EP3788018A1 - Materiau d'isolation thermique comprenant des particules d'oyde de graphite partiellement oxydees - Google Patents
Materiau d'isolation thermique comprenant des particules d'oyde de graphite partiellement oxydeesInfo
- Publication number
- EP3788018A1 EP3788018A1 EP19728482.1A EP19728482A EP3788018A1 EP 3788018 A1 EP3788018 A1 EP 3788018A1 EP 19728482 A EP19728482 A EP 19728482A EP 3788018 A1 EP3788018 A1 EP 3788018A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxide particles
- graphite oxide
- insulation material
- material according
- peaks
- 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
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002245 particle Substances 0.000 title claims abstract description 67
- 239000010439 graphite Substances 0.000 title claims abstract description 64
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 64
- 239000012774 insulation material Substances 0.000 title claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000006260 foam Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 26
- 238000007254 oxidation reaction Methods 0.000 claims description 26
- 230000008033 biological extinction Effects 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000000835 fiber Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000001413 cellular effect Effects 0.000 claims description 6
- 239000011810 insulating material Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011496 polyurethane foam Substances 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 210000002268 wool Anatomy 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000011094 fiberboard Substances 0.000 claims description 2
- 239000002557 mineral fiber Substances 0.000 claims 2
- 238000002798 spectrophotometry method Methods 0.000 claims 2
- 239000003605 opacifier Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000004794 expanded polystyrene Substances 0.000 description 4
- 239000011491 glass wool Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229920006327 polystyrene foam Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 150000008163 sugars Chemical class 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- -1 amine compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/23—Oxidation
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
- E04B1/7654—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only comprising an insulating layer, disposed between two longitudinal supporting elements, e.g. to insulate ceilings
- E04B1/7658—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only comprising an insulating layer, disposed between two longitudinal supporting elements, e.g. to insulate ceilings comprising fiber insulation, e.g. as panels or loose filled fibres
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/42—Coatings containing inorganic materials
- C03C25/44—Carbon, e.g. graphite
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- 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
- C08J9/16—Making expandable particles
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
- E04B1/78—Heat insulating elements
-
- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B2001/742—Use of special materials; Materials having special structures or shape
Definitions
- the thermal insulation of buildings reduces heat loss and thus contributes to improving comfort, reduce the risk of damage to buildings related to early aging, and reduce energy consumption for both the heating only for possible cooling.
- Heat exchanges with the outside through the building envelope are usually by conduction and / or radiation.
- Traditional thermal insulation materials tend to reduce these exchanges: air immobilized for example in foams or between fibers reduces the thermal conduction of the walls and the walls of the cells of the foams where the fibers contribute to screen the radiation.
- An opacifying agent is a component
- graphite particles as opacifying agent in polymer foams such as expanded polystyrene (EPS) has for example been proposed (EP 0981574, EP 1758951, EP 1819758, EP 2683763, EP 1945700, EP 2010601).
- Graphite particles have the advantage of having high extinction coefficients in the infrared while being inexpensive. However, they may have certain disadvantages, especially for their implementation. Graphite being extremely hydrophobic, its implementation in existing processes is not easy. It can indeed be difficult to obtain a homogeneous dispersion of the graphite particles in the insulation materials. Poor dispersion resulting in loss of efficiency
- the objective of the present invention is to obviate the disadvantages mentioned above by providing a opacifying agent having improved opacification properties, low cost and the quality of dispersion in different media can to be assured.
- one aspect of the present invention relates to an insulation material
- the term "partially oxidized graphite oxide particles” means that the graphite particles have undergone a mild oxidation. It has indeed been observed that the partial oxidation of graphite particles, in contrast to a high oxidation (to which the term graphite oxide generally refers), allowed to significantly improve their opacification efficiency by a better dispersion of the particles and / or an improvement in their opacification properties. While not wishing to be bound by any theory, it is believed that the partially oxidized graphite oxide particles have a core-shell structure with an infra-red absorbing graphite conductive core and an infrared reflective oxidized shell.
