WO2015165870A1 - Procédé d'amélioration de la stabilité dimensionnelle de mousses dures de polyuréthane - Google Patents

Procédé d'amélioration de la stabilité dimensionnelle de mousses dures de polyuréthane Download PDF

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Publication number
WO2015165870A1
WO2015165870A1 PCT/EP2015/059136 EP2015059136W WO2015165870A1 WO 2015165870 A1 WO2015165870 A1 WO 2015165870A1 EP 2015059136 W EP2015059136 W EP 2015059136W WO 2015165870 A1 WO2015165870 A1 WO 2015165870A1
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Prior art keywords
shaped body
bar
temperature
rigid
water vapor
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PCT/EP2015/059136
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German (de)
English (en)
Inventor
Joachim KLESER
Uwe Kuenzel
Stephan Schleiermacher
Lutz Brassat
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Covestro Deutschland Ag
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Publication of WO2015165870A1 publication Critical patent/WO2015165870A1/fr

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    • 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
    • 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
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B29/007—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to 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
    • 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
    • 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
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • 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
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • 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
    • C08J2205/10—Rigid foams
    • 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

Definitions

  • the invention relates to a method for improving the dimensional stability of PUR and PIR rigid foams.
  • the invention also relates to a molded article of PUR and PIR rigid foams, which is obtainable by this method and its use.
  • PUR and PIR rigid foams collectively referred to as PU hard foam, are used in construction as thermal insulation materials according to the standard DIN EN 13 165. This standard specifies the requirements for factory made rigid polyurethane foam products with and without lamination or coating used for the thermal insulation of buildings. The products are produced in the form of plates and are used primarily to reduce heat and cold losses from the building. Since they reduce the energy expenditure of the heating or cooling system in this respect, such insulation contributes to the protection of the environment.
  • US Pat. No. 3,243,492 describes a process for the production of rigid PU foams, in which the produced plates pass through a stabilization zone immediately after manufacture, in which a treatment at elevated temperature and a relative humidity of 30-95% at a vapor pressure of 145 to 760 mm Hg he follows. Due to the continuous process control, however, a preferred extended storage of the plates is not possible because the residence time in the stabilization zone is limited in time.
  • a disadvantage of the known methods is further that the dimensional stability of the foam panels is not satisfactory in every respect.
  • the object of the present invention was to provide a method which allows over the prior art, an improvement in the dimensional stability of moldings made of PU rigid foams under temperature and humidity.
  • Step a) providing a shaped body of rigid polyurethane foam, followed by the steps b) and c), and optionally step d), wherein
  • Step b) the treatment of the shaped article by storage at a water vapor pressure pz of ⁇ 0.12 bar and a temperature Tz ⁇ 70 ° C for a period of time tz ("intermediate storage") and step e) the subsequent treatment of the shaped article by storage at a water vapor pressure ⁇ > 0.12 bar and a temperature ⁇ > 50 ° C ("conditioning"), as well as
  • Step d) optionally a subsequent storage of the molding at the respective ambient temperature and humidity (“reconditioning") comprise, characterized in that in step b) a time tz of at least 5 hours is maintained.
  • the shaped body used in the process according to the invention is typically produced in a manner known per se by chemical reaction of at least one polyol compound with at least one polyisocyanate compound.
  • the process according to the invention is carried out directly after the production of the shaped body.
  • the present invention is based on the finding that in freshly produced moldings of rigid polyurethane foam by intermediate storage for at least 5 hours at a water vapor pressure of less than 0.12 bar and a temperature of at most 70 ° C, in particular room temperature, and subsequent conditioning at increased temperature and increased humidity, increased dimensional stability of the molding can be achieved.
  • the dimensional stability of the treated moldings is markedly improved at elevated air humidity and elevated temperature compared to not Conditioned moldings or conditioned moldings, which experienced only a short intermediate storage.
  • the improvement in dimensional stability achieved by the process according to the invention can advantageously be verified by subjecting the conditioned shaped body to a temperature of 70 ° C. and a relative humidity of 95% relative humidity for a period of 24 to 48 hours following the process (" Weathering ”) This measure simulates the behavior of an insulation board when installed under extreme climatic conditions.
  • the process according to the invention gives a conditioned molded body of rigid polyurethane foam which under climatic variations / weathering has a dimensional change of less than 2.5%, preferably less than 1.5% and particularly preferably less than 1%, based on at least one component dimension has.
  • the treatment of the molding in step b) of the process according to the invention at a water vapor pressure p z ⁇ 0.12 bar, preferably ⁇ 0.08 bar, more preferably ⁇ 0.06 bar and a temperature T z ⁇ 70 ° C, preferably ⁇ 55 ° C, more preferably ⁇ 35 ° C.
