WO2017050887A1 - Mousses rigides de polyuréthane présentant une propriété isolante et propriété mécanique améliorées - Google Patents

Mousses rigides de polyuréthane présentant une propriété isolante et propriété mécanique améliorées Download PDF

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Publication number
WO2017050887A1
WO2017050887A1 PCT/EP2016/072527 EP2016072527W WO2017050887A1 WO 2017050887 A1 WO2017050887 A1 WO 2017050887A1 EP 2016072527 W EP2016072527 W EP 2016072527W WO 2017050887 A1 WO2017050887 A1 WO 2017050887A1
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Prior art keywords
rigid polyurethane
weight
polyurethane foam
compounds
foam according
Prior art date
Application number
PCT/EP2016/072527
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English (en)
Inventor
Bangwei Xi
Zaixia FAN
Lee YUNHO
Sen MIAO
Liyia WANG
Yujie ZHUANG
Original Assignee
Basf Se
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Application filed by Basf Se filed Critical Basf Se
Priority to CN201680068266.7A priority Critical patent/CN108368224B/zh
Priority to KR1020187011424A priority patent/KR20180059491A/ko
Publication of WO2017050887A1 publication Critical patent/WO2017050887A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
    • B60K15/03—Fuel tanks
    • B60K15/04—Tank inlets
    • B60K15/05—Inlet covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/48—Polyethers
    • C08G18/487—Polyethers containing cyclic groups
    • C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
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    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0085—Use of fibrous compounding ingredients
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C3/00—Vessels not under pressure
    • F17C3/02—Vessels not under pressure with provision for thermal insulation
    • F17C3/025—Bulk storage in barges or on ships
    • F17C3/027—Wallpanels for so-called membrane tanks
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G2110/0058—≥50 and <150kg/m3
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G2390/40—Inner coatings for containers
    • 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
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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
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • F17C2221/00—Handled fluid, in particular type of fluid
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    • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
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    • F17C2223/0146—Two-phase
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    • F17C2270/00—Applications
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    • F17C2270/0102—Applications for fluid transport or storage on or in the water
    • F17C2270/0105—Ships

Definitions

  • the invention relates to a rigid polyurethane foam, to a process for producing it, and to its use as an insulating material, specifically for liquefied natural gas tanks.
  • natural gas is one of the most important energy sources of our time.
  • it usually has to be transported over great distances. This is achieved, for example, via pipelines.
  • the transport of natural gas via pipelines to outlying areas or over very large distances is very expensive.
  • the political situation in some countries may make it impossible to construct pipelines.
  • transport in natural gas tankers (known as liquefied natural gas (LNG) carriers) is frequently chosen as an alternative.
  • LNG liquefied natural gas
  • insulation material use is primarily made of rigid polyurethane foams because of their excellent insulating properties compared to other insulation materials such as polystyrene foam or mineral wool.
  • the overall construction of insulation in liquefied natural gas carriers is extremely complex.
  • the insulation of the tanks not only has to prevent evaporation of natural gas but also has to give the tanks a certain degree of stability.
  • use is made of, for example, plywood, fiberglass and stainless steel layers to reinforce the tanks.
  • the industry tanks comprise mainly a very thin barrier layer of stainless steel, so that the insulation structure provides a major part of the required stability.
  • the rigid polyurethane foam which is frequently used thus has quite a high density.
  • it preferably comprises reinforcing materials, usually glass fiber mats (CSMs - continuous strand mats), which provide the necessary mechanical properties. To ensure the optimal stability, uniform distribution of these continuous strand mats over the total thickness of the foam is an important parameter.
  • the object of the invention is achieved by a rigid polyurethane foam obtained by reacting
  • the prepolymer can be prepared by reacting at least one aromatic diisocyanate and/or polyisocyanate with one or more chain extenders and/or crosslinkers.
  • the amount of extender and/or crosslinker can be calculated according to the desired NCO content of the prepolymer. It is preferred that the prepolymer has a NCO content of from 26% to 32% by weight, more preferably from 27 to 30%> by weight.
  • aromatic diisocyanates and/or polyisocyanates have a viscosity of less than 600 mPas, preferably less than 500 mPas and particularly preferably less than 250 mPas, measured at 25°C.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • PMDI polymeric diphenylmethane diisocyanate
  • isocyanates can be entirely or partially modified with uretdione, carbamate, isocyanurate, carbodiimide, allophanate and preferably urethane groups.
  • the prepolymer has a viscosity of less than 3000 mPas, preferably less than 2000 mPas at 25°C, for example from 400 to 1500 mPas at 25°C.