- the graphite oxide particles can be obtained by oxidation of graphite using methods well known to those skilled in the art, as described for example by Brodie et al., Philos. Trans. R. Soc. London, 1859, 149, 249-259, Staudenmaier, Ber. Dtsch. Chem. Ges., 1898, 31 (2), 1481-1487, Hummers et al., J. Am. Chem. Soc. 1958, 80 (6), 1339, Moritomo et al., Self. Rep., 2016, 6, 21715, Lee et al., J. Phys. Chem. C, 2011, 115 (6), pp 2705-2708, Zhao et al. ACS Nano, 2010, 4 (9), pp 5245-5252 or Muzyka et al. New Carbon
- the graphite oxide particles used in the present invention exhibit extinction coefficients.
- the insulation material according to the invention can thus be characterized in that the partially oxidized graphite oxide particles have an absolute mass extinction coefficient at room temperature in the range 2 to 18 miti, greater than 5000 m 2 / kg, preferably greater than 7000 m 2 / kg, more preferably greater than 10000 m 2 / kg, or even greater than 13000 m 2 / kg, and typically less than 30000 m 2 / kg, even 25000 m 2 / kg.
- the degree of oxidation of the graphite oxide particles can be evaluated by X-ray photoelectron spectrometry (XPS). More precisely, a deconvolution is carried out starting from an XPS spectrum of the carbon (C1 s) by considering the contribution of four peaks: the C1 peak at 284 eV attributed to the carbon bonds:
- the insulating material according to the invention can be characterized in that the partially oxidized graphite oxide particles preferably have an oxidation ratio greater than 6%, more preferably greater than 7%, 8% or 9%, in particular 9.5% or even 10%, 10.5% or even 11%, and up to 50% or even 40%, 30% or even 20% .
- the ratio A2 / (A2 + A3 + A4) is preferably at least 15.0%, plus
- the insulation material according to the invention can also be characterized in that the partially oxidized graphite oxide particles have both an extinction coefficient of greater than 5000 m 2 / kg, preferably greater than at 7000 m 2 / kg, more preferably greater than 10000 m 2 / kg, or even greater than 13000 m 2 / kg, and typically less than 30000 m 2 / kg, or even 25000 m 2 / kg, and an oxidation ratio , or even a ratio A2 / (A2 + A3 + A4), as defined above.
- the thermal insulation material may be any type of material well known to those skilled in the art. It can be in particular in the form of insulation blanket, insulation board or bulk.
- fibrous insulation materials based on natural fibers of animal or vegetable origin, or synthetic / mineral such as glass wool or wool. rock.
- the fibrous insulation material is preferably based on glass wool or rockwool.
- a conventional glass wool composition comprises the following constituents, expressed as weight percentages:
- Glass wool may also be rich in alumina, in which case it
- a conventional rock wool composition generally comprises the following constituents, expressed in percentages by weight:
- the fibers may be bonded by a binder.
- the binder can be a binder
- thermoplastic or thermosetting examples of binders thermoplastic or thermosetting examples of binders
- thermosetting agents include phenol / formaldehyde binders, polymeric binders based on acrylates and / or polyols, as well as biosourced binders as described in particular in WO 2009/080938, WO 2009/080938 or WO 2007/014236.
- the material according to the invention may comprise fibers not bound by a binder.
- the graphite oxide particles may be dispersed on the surface of the fibers in powder form or via a sizing composition, before the possible application of the binder using a sizing composition.
- the graphite oxide particles can be dispersed in the binder when it is present. In this case, the graphite oxide particles are introduced into the sizing composition before it is applied to the fibers.
- the fibrous insulation material may be in the form of fiber mat, fiber board or wool to blow. It typically comprises 1%, or even 2% or 3%, and up to 100%, even 60%, or even 20% by weight of graphite oxide particles based on the weight of fibers. Insulating materials comprising a large amount of opacifier, especially greater than 20% by weight, are particularly suitable for high temperature applications. [0030] Mention may also be made of cellular insulation materials of the expanded polymer foam type such as expanded (EPS) or extruded polystyrene (XPS), phenolic foams, polyurethane foams or biosourced foams.
- EPS expanded
- XPS extruded polystyrene
- phenolic foams polyurethane foams or biosourced foams.
- biosourced foams examples include foams obtained from reducing sugars and amine compounds, described for example in WO 2016/139401, foams obtained from sugars and strong acids, described for example in WO 2016/174328, or foams obtained from polyols and polyacids, described for example in WO 2016/207517.
