WO2013032350A2 - Matériaux composites calorifuges et leur procédé de production - Google Patents

Matériaux composites calorifuges et leur procédé de production Download PDF

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Publication number
WO2013032350A2
WO2013032350A2 PCT/PL2012/050030 PL2012050030W WO2013032350A2 WO 2013032350 A2 WO2013032350 A2 WO 2013032350A2 PL 2012050030 W PL2012050030 W PL 2012050030W WO 2013032350 A2 WO2013032350 A2 WO 2013032350A2
Authority
WO
WIPO (PCT)
Prior art keywords
foamed polystyrene
heat insulating
layer
insulating composite
polyurethane mixture
Prior art date
Application number
PCT/PL2012/050030
Other languages
English (en)
Other versions
WO2013032350A3 (fr
Inventor
Wiesław Ludwik GALUS
Henryk Jaremek
Piotr Paweł KONIORCZYK
Marcin Grzegorz TRZYNA
Original Assignee
Hit Konsulting Sp Z O.O.
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 Hit Konsulting Sp Z O.O. filed Critical Hit Konsulting Sp Z O.O.
Publication of WO2013032350A2 publication Critical patent/WO2013032350A2/fr
Publication of WO2013032350A3 publication Critical patent/WO2013032350A3/fr

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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
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • 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
    • B32B5/20—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 foamed in situ
    • 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
    • B32B5/32—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 at least two layers being foamed and next to each other
    • 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
    • B32B2266/0221—Vinyl resin
    • B32B2266/0228—Aromatic vinyl resin, e.g. styrenic (co)polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • 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
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