  • chain extenders and/or crosslinkers for the preparation of prepolymer use is made of, in particular, bifunctional or trifunctional amines and alcohols, in particular diols, trio Is or both, in each case having molecular weights of less than 350, preferably from 60 to 300 and in particular from 60 to 250.
  • bifunctional compounds are referred to as chain extenders and trifunctional or higher- functional compounds are referred to as crosslinkers.
  • aliphatic, cycloaliphatic and/or aromatic diols having from 2 to 14, preferably from 2 to 10, carbon atoms, e.g. ethylene glycol, 1,2-, 1,3 -propanediol, 1,2-, 1,3-pentanediol, 1,10-decanediol, 1,2-, 1,3-, 1,4-dihydroxycyclohexane, diethylene glycol and triethylene glycol, dipropylene glycol and tripropylene glycol, 1,4-butanediol, 1,6-hexanediol and bis(2-hydroxyethyl)hydroquinone, trio Is such as 1,2,4-, 1,3,5-trihydroxycyclohexane, glycerol and trimethylolpropane and low molecular weight hydroxyl-comprising polyalkylene oxides based on ethylene oxide and/or 1 ,2-propylene oxide and the abovementi
  • the chain extender can be an individual compound or a mixture.
  • the chain extender preferably comprises propylene glycol, dipropylene glycol, tripropylene glycol and/or 2,3-butanediol either alone or optionally in mixtures with one another or with further chain extenders.
  • dipropylene glycol is used together with a second chain extender, for example 2,3-butanediol, mono -propylene glycol or diethylene glycol, as chain extender.
  • crosslinkers preference is given to using 1,2,4-, or 1,3,5-trihydroxycyclohexane, glycerol and/or trimethylolpropane. Preference is given to using glycerol as crosslinker.
  • compounds (a) having groups which are reactive toward isocyanates it is possible to use all compounds which have at least two groups which are reactive toward isocyanates, e.g. -OH, -SH, -NH 2 and -COOH. It is usual to use polyether polyols and/or polyester polyols having from 2 to 8 hydrogen atoms which are reactive toward isocyanate.
  • the polyether polyols are obtained by known methods, for example by anionic polymerization of alkylene oxides with addition of at least one starter molecule which comprises from 2 to 8, preferably from 2 to 6, reactive hydrogen atoms in bound form in the presence of catalysts.
  • catalysts it is possible to use alkali metal hydroxides such as sodium or potassium hydroxide or alkali metal alkoxides such as sodium methoxide, sodium or potassium ethoxide or potassium isopropoxide or, in the case of cationic polymerization, Lewis acids such as antimony pentachloride, boron trifluoride etherate or bleaching earth as catalysts.
  • double metal cyanide compounds known as DMC catalysts, can also be used as catalysts.
  • alkylene oxides preference is given to using one or more compounds having from 2 to 4 carbon atoms in the alkylene radical, e.g. tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, in each case either alone or in the form of mixtures, and preferably ethylene oxide and/or 1 ,2-propylene oxide.
  • alkylene radical e.g. tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, in each case either alone or in the form of mixtures, and preferably ethylene oxide and/or 1 ,2-propylene oxide.
  • Possible starter molecules are, for example, ethylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, sugar derivatives such as sucrose, hexitol derivatives such as sorbitol, methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, toluidine, toluenediamine, naphthylamine, ethylenediamine, diethylenetriamine, 4,4 ' -methylenedianiline, 1,3-propanediamine, 1,6-hexanediamine, ethanolamine, diethanolamine, triethanolamine and other dihydric or polyhydric alcohols or monofunctional or polyfunctional amines.
  • Poly ether polyols can also include natural oil-based polyols like castor oil or also alkoxylated modified natural oils or fatty acids.
  • polyether polyol has a functionality of from 3.5 to 5 and a hydroxyl number of from 450 to 600 mg KOH/g, for example from 480 to 580 mg KOH/g.
  • the polyester polyols are usually prepared by condensation of polyfunctional alcohols having from 2 to 12 carbon atoms, e.g. ethylene glycol, diethylene glycol, butanediol, trimethylolpropane, glycerol or pentaerythritol, with polyfunctional carboxylic acids having from 2 to 12 carbon atoms, for example succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, the isomers of naphthalenedicarboxylic acids or the anhydrides of the acids mentioned.
  • DMT dimethylterephthalate
  • PET polyethyleneglycol-terephthalate
  • hydrophobic materials are water-insoluble materials comprising a nonpolar organic radical and also having at least one reactive group selected from among hydroxyl, carboxylic acid, carboxylic ester and mixtures thereof.