- the polymer matrix forming the polystyrene foams comprise
- styrene typically a homopolystyrene or a styrene copolymer which may contain up to 20%, based on the weight of the polymers, of
- ethylenic unsaturation in particular alkylstyrene, divinylbenzene, acrylonitrile or ⁇ -methylstyrene.
- Mixtures of polystyrene and other polymers, particularly with rubber and polyphenylene ether are also possible.
- the polymer matrix may also contain customary and known additives, for example flame retardants, nucleating agents, UV stabilizers, chain transfer agents, blowing agents, plasticizers, pigments and antioxidants.
- cellular insulation materials are generally in the form of panels or blocks. They can be associated with other materials in the form of composite panels comprising for example a layer of polymeric foam such as expanded polystyrene and a layer of a more rigid material such as a wood panel or a plasterboard.
- the graphite oxide particles are preferably dispersed in the polymer matrix of the foam, either by introduction during the mixing of the precursor solutions, or by prior introduction into one of the precursor solutions.
- the graphite oxide particles may be mixed with the melt polymer, preferably in an extruder.
- an expanding agent can be present in the molten polymer at the time of adding the graphite oxide particles or added simultaneously thereto.
- Foams of expanded polymer in particular polystyrene, have
- the cellular insulation material typically comprises 1%, even 2% or 3%, and up to 100%, even 60%, or even 20% by weight of graphite oxide particles with respect to the weight of foam.
- the thermal insulation material according to the invention may also be an insulation material based on airgel or amorphous silica, in particular pyrogenic or precipitated, or a vacuum insulation material.
- Aerogels typically in the form of translucent granules or of powder having grain sizes or granules conventionally of the order of one millimeter, are generally used with protections or a reinforcing agent, for example in mats formed of mechanically entangled fibers. resistant. Examples of such insulating materials are described in particular in WO 01/28675, US 2007/154698 or EP 0171722.
- the present invention also relates to a method of manufacturing a thermal insulation material having improved thermal conductivity properties, especially as described above, comprising the introduction of graphite oxide particles into the material.
- thermal insulation comprising the introduction of graphite oxide particles into the material.
- the introduction of the graphite oxide particles can be carried out by applying a solution comprising the graphite oxide particles (for example a sizing composition, a sizing composition or a surface coating composition) on the insulation material.
- the particles can also be introduced into the insulation material by incorporating into the matrix of the insulation material during its manufacture.
- the present invention also relates to the use of graphite oxide particles as described above as an opacifying agent in a thermal insulation material, as well as a process for reducing the
- thermal conductivity of a thermal insulation material comprising introducing graphite oxide particles into the thermal insulation material.
- the thermal insulation material according to the invention can be used in the field of construction, in particular for the interior and / or exterior insulation of walls, floors or roofs of buildings. Other areas of application also include the isolation of means of transport, including rail or sea, high temperature devices (furnaces, inserts ...), ventilation ducts, ducting, etc.
- opacifiers Four types of opacifiers (OPO, OP1, OP2 and OP3) have been characterized.
- the OPO opacifier consists of graphite particles that have not undergone any oxidation.
- OP1 and OP2 opacifiers are graphite particles
- partially oxidized graphite particles can be obtained by methods well known to those skilled in the art, especially by ultrasonic treatment.
- Particles OP2 were, for example, obtained in the following manner: an aqueous dispersion of 1% by weight of graphite particles was subjected to ultrasonic treatment for one hour. The dispersion produced is then frozen and lyophilized to recover partially oxidized graphite particles.
- OP3 particles are particles that have undergone extensive oxidation by conventional chemical means. Ultrasonic treatment methods have the advantage of being inexpensive and easy to implement, particularly from the point of view of safety or environmental considerations, compared to chemical oxidation methods.