  • the treatment of the shaped body in step b) takes place at room temperature.
  • a time tz of at least 5 hours is maintained according to the invention.
  • the time duration tz denotes the period beginning with the foaming time until the subsequent conditioning of the shaped body in step c).
  • the time tz is more than 12 hours, more preferably more than 24 hours and most preferably more than 48 hours.
  • the conditioning of the shaped body in step c) takes place according to the invention at a water vapor pressure ⁇ of> 0.12 bar, preferably of> 0.2 bar, more preferably of> 0.3 bar at a temperature ⁇ of at least 50 ° C, in particular at least 60 ° C, preferably at least 65 ° C and more preferably at least 70 ° C.
  • a temperature ⁇ during conditioning does not exceed 100 ° C.
  • T K is therefore ⁇ 100 ° C, in particular ⁇ 90 ° C.
  • the abovementioned preferred value ranges for the water vapor pressures and temperatures during the conditioning in step c) are advantageously distinguished by the fact that the dimensional stability of the correspondingly treated molding is markedly improved. This applies in particular to the combination of a temperature ⁇ of at least 70 ° C at a water vapor pressure ⁇ of> 0.24 bar (corresponding to a relative humidity of at least 80% RH), and in particular at a water vapor pressure ⁇ of> 0.27 bar (corresponding a relative humidity of at least 90% RH).
  • the duration for efficient conditioning of the shaped body in step c) depends on the chosen conditioning conditions, ie the prevailing water vapor pressure ⁇ and the temperature ⁇ during the conditioning.
  • the value pair of pi and ⁇ is adjusted so that the desired conditioning effect is achieved after a period of time ⁇ , which can be, for example, between about 5 h to 24 h.
  • ⁇ which can be, for example, between about 5 h to 24 h.
  • the intermediate storage and the conditioning of the shaped body in steps b) and c) of the process according to the invention at fixed water vapor pressures and temperatures in principle be carried out in any manner known to the skilled person, wherein the use of a climate chamber is most convenient because in a such that the control of the vapor pressure can be made precisely.
  • the climatic chamber to be used for this purpose is equipped with a thermostatic control unit and a humidity control unit.
  • the conditioning of the shaped body in step c) is therefore carried out in a climatic chamber.
  • the relative humidity indicates for the current temperature and the current pressure the ratio of the instantaneous water vapor content to the maximum possible water vapor content and is defined as the percentage ratio between the absolute humidity and the maximum humidity, or analogously between vapor pressure / saturation vapor pressure.
  • the intermediate storage and the conditioning are carried out under atmospheric pressure.
  • these steps are carried out under a slight overpressure or underpressure.
  • the molded articles treated by the process according to the invention can be used directly after completion of the treatment or can also be cut to the desired level after the treatment.
  • the molding can be "reconditioned" at ambient temperature and ambient humidity, in particular at 23 ° C. +/- 5 ° C. and 50% +/- 10% relative atmospheric humidity (step d)).
  • step d the preceding conditioning is carried out at relatively high humidities / temperatures, this can lead to water condensing in a subsequent rapid cooling of the molded body, in particular in the region of the foam cells (micro), so that a subsequent Reconditioning is beneficial here.
  • steps b) and / or c) can subsequently be repeated. This procedure can also be carried out several times in succession, for example once, twice or even three times.
  • PU rigid foams are understood to mean those rigid polyurethane foams which contain urethane structures and optionally isocyanurate structures. Reaction systems for PU rigid foams are particularly suitable for the production of rigid polyurethane foam products, such as polyurethane insulation boards, metal composite elements and polyurethane block foam.
  • the aforementioned rigid foams are known to be composed of at least one polyisocyanate component and at least one component with isocyanate-reactive groups.
  • the organic polyisocyanate component contains aromatic polyisocyanates.
  • polyisocyanates which are technically readily available. These include, in particular, isomeric methyldiphenyl diisocyanates and their higher homologs, the polyphenyl polymethylene polyisocyanates. Both are obtained by aniline-formaldehyde condensation and subsequent treatment with phosgene (crude MDI). Also preferred are polyisocyanates derived from 4,4'- and / or 2,4'-diphenylmethane diisocyanate and / or 2,2'-diphenylmethane diisocyanate and their homologs, the carbodiimide, urethane, allophanate, isocyanurate, urea or biuret groups contained (modified polyisocyanates).
  • the organic polyisocyanate component used is preferably mixtures of isomers of diphenylmethane diisocyanate (MDI) and its oligomers. Such blends are generally referred to as "polymeric MDI” (pMDI) Moreover, it is possible to use suitable NCO prepolymers formed via reaction of polymeric MDI with aliphatic and / or aromatic polyether polyols, polyester polyols, polyether polyester polyols, and / or polyether carbonate polyols can.
  • MDI diphenylmethane diisocyanate
  • pMDI polymeric MDI
  • suitable NCO prepolymers formed via reaction of polymeric MDI with aliphatic and / or aromatic polyether polyols, polyester polyols, polyether polyester polyols, and / or polyether carbonate polyols can.
  • polyols there may be included, among others, polyols, polyether polyols, polyester polyols, polyetherester polyols, polyethercarbonate polyols, and combinations thereof.
  • Preferred polyether polyols are addition products of ethylene oxide and / or propylene oxide, and / or epichlorohydrin to di- or polyfunctional starter molecules.