  • the molecular weight of the hydrophobic materials is preferably in the range from 130 to 1000. It is possible to use, for example, fatty acids such as stearic acid, oleic acid, palmitic acid, lauric acid or linoleic acid and also fats and oils such as castor oil, maize oil, sunflower oil, soybean oil, coconut oil, olive oil or tall oil.
  • the proportion of the hydrophobic materials based on the total monomer content of the polyester alcohols is preferably from 1 to 30 mol%, particularly preferably from 4 to 15 mol%.
  • rigid polyurethane foams according to the invention wherein the aromatic polyester polyol has a functionality of from 2 to 2.8 and a hydroxyl number of from 250 to 650 mg KOH/g, for example from 300 to 400 mg KOH/g.
  • the aromatic polyester polyols used are usually prepared by condensation of polyfunctional alcohols having from 2 to 12 carbon atoms, e.g. ethylene glycol, diethylene glycol, butanediol, trimethylolpropane, glycerol or pentaerythritol, with polyfunctional aromatic carboxylic acids having from 8 to 12 carbon atoms, for example phthalic acid, isophthalic acid, terephthalic acid, the isomers of naphthalenedicarboxylic acids or the anhydrides of the acids mentioned.
  • DMT dimethylterephthalate
  • PET polyethyleneglycol-terephthalate
  • the polyols (al) and (a2) can be single polyols or mixtures of polyols in a way that the mixture of polyols complies with the definitions of (al) and (a2), respectively.
  • the compounds (a) having groups which are reactive toward isocyanates further comprise chain extenders and/or crosslinkers (a3).
  • Chain extenders and/or crosslinkers refer to the above description of chain extenders and/or crosslinkers for the preparation of the prepolymer.
  • the proportion of the aromatic polyester polyols (al) is preferably from 50 to 70% by weight, based on the total weight of the compounds (a).
  • the proportion of the polyether polyols (a2) is preferably from 30 to 45% by weight, based on the total weight of the compounds (a).
  • the proportion of the compounds (a3) is preferably no more than 8% by weight, particularly preferably no more than 6% by weight, in particular no more than 4% by weight, for example from 1 to 3%) by weight, based on the total weight of the compounds (a).
  • the proportion of the aromatic polyester polyols (al), polyether polyols (a2) and compounds (a3) in the compounds (a) having groups which are reactive toward isocyanates is preferably at least 95% by weight, particularly preferably at least 98% by weight and in particular 100% by weight, based on the total weight of the compounds (a) having groups which are reactive toward isocyanates.
  • Other compounds (a) having groups which are reactive toward isocyanates can be polyester polyols different from aromatic polyester polyols (al), for example aliphatic polyester polyols, or polyether polyols different from polyols (a2).
  • Physical blowing agents are compounds which are inert toward the starting components and are usually liquid at room temperature and vaporize under the conditions of the urethane reaction. The boiling point of these compounds is preferably below 50°C. Physical blowing agents also include compounds which are gaseous at room temperature and are introduced into or dissolved in the starting components under pressure, for example carbon dioxide, low-boiling alkanes, fluoroalkanes and fluoroolefms.
  • the physical blowing agents are usually selected from the group consisting of alkanes and cycloalkanes having at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals, fluoroalkanes, fluoroolefms having from 1 to 8 carbon atoms and tetraalkylsilanes having from 1 to 3 carbon atoms in the alkyl chain, in particular tetramethylsilane.
  • Examples which may be mentioned are propane, n-butane, isobutane and cyclobutane, n-pentane, isopentane and cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl formate, acetone and fluoroalkanes which can be degraded in the troposphere and therefore do not damage the ozone layer, e.g.
  • fluoroolefms are l-chloro-3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluorobutene.
  • the physical blowing agents mentioned can be used alone or in any combinations with one another.
  • the physical blowing agent (c) is used in such an amount that the density of the rigid polyurethane foam is, without taking into account the reinforcing material, preferably in the range from 75 to 150 kg/m 3 , more preferably from 90 to 130 kg/m 3 , most preferably from 100 to 110 kg/m 3 .
  • the reaction for forming the rigid polyurethane foam is carried out in the presence of a catalyst (d).
  • catalysts (d) it is possible to use all compounds which accelerate the isocyanate-polyol reaction. Such compounds are known and are described, for example, in “Kunststoffhandbuch, volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 3.4.1. These comprise amine-based catalysts and catalysts based on organic metal compounds.
  • organic tin compounds such as tin(II) salts of organic carboxylic acids, e.g. tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate and tin(II) laurate, and the dialkyltin(IV) salts of organic carboxylic acids, e.g. dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, and also bismuth carboxylates e.g.