- the absolute mass extinction coefficients (EC m ), expressed in m 2 / kg, at room temperature over the range 2 to 18 miti, OPO, OP1, OP2 and OP3 opacifiers were determined in two stages: i) determining the mass extinction coefficient of a polymer / opacifier system; and (ii) subtracting the polymer contribution to this system. [0043] (i) The determination of the mass extinction coefficients of the polymer / opacifier systems is based on the approach proposed by Zeng el al., J. Mater. Res., Vol.11, No.3, Mar 1996. It consists of a characterization
- the mass extinction coefficient of the ECs system ys is determined according to the following relation:
- E thin expressed in m, is the thickness of the optically thin film
- Thin is the transmission of the optically thin film over the length range
- R thick is the reflection of the optically thick film on the length range
- the films are made from a mixture of opacifier (OPO, OP1, OP2 and OP3) dispersed in a polystyrene matrix with an amount of opacifier particles - 6% - and constant dispersion quality.
- the optically thin films have a thickness of 10 to 25 ⁇ m while the optically thick films have a thickness greater than 350 ⁇ m.
- OR is the percentage of opacifying particles in the polymer / opacifier system.
- the extinction coefficient of a material over a given wavelength range represents the capacity of the material to absorb and / or scatter the radiation over this range of wavelengths.
- the characteristics of the opacifiers OPO, OP1 OP2 and OP3 are summarized in the table below.
- the partially oxidized graphite particles OP1 and OP2 have extinction coefficients that are significantly greater than the extinction coefficient of the unoxidized graphite particles OPO.
- the OP3 graphite particles having undergone a high oxidation have an extinction coefficient comparable to the unoxidized graphite particles OPO.
- Expanded polystyrene foam panels with a density of 10kg / m 3 and comprising 6% by weight of opacifier with respect to polystyrene were prepared with each of OPO, OP1, OP2 and OP3 opacifiers.
- the panels according to the invention comprising the opacifiers OP1 and OP2 have been found to have significantly lower thermal conductivities (1), which can be reduced by up to 12%, compared with panels comprising opacifier OPO or OP3.
- the absolute mass extinction coefficient of the opacifier can be evaluated from the measurements of the effective thermal conductivity carried out on the insulation material, for example according to DIN 52612, using the additive approximation. the thermal conductivity of light porous media and the Rosseland approximation (valid for an optically thick sample, for example a thickness greater than 10 mm for EPS foams).
- l 9 is the gaseous conductivity
- X s is the solid conductivity
- l G is the radiative conductivity
- the Rosseland approximation also makes it possible to connect the radiative conductivity G to the extinction coefficient of the opacifying powder EC op by the following relationship:
- S s is the Stefan-Boltzmann constant (5.67 ⁇ 10 8 W / (m 2 ⁇ K 4 ));
- T expressed in K, is the temperature of the medium
- OR is the rate of opacification (mass percentage of opacifier in the insulation material).
- EC M a t expressed in m 2 / kg, is the mass extinction coefficient of the non-opacified insulation material (typically 35 m 2 / kg for an EPS foam of
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Architecture (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Acoustics & Sound (AREA)
- Electromagnetism (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Building Environments (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Carbon And Carbon Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1870534A FR3080850B1 (fr) | 2018-05-04 | 2018-05-04 | Materiau d’isolation thermique |
PCT/FR2019/051006 WO2019211559A1 (fr) | 2018-05-04 | 2019-04-30 | Materiau d'isolation thermique comprenant des particules d'oyde de graphite partiellement oxydees |
Publications (1)
Publication Number | Publication Date |