  • Suitable starter molecules are, for example, water, ethylene glycol, diethylene glycol, butyl diglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, dipropylene glycol, pentaerythritol, sorbitol, sucrose, ethylenediamine, toluenediamine, triethanolamine, 1,4-butanediol, 1,6-hexanediol and low molecular weight, hydroxyl groups having esters of such polyols with dicarboxylic acids.
  • Suitable polyester polyols include polycondensates of di- as well as tri- and tetraols and di- and furthermore tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones.
  • free polycarboxylic acids it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols for the preparation of the polyesters.
  • diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1, 2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (1,6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters.
  • polyalkylene glycols such as polyethylene glycol, furthermore 1, 2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (1,6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters.
  • polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate.
  • polycarboxylic acids examples include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid, 2 2-dimethyl succinic acid, dodecanedioic acid, endomethylenetetrahydrophthalic acid, dimer fatty acid, trimer fatty acid, citric acid, or trimellitic acid.
  • the acid source used can also be the corresponding anhydrides, for example phthalic anhydride.
  • Useful polyetherester polyols are those compounds containing ether groups, ester groups and OH groups.
  • Polyether carbonate polyols are obtainable by addition of carbon dioxide and alkylene oxides to suitable H-functional starter substances.
  • Flame retardants may be added to the polyol component, preferably in an amount of from 5 to 50% by weight, based on the total amount of compounds having isocyanate-reactive hydrogen atoms in the polyol component, in particular from 7 to 40% by weight, particularly preferably from 12 to 30% by weight. -%.
  • Such flame retardants are known to those skilled in principle and described for example in "Plastics Handbook", Volume 7 "Polyurethane", Chapter 6.1. These may be, for example, bromine- and chlorine-containing polyols or phosphorus compounds such as the esters of orthophosphoric acid and metaphosphoric acid, which may also contain halogen.
  • liquid flame retardants are selected at room temperature.
  • the proportion may be, for example, from 0 to 6.0% by weight of co-propellant and from 1.0 to 30.0% by weight of propellant, in each case based on 100% by weight of polyol component.
  • the proportion of co-propellant to propellant may be from 20: 1 to 0: 100 as needed.
  • hydrocarbons e.g. the isomers of pentane, or fluorohydrocarbons, e.g. HFC 245fa (1,1,1,3,3-pentafluoropropane), HFC 365mfc (1,1,1,3,3-pentafluorobutane) or mixtures thereof with HFC 227ea (heptafluoropropane), or fluorinated olefins, e.g. Trans-chloro-3,3,3-trifluoropropene and cis-l, l, l, 4,4,4-hexafluoro-2-butene used. It is also possible to combine different propellant classes.
  • fluorohydrocarbons e.g. HFC 245fa (1,1,1,3,3-pentafluoropropane), HFC 365mfc (1,1,1,3,3-pentafluorobutane) or mixtures thereof with HFC 227ea (heptafluor
  • the co-blowing agent used is preferably water, preferably in an amount of up to 6% by weight, particularly preferably 0.5 to 4% by weight, based on the total amount of compounds having isocyanate-reactive hydrogen atoms in the polyol component.
  • the polyol component is conveniently added in polyurethane chemistry conventional catalysts.
  • the amine catalysts necessary for producing a PU rigid foam and the salts used as trimerization catalysts are used in amounts such that e.g. On continuous production lines elements with flexible cover layers can be produced with speeds of up to 60 m / min depending on the element thickness as well as for insulation on pipes, walls, roofs and tanks and in refrigerators in the spray foam process with sufficient curing time can be produced. A discontinuous production is possible.
  • Such catalysts are: triethylenediamine, ⁇ , ⁇ -dimethylcyclohexylamine, tetramethylenediamine, 1-methyl-4-dimethylaminoethylpiperazine, triethylamine, tributylamine, dimethylbenzylamine, ⁇ , ⁇ ', ⁇ "-tris (dimethylaminopropyl) hexahydrotriazine, Dimethylaminopropylformamide, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylbutanediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, dimethylpiperazine, 1, 2-dimethylimidazole, 1-azabicyclo [3.3.
  • octane bis (dimethylaminopropyl) urea, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, triethanolamine, diethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, dimethylethanolamine, stannous acetate, stannous octoate, stannous ethylhexoate, stannous laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dioctyltin diacetate, Tris- (N, N-dimethylaminopropyl) -s-hexahydrotriazine, Tet ramethyl ammonium hydroxide, sodium acetate, sodium octoate, potassium format
  • foam stabilizers may be added to the polyol component, for which purpose polyethersiloxanes are particularly suitable.
  • polyethersiloxanes are particularly suitable.
  • These compounds are generally designed so that a copolymer of ethylene oxide and propylene oxide is connected to a Polydimethylsiloxanrest.
  • Such substances are available on the market for example under the name Struksilon 8031 from the company Schill and Seilacher.
  • Even silicone-free stabilizers, such as the product LK 443 from Air Products, can be used.
  • the organic polyisocyanate cyanate component and the polyol component in such a ratio to each other that results in a ratio of 100 to 600, in particular from 200 to 600.
  • Under code is multiplied by 100 ratio of the mass actually used Isocyanate understood to stoichiometrically required mass of isocyanate.
  • the stoichiometrically required mass of isocyanate corresponds to that mass of isocyanate in which exactly one NCO-reactive group exists in the reaction system for each NCO group.