Definitions

  • the invention refers to heat insulating composite materials, consisting of layers of rigid polyurethane foam and classic layers of expanded or extruded foamed polystyrene, and a method of their production.
  • the materials according to the invention can be successfully used as cores of composite panels, as well as materials for elevation panels, roof planks, floor planks and suspended ceilings.
  • EPS foamed polystyrene
  • PUR/PIR rigid polyurethane foam
  • MW mineral wool
  • composite panels mainly in the form of prefabricated elements of roofs and external and internal walls constructions, as well as suspended ceilings in buildings of various purposes, e.g.: agricultural, industrial, commercial (shops, supermarkets, hypermarkets etc.), logistic, storage, distribution, sports and recreation, public buildings, etc.
  • the main use of composite panels is in buildings which are to be built quickly and meet precisely determined characteristics following from the purpose of the building and technical requirements demanded from a specific building.
  • Foamed polystyrene is one of the most commonly known synthetic plastics. This material is obtained as a result of free radical polymerisation of styrene.
  • foam structure foaming substances e.g. pentane isomers
  • the porous structure foamed polystyrenes are light (apparent density from 10 to 40 kg/m 3 ) and are characterized by a low thermal conductivity coefficient (depending on the class of density this coefficient ranges from 0,030 to 0,045 W/mK).
  • foamed polystyrene used for insulating external walls with the use of the light wet method must be characterised by a minimal compressive strength of 70 kPa (density from 12 to 1 5 kg/m 3 ), for floors or flat roofs 100 kPa (20 kg/m 3 density), whereas as heat insulation of floors subjected to special loads, this value amounts to minimally 200 kPa (density from 30 to 40 kg/m 3 ).
  • foamed polystyrenes are self-extinguishing plastics (class of fire resistance: E) and on a continuous running basis can be applied at a maximum temperature of 80 °C.
  • E class of fire resistance
  • Rigid polyurethane foams are manufactured by way of an exothermic reaction of polymerisation of the isocyanate component (usually PMDI) with a polyol component, constituting a mixture of modified polyhydric alcohols.
  • the generated heat causes evaporation of low-boiling foaming agents (e.g. n-pentane), which initiates growth of volume of the material, and at the same time forming of the porous cell structure (apparent density from 35 to 60 kg/m 3 ).
  • Rigid polyurethane foams are characterised by better heat insulating parameters than these of foamed polystyrene (depending on the used foaming agent and density, the thermal conductivity coefficient ranges from 0,023 to 0,035 W/mK), as well as the mechanical ones.
  • polyurethane foams are self- extinguishing plastics (class of fire resistance E), but on a continuous running basis they can be used even at a temperature as high as up to 1 50°C, and in the case of polyisocyanurate foams (PIR) even up to 180 .
  • PIR polyisocyanurate foams
  • Their price compares unfavourably with that of foamed polystyrenes, which translates directly into the cost increase if they are used for heat insulation of housing units.
  • panels with a foamed polystyrene core the core is glued to the facings with the use of a special polyurethane-based glue. In this case discontinuity of the core is mentioned. Gluing is an additional single manufacturing process in the technology of obtaining such a material, and at the same time increases its cost.
  • panels with a polyurethane core are characterised by continuity of the core (physical and thermal continuity), because the core constitutes an insulating element as well as the gluing one (adhesion for facings).
  • polyurethane panels are characterised by higher rigidity, better heat insulating power.
  • foamed polystyrene panels are relatively light and considerably cheaper than panels with polyurethane cores.
  • fillers such as granulated rubber, sawdust, granulated waste material made from polyurethane foam, PVC, saturated polyesters, as well as polystyrene for foaming (EPS) and expanded graphite (EG) are introduced into the polyurethane reaction mass.
  • EPS polystyrene for foaming
  • EG expanded graphite
  • Polystyrene for foaming as filler for rigid polyurethane foams was also described in the Polish patent specification No. PL 189498.
  • the heat of formation of polyurethane allows for partial plasticization and growth of the EPS beads. This way a heat insulating composite is obtained which contains up to volumetric 50% of foamed polystyrene phase of physical and mechanical parameters as near as possible to foamed polystyrene.
  • the combination of polyurethane foam and foamed polystyrene in the form of laminar composite materials could be characterised by favourable properties, combining the low cost of foamed polystyrenes with the excellent heat insulating parameters of rigid polyurethane foams (PUR).
  • the purpose of the invention is to develop a method of producing heat insulating composite materials based on rigid polyurethane or/and polyisocyanurate foams, in some particular cases containing fillers capable of phase changes, joined together to create a whole without the participation of adhesive agents (glues) with classic layers of expanded or extruded foamed polystyrene, combining the low cost of foamed polystyrenes with the excellent heat insulating properties of rigid polyurethane foams, as well as to obtain thus such heat insulating laminar materials.
  • the subject of the invention is a method of production of heat insulating composite materials based on polyurethanes or/and polyisocyanurates, joined together to create a whole without the participation of adhesive agents (glues) with classic layers of foamed polystyrene, characterised in that a polyurethane mixture containing a polyol and isocyanate component is directly poured out on the layer of foamed polystyrene, with the formation of a permanent weld exhibiting thermal continuity. Then, on the polyurethane mixture poured out on the first layer of foamed polystyrene optionally a second layer of foamed polystyrene is placed with the formation of a permanent weld exhibiting thermal continuity.
  • a filler is introduced which is capable of phase changes in the amount from 20 to 120 % by weight in relation to the weight of the polyurethane mixture, depending on the amount of heat energy generated by the used polyurethane system.
  • the amount of the introduced filler is selected to the total weight of the polyurethane system in such a way that the maximum temperature of the reaction is lower than the temperature of degradation of foamed polystyrene i.e. from 120°C, and the time of lasting of temperatures above 80 °C is not longer than 20 minutes.
  • the amount of filler thus selected will not cause the degradation of foamed polystyrene in the near- surface layer, as well as collapsing of its structure as a result of excessively long load above the working temperature of foamed polystyrene, apart from that, it will form a permanent weld with it.
  • a modification of rigid polyurethane foams with the use of filler capable of phase changes is not necessary.
  • polystyrene for foaming EPS
  • EPS polystyrene for foaming