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EP3788018A1 true EP3788018A1 (fr) | 2021-03-10 |
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ID=63579505
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP19728482.1A Pending EP3788018A1 (fr) | 2018-05-04 | 2019-04-30 | Materiau d'isolation thermique comprenant des particules d'oyde de graphite partiellement oxydees |
Country Status (7)
Country | Link |
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US (1) | US20210230864A1 (fr) |
EP (1) | EP3788018A1 (fr) |
JP (1) | JP7411572B2 (fr) |
KR (1) | KR20210003134A (fr) |
CA (1) | CA3100134A1 (fr) |
FR (1) | FR3080850B1 (fr) |
WO (1) | WO2019211559A1 (fr) |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3429671A1 (de) | 1984-08-11 | 1986-02-20 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von aerogelen |
ES2151268T3 (es) | 1997-05-14 | 2000-12-16 | Basf Ag | Polimeros de estireno expandibles que contienen particulas de grafito. |
RU2002113291A (ru) | 1999-10-21 | 2004-03-27 | Эспен Системз, Инк. (Us) | Способ ускоренного изготовления аэрогеля |
DE102004028768A1 (de) | 2004-06-16 | 2005-12-29 | Basf Ag | Styrolpolymer-Partikelschaumstoffe mit verringerter Wärmeleitfähigkeit |
DE102004058586A1 (de) | 2004-12-03 | 2006-06-14 | Basf Ag | Halogenfrei flammgeschützte, expandierbare Styrolpolymerisate |
AU2006272595C1 (en) | 2005-07-26 | 2014-08-28 | Knauf Insulation Gmbh | Binders and materials made therewith |
IT1366567B (it) | 2005-10-18 | 2009-10-06 | Polimeri Europa Spa | Granulati espandibili a basemdi polimeri vinilaromatici dotati di migliorata espansibilita'e procedimento per la loro preparazione |
US20070154698A1 (en) | 2005-12-30 | 2007-07-05 | Aspen Aerogels, Inc. | Highly flexible aerogel insulated textile-like blankets |
DE102006018528A1 (de) | 2006-04-21 | 2007-11-08 | Deutsche Amphibolin-Werke Von Robert Murjahn Stiftung & Co Kg | Dämmender geschäumter Werkstoff |
FR2924719B1 (fr) | 2007-12-05 | 2010-09-10 | Saint Gobain Isover | Composition d'encollage pour laine minerale comprenant un monosaccharide et/ou un polysaccharide et un acide organique polycarboxylique, et produits isolants obtenus. |
EP2683763A1 (fr) | 2011-06-27 | 2014-01-15 | Total Research & Technology Feluy | Polymères aromatiques vinyliques expansibles contenant du graphite |
EP2724780B1 (fr) | 2012-10-26 | 2015-07-22 | Evonik Degussa GmbH | Procédé de fabrication d'un mélange d'isolation thermique |
KR101575989B1 (ko) | 2014-12-24 | 2015-12-09 | 고영신 | 팽창흑연을 이용한 경량화된 흡음내화 단열재 및 그 제조방법 |
MA41344B1 (fr) * | 2015-01-14 | 2019-01-31 | Synthos Sa | Combinaison de silice et de graphite et son utilisation pour réduire la conductivité thermique d'une mousse de polymère aromatique vinylique |
FR3033326B1 (fr) | 2015-03-02 | 2018-10-26 | Saint-Gobain Isover | Mousses thermodurcies et procede de fabrication |
FR3035402B1 (fr) | 2015-04-27 | 2019-04-05 | Saint-Gobain Isover | Mousses thermodurcies et procede de fabrication |
FR3037964B1 (fr) | 2015-06-24 | 2019-12-20 | Saint-Gobain Isover | Mousses polyester thermodurcies et procede de fabrication |
CN106009493A (zh) * | 2016-08-01 | 2016-10-12 | 合肥广能新材料科技有限公司 | 酚醛泡沫外墙保温材料及其制备方法 |
CN107827479A (zh) * | 2017-10-24 | 2018-03-23 | 安徽艾米伦特建材科技有限公司 | 高强度岩棉板及其制备方法 |
-
2018
- 2018-05-04 FR FR1870534A patent/FR3080850B1/fr active Active
-
2019
- 2019-04-30 KR KR1020207031865A patent/KR20210003134A/ko active IP Right Grant
- 2019-04-30 US US17/052,535 patent/US20210230864A1/en active Pending
- 2019-04-30 JP JP2020561659A patent/JP7411572B2/ja active Active
- 2019-04-30 EP EP19728482.1A patent/EP3788018A1/fr active Pending
- 2019-04-30 CA CA3100134A patent/CA3100134A1/fr active Pending
- 2019-04-30 WO PCT/FR2019/051006 patent/WO2019211559A1/fr active Application Filing
Also Published As
Publication number | Publication date |
---|---|
US20210230864A1 (en) | 2021-07-29 |
JP2021522395A (ja) | 2021-08-30 |
WO2019211559A1 (fr) | 2019-11-07 |
JP7411572B2 (ja) | 2024-01-11 |
FR3080850B1 (fr) | 2022-08-12 |
KR20210003134A (ko) | 2021-01-11 |
FR3080850A1 (fr) | 2019-11-08 |
CA3100134A1 (fr) | 2019-11-07 |
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