  • the preparation of the rigid PU foams according to the invention is typically carried out by the one-step process known to those skilled in the reaction in which the reaction components are reacted continuously or discontinuously with each other and then subsequently either manually or by means of mechanical equipment in high-pressure or low-pressure process after discharge to a conveyor belt or be made into suitable forms for curing. Examples are described in US-A 2,764,565, in G. Oertel (ed.) "Plastics Handbook", Volume VII, Carl Hanser Verlag, 3rd edition, Kunststoff 1993, p 267 ff, and in K. Uhlig (ed .) "Polyurethane paperback", Carl Hanser Verlag, 2nd edition, Vienna 2001, pp. 83-102 described. In a preferred embodiment, the rigid polyurethane foam is produced in a continuous process.
  • the molded body of rigid polyurethane foam may have flexible and / or rigid cover layers.
  • flexible cover layers can be used for example: mineral nonwovens (eg glass fiber fabric), paper topcoats, flexible metal foils (eg 50 ⁇ AI film) or multilayer films (eg one or more thin AI films paper and PE film).
  • the moldings according to the invention may also be in the form of a sandwich composite element consisting of a rigid and a flexible or two rigid cover layers and a core layer lying therebetween.
  • metal (foam) composite elements consist of at least two metal cover layers and a foam core layer. Further layers may be provided between the core layer and the cover layers.
  • the outer layers for example, with a paint, coated.
  • the molded body of rigid PU foam is closed-cell, wherein the proportion of open cells is at most 10% of the total cell volume, in particular at most 7%.
  • the measurement is carried out according to DIN ISO 4590 "Determination of the volume fraction of open and closed cells in hard foams".
  • the rigid PU foam preferably has a core density of> 26 kg / m 3 to ⁇ 50 kg / m 3 .
  • the core density is determined according to DIN EN 1602: 1996.
  • the core density is in a range of> 27 kg / m 3 to ⁇ 45 kg / m 3 and particularly preferably from> 29 kg / m 3 to ⁇ 42 kg / m 3 .
  • Another object of the present invention relates to a molded body of rigid polyurethane foam, which is obtainable by a process according to the invention.
  • the conditioned moldings can be used in applications in which the dimensional stability of the components used is of great importance. This is an example of thermal insulation elements of walls, floors and roofs, especially flat roofs or when used in thermal insulation systems of the case.
  • Another object of the present invention is the use of the inventive shaped molded body made of rigid polyurethane foam as a construction element, in particular for the thermal insulation of the building envelope.
  • Formulation PU rigid foam / in parts by weight Polyol formulation A:
  • polyester polyol of phthalic anhydride diethylene glycol
  • polyesterpolyol from phthalic anhydride and diethylene glycol, functionality 2 OH number 705 mg KOH / g:
  • Two-sided aluminum-laminated rigid polyurethane foam panels were produced continuously on a double belt according to recipe 1 and immediately cut to length and trimmed to 600 mm ⁇ 600 mm ⁇ 100 mm.
  • the edged moldings were stored for a period of time tz (see Table 1) measured from the foaming time at a water vapor pressure pz of 0.01 bar and a temperature of 23 ° C (corresponding to a relative humidity of 50% RH). Subsequently, the moldings were trimmed to 90 mm x 90 mm x 100 mm and at a water vapor pressure p K of 0.3 bar and a temperature T K of 70 ° C (corresponding to a relative humidity of 95% RH) for a period of 20 hours conditioned in a climatic chamber made by Espec, model PL-4KPH. Finally, the moldings were reconditioned for a period of 7 days at a temperature of 23 ° C and a relative humidity of 50% RH.
  • the conditioned moldings were stored for 24 h at a temperature of 70 ° C and a relative humidity of 95% RH.
  • the effect of the above-described steps was checked by measuring the dimensional changes of length LI, width L2 and thickness D of the moldings with a caliper each before and after this storage. The relative change of the dimension compared to the zero value has been documented.
  • Table 1 shows the advantageous effect of a prolonged intermediate storage time, in particular on the component thickness change D.
  • a molded body which was subjected to the subsequent conditioning after a longer intermediate storage time, shows a significantly smaller dimensional change in the subsequent measurements (experiment 5).
  • polyester polyol from phthalic anhydride and diethylene glycol functionality 2, OH number 240 mg KOH / g
  • Aluminum strip 99/52, hard, gloss / matt, both sides painted with 310g 743, coined with coarse coarse grain (manufacturer: Hydro Aluminum Roiled Products GmbH) .
  • the edged moldings were stored for a period of time tz (see Table 2) measured from the foaming time at a water vapor pressure pz of 0.01 bar and a temperature of 23 ° C (corresponding to a relative humidity of 50% RH). Subsequently, the moldings were conditioned at a water vapor pressure p K of 0.28 bar and a temperature ⁇ of 70 ° C (corresponding to a relative humidity of 90% RH) for a period of 24 hours in a climate chamber Espec, model PL-4KPH ,
  • the moldings were reconditioned for a period of 7 days at a temperature of 23 ° C and a relative humidity of 50% RH.
  • the conditioned moldings were stored for 48 h at a temperature of 70 ° C and a relative humidity of 95% RH.
  • Analogous to Examples 1 to 5 the dimensional changes of length LI, width L2 and thickness D of the shaped bodies were respectively measured before and after this storage and documented.
  • Table 2 Dimensional stability of the conditioned shaped bodies.
  • the series of Table 2 also shows that moldings which have been stored according to the invention have an improvement in the dimensional stability, in particular with regard to the component thickness change D, this effect increasing with the duration of the intermediate storage.