  • foamed polystyrene of density from 10 to 20 kg/m 3 and thermal conductivity coefficient at a temperature of 10°C from 0,035 to 0,045 W/mK is used.
  • expanded or extruded foamed polystyrene is used.
  • the subject of the invention is also heat insulating composite material based on polyurethanes and/or polyisocyanurates, characterised in that it consists of layers of rigid polyurethane foam and foamed polystyrene joined together to create a whole without the use of adhesive agents (glues), and is obtained by pouring polyurethane mixture containing a polyol and isocyanate component directly out on the layer of foamed polystyrene with the formation of a permanent weld exhibiting thermal continuity.
  • the heat insulating composite material according to the present invention is obtained by applying on the polyurethane mixture poured out on the first layer of foamed polystyrene mixture a second layer of foamed polystyrene with the formation of a permanent weld exhibiting thermal continuity.
  • a second layer of foamed polystyrene with the formation of a permanent weld exhibiting thermal continuity.
  • three-layer materials consisting of two external layers of foamed polystyrene, joined together to create a whole without the use of adhesive agents with a layer of rigid polyurethane foam inside, according to the above described method.
  • the external layers of foamed polystyrene make a diffusion barrier, and the three-layer material manufactured in this way maintains its heat insulating properties for longer periods of time.
  • the polyurethane mixture additionally contains filler capable of phase changes from 20 to 120 % by weight in relation to the weight of polyurethane mixture.
  • the heat insulating composite material according to the invention contains polystyrene for foaming (EPS) as filler capable of phase changes.
  • the heat insulating composite material according to the invention contains foamed polystyrene of density from 10 to 20 kg/m 3 and thermal conductivity coefficient at a temperature of - ⁇ 0°C from 0,035 to 0,045 W/mK.
  • the heat insulating composite material according to the invention contains expanded foamed polystyrene.
  • the heat insulating composite material according to the invention contains extruded foamed polystyrene.
  • foamed polystyrenes Because thermal stability temperatures of foamed polystyrenes reach maximum 80 °C, and the temperature of their degradation is 120°C direct contact of the foamed polystyrene phase with the forming polyurethane phase can lead to the destruction of the first, and at the same time to collapsing of the material. It should also be remembered that foamed polystyrene is also a material with heat insulating properties, which additionally hinders the diffusion of heat from the interior of the forming polyurethane.
  • the layer of foamed polystyrene, onto whose surface polyurethane mixture is poured out ensures a favourably reduced heat energy gradient, which eliminates the necessity of heating the mould, and at the same time can lower the cost of manufacturing of such material.
  • the heat insulating composite materials according to the invention can be found in the form of two- or three-layer laminar composites.
  • foamed polystyrene layers Depending on the thickness of foamed polystyrene layers being used, pure polyurethane foam or polyurethane foam modified with fillers capable of phase changes, such as e.g. polystyrene for foaming (EPS) or expanding graphite (EG) are used.
  • EPS polystyrene for foaming
  • EG expanding graphite
  • the heat insulating composite materials according to the invention are characterized by good heat insulating parameters (heat transmission coefficient is no higher than 0,30 W/m2-K). Moreover, these properties can be modelled by using different variants of thickness and density of particular layers, as well as using polyurethane and foamed polystyrene of different composition.
  • polystyrene for foaming beads OWIPIAN FS 1325 produced by Synthos S.A. of 1 ,3 - 2,5 mm grain size, containing approximately 6% by weight of pentane mixture (64 - 75% of n-pentane and 25 - 34% of isopentane) and 1 ,0% by weight of moisture.
  • the above components were mixed together with the use of a stirrer (about 600 rpm) after being heated to a temperature of 20 °C, and then 59,5 g of polyol component WG 2034 NF manufactured by Polychem Systems Ltd.
  • the material obtained this way was characterized by the following properties: apparent density 30 kg/m 3 , heat transmission coefficient 0,30 W/m 2 -K.
  • Example 2 The components were prepared as in Example 1 , except that a foamed polystyrene panel of 50 mm thickness, 5,2 kg/m 3 density and thermal conductivity coefficient of 0,038 W/mK was used.
  • the material obtained in this way was characterized by the following properties: apparent density 32,6 kg/m 3 , heat transmission coefficient 0,29 W/m 2 -K.
  • the material obtained in this way was characterized by the following properties: apparent density 35 kg/m 3 ; heat transmission coefficient 0,23 W/m 2 -K.
  • the above components were mixed together with the use of a stirrer (about 1200 rpm) after being heated to a temperature of 20°C and were transferred to a mould, and then on the surface of the polyurethane mixture was placed a foamed polystyrene panel of 20 mm thickness, 1 5,2 kg/m 3 density and thermal conductivity coefficient 0,038 W/mK.
  • the composite was left for approximately 20 minutes, enabling the mixture to rise freely in the mould.
  • the material obtained in this way was characterized by the following properties: apparent density 30 kg/m 3 ; heat transmission coefficient 0,25 W/m 2 -K.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention a pour objet un procédé de production de matériaux composites calorifuges à base de polyuréthanes et/ou de polyisocyanurates, unis, pour créer un tout, sans l'utilisation d'agents adhésifs (colles) à des couches classiques de polystyrène expansé, caractérisé en ce qu'un mélange de polyuréthanes contenant un composant polyol et un composant isocyanate est directement versé sur la couche de polystyrène expansé, la formation d'une soudure permanente présentant une continuité thermique. Ensuite, une seconde couche de polyester expansé est placée sur le mélange de polyuréthanes versé sur la première couche de polystyrène expansé avec la formation d'une soudure permanente présentant une continuité thermique. Dans le cas de matériaux dans lesquels l'épaisseur de la couche de polystyrène expansé est inférieure ou égale à 20 mm, une charge susceptible de subir des changements de phase est introduite dans le mélange de polyuréthanes, et en particulier dans le composant isocyanate, à hauteur de 20 à 120 % en poids par rapport au poids du mélange de polyuréthanes, en fonction de la quantité d'énergie thermique produite par le système de polyuréthanes appliqué. L'invention a également pour objet un matériau composite calorifuge à base de polyuréthanes et/ou de polyisocyanurates, obtenu au moyen du procédé décrit ci-dessus.
PCT/PL2012/050030 2011-08-31 2012-08-30 Matériaux composites calorifuges et leur procédé de production WO2013032350A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PLPL396151 2011-08-31
PL396151A PL396151A1 (pl) 2011-08-31 2011-08-31 Kompozytowe materialy termoizolacyjne i sposób ich wytwarzania

