縁材料、接着剤および外層の複合要素
JPH10509922A (ja) 断熱体
CN113710715A (zh) 一种基于整体有机气凝胶的模制品
EP0297317B1 (en) Manufacturing method of a rigid or semi-rigid foamed material and of a composite panel made therefrom
US20130068990A1 (en) Composite materials comprising a polymer matrix and granules embedded therein
US20070259979A1 (en) Organic aerogels reinforced with inorganic aerogel fillers
US20210206926A1 (en) Polymeric aerogel composite and synthesis by ambient and freeze-drying`
CN106832204B (zh) 一种改性聚氨酯屋面保温材料及其制备方法
EP4121469A1 (en) Thin and flexible thermal insulation material based on a monolithic organic aerogel
CA2294854A1 (en) Combined polystyrene and polyurethane vacuum insulating panel and the use thereof for producing insulating elements
CN109096459A (zh) 一种环保型低密度聚氨酯夹芯板
CA2962110C (en) Method for manufacturing a composite element for vacuum insulation elements
EP2657280A1 (de) Mineralstoffpartikel enthaltender Polyurethan-Verbundwerkstoff
KR100246034B1 (ko) 개방 셀 발포체를 이용한 진공 단열판 및 그 제조 방법
US20230348686A1 (en) Aerogel articles made from aerogel particles and methods for making the same
EP3831869B1 (en) Composite polystyrene foam molding with low thermal conductivity
CN115703277A (zh) 高强度聚氨酯复合板材及其制备方法与用途
CN115723386A (zh) 天线罩用复合材料、耐功率天线罩及其制备方法
JPH0272294A (ja) 断熱体
JPH0262381B2 (zh)

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20221008

Address after: German Aus Knapp Luc

Applicant after: Elig-Itt GmbH

Address before: Germany's Rhine River in Ludwigshafen

Applicant before: BASF SE

TA01 Transfer of patent application right