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  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé d'amélioration de la stabilité dimensionnelle d'éléments façonnés en mousse dure de PU, comprenant les étapes suivantes : • a) préparation d'un article façonné en mousse dure de PU, • b) stockage intermédiaire de l'article façonné sous une pression de vapeur d'eau pz < 0,12 bar et à une température Tz ≤ 70 °C pendant au moins 5 heures, • c) conditionnement de l'article façonné sous une pression de vapeur d'eau pK ≥ 0,12 bar et à une température Tκ ≥ 50°C. L'invention concerne en outre un article façonné en mousse dure de PU qui peut être obtenu par ce procédé, ainsi que son utilisation comme élément de construction.
PCT/EP2015/059136 2014-04-30 2015-04-28 Procédé d'amélioration de la stabilité dimensionnelle de mousses dures de polyuréthane WO2015165870A1 (fr)

Applications Claiming Priority (2)

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EP14166609 2014-04-30
EP14166609.9 2014-04-30

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WO2015165870A1 true WO2015165870A1 (fr) 2015-11-05

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200353716A1 (en) * 2017-11-28 2020-11-12 Dow Global Technologies Llc Polyurethane-based insulation board

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3243492A (en) * 1962-02-08 1966-03-29 Allied Chem Stabilized panel production
US4537912A (en) * 1984-09-05 1985-08-27 Reeves Brothers, Inc. Process for rapid curing of polyether polyurethane foam

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3243492A (en) * 1962-02-08 1966-03-29 Allied Chem Stabilized panel production
US4537912A (en) * 1984-09-05 1985-08-27 Reeves Brothers, Inc. Process for rapid curing of polyether polyurethane foam
US4537912B1 (fr) * 1984-09-05 1989-01-03

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200353716A1 (en) * 2017-11-28 2020-11-12 Dow Global Technologies Llc Polyurethane-based insulation board
US11745465B2 (en) * 2017-11-28 2023-09-05 Dow Global Technologies Llc Polyurethane-based insulation board

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