Publications (2)

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WO2013032350A2 true WO2013032350A2 (fr) 2013-03-07
WO2013032350A3 WO2013032350A3 (fr) 2013-05-23

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PCT/PL2012/050030 WO2013032350A2 (fr) 2011-08-31 2012-08-30 Matériaux composites calorifuges et leur procédé de production

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WO (1) WO2013032350A2 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL230119B1 (pl) 2013-12-03 2018-09-28 Eutherm Spolka Z Ograniczona Odpowiedzialnoscia Kompozytowy panel elewacyjno-termoizolacyjny, sposób jego wytwarzania oraz zastosowanie kompozytowego panelu elewacyjno- termoizolacyjnego

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL177966B1 (pl) 1994-01-18 2000-02-29 Jan Holm Hansen Sposób wytwarzania wielowarstwowej płyty zwłaszcza dla lekkich konstrukcji budowlanych
US6605650B1 (en) 2002-03-11 2003-08-12 Hunter Paine Enterprises, Llc Process of making lightweight, rigid polyurethane foam
US6727290B2 (en) 2002-03-11 2004-04-27 Hunter Paine Enterprises, Llc Process of making rigid polyurethane foam
PL187591B1 (pl) 1998-03-19 2004-08-31 Bogdan Jaworski Element warstwowy do izolacji termicznej
PL189498B1 (pl) 1998-09-14 2005-08-31 Politechnika Krakowska Sposób otrzymywania kompozytowych materiałów porowatych opartych o poliuretany
PL191471B1 (pl) 1999-04-27 2006-05-31 Przed Produkcji Elementow Budo Warstwowa płyta ścienna
PL193199B1 (pl) 1999-08-27 2007-01-31 Harmulowicz Arkadiusz Sposób wytwarzania płyt warstwowych

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Publication number Priority date Publication date Assignee Title
DE29718016U1 (de) * 1997-10-10 1997-11-27 Bender, Roland, 74831 Gundelsheim Dämmelement für eine Isolierverkleidung
DE20003888U1 (de) * 2000-03-02 2000-07-06 Basf Ag, 67063 Ludwigshafen Fußbodenplatte
DE102008011562A1 (de) * 2008-02-28 2009-09-03 Lanxess Deutschland Gmbh Schalldämpfende Dämmstoffe mit hoher Feuerwiderstandsdauer
DE202010001674U1 (de) * 2009-09-22 2010-05-20 Deutsche Amphibolin-Werke Von Robert Murjahn Stiftung & Co Kg Dämmplatte

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL177966B1 (pl) 1994-01-18 2000-02-29 Jan Holm Hansen Sposób wytwarzania wielowarstwowej płyty zwłaszcza dla lekkich konstrukcji budowlanych
PL187591B1 (pl) 1998-03-19 2004-08-31 Bogdan Jaworski Element warstwowy do izolacji termicznej
PL189498B1 (pl) 1998-09-14 2005-08-31 Politechnika Krakowska Sposób otrzymywania kompozytowych materiałów porowatych opartych o poliuretany
PL191471B1 (pl) 1999-04-27 2006-05-31 Przed Produkcji Elementow Budo Warstwowa płyta ścienna
PL193199B1 (pl) 1999-08-27 2007-01-31 Harmulowicz Arkadiusz Sposób wytwarzania płyt warstwowych
US6605650B1 (en) 2002-03-11 2003-08-12 Hunter Paine Enterprises, Llc Process of making lightweight, rigid polyurethane foam
US6727290B2 (en) 2002-03-11 2004-04-27 Hunter Paine Enterprises, Llc Process of making rigid polyurethane foam

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PL396151A1 (pl) 2013-03-04
WO2013032350A3 (fr) 2013-05-23

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