  • organic carboxylic acids e.g. tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate and tin(II) laurate
  • dialkyltin(IV) salts of organic carboxylic acids e.g. dibutylt
  • bismuth(III) neodecanoate bismuth 2-ethylhexanoate and bismuth octanoate, or alkali metal salts of carboxylic acids, e.g. potassium acetate or potassium formate.
  • tertiary amine or a mixture comprising at least one tertiary amine as catalyst (d).
  • tertiary amines are usually compounds which can also bear groups which are reactive toward isocyanate, e.g. OH, NH or NH 2 groups.
  • Some of the most frequently used catalysts are bis(2-dimethylaminoethyl) ether, ⁇ , ⁇ , ⁇ , ⁇ , ⁇ -pentamethyldiethylenetriamine, ⁇ , ⁇ , ⁇ -triethylaminoethoxyethanol, dimethylcyclohexylamine, dimethylbenzylamine, triethylamine, triethylenediamine, pentamethyldipropylenetriamine, dimethylethanolamine, N-methylimidazole, N-ethylimidazole, tetramethylhexamethylenediamine, tris(dimethylaminopropyl)hexahydrotriazine, dimethylaminopropylamine, N-ethylmorpholine, diazabicycloundecene and diazabicyclononene.
  • the reaction for forming the rigid polyurethane foam is carried out in the presence of one or more foam stabilizer (e).
  • foam stabilizer refers to materials which promote formation of a regular cell structure during foam formation. Examples which may be mentioned are: silicon-comprising foam stabilizers such as silo xane-oxy alky lene copolymers and other organopolysiloxanes.
  • Foam stabilizers are preferably used in an amount of from 0.5 to 4% by weight, particularly preferably from 1 to 3% by weight, based on the total weight of the rigid polyurethane foam.
  • the reaction for forming the rigid polyurethane foam is carried out in the presence of further additives (f).
  • further additives it is possible to use flame retardants, plasticizers, further fillers and other additives such as antioxidants.
  • Suitable flame retardants are, for example, brominated ethers (Ixol B 251), brominated alcohols such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol, and also chlorinated phosphates such as tris(2-chloroethyl) phosphate, tris(2-chloroisopropyl) phosphate (TCPP), tris(l,3-dichloroisopropyl) phosphate, tris(2,3-dibromopropyl) phosphate and tetrakis(2-chloroethyl) ethylenediphosphate, or mixtures thereof.
  • brominated ethers Ixol B 251
  • brominated alcohols such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol
  • chlorinated phosphates such as tris(2-chloroethyl) phosphate
  • inorganic flame retardants such as red phosphorus, preparations comprising red phosphorus, expandable graphite, aluminum oxide hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate or cyanuric acid derivatives such as melamine or mixtures of at least two flame retardants such as ammonium polyphosphates and melamine.
  • liquid halogen-free flame retardants it is possible to use diethyl ethanephosphonate (DEEP), triethyl phosphate (TEP), dimethyl propylphosphonate (DMPP), diphenyl cresyl phosphate (DPC) and others.
  • DEEP diethyl ethanephosphonate
  • TEP triethyl phosphate
  • DMPP dimethyl propylphosphonate
  • DPC diphenyl cresyl phosphate
  • the flame retardants are preferably used in an amount of from 0 to 25% based on the total weight of the rigid polyurethane foam.
  • esters of polybasic, preferably dibasic, carboxylic acids with monohydric alcohols can, for example, be derived from succinic acid, isophthalic acid, terephthalic acid, trimellitic acid, citric acid, phthalic anhydride, tetrahydrophthalic and/or hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, fumaric acid and/or dimeric and/or trimeric fatty acids such as oleic acid, optionally in admixture with monomeric fatty acids.
  • the alcohol component of such esters can, for example, be derived from branched and/or unbranched aliphatic alcohols having from 1 to 20 carbon atoms, e.g. methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, the various isomers of pentyl alcohol, of hexyl alcohol, of octyl alcohol (e.g.
  • 2-ethylhexanol of nonyl alcohol, of decyl alcohol, of lauryl alcohol, of myristyl alcohol, of cetyl alcohol, of stearyl alcohol and/or of fatty and wax alcohols which occur naturally or can be obtained by hydrogenation of naturally occurring carboxylic acids.
  • Possible alcohol components also include cycloaliphatic and/or aromatic hydroxy compounds, for example cyclohexanol and its homologues, phenol, cresol, thymol, carvacrol, benzyl alcohol and/or phenylethanol.
  • Esters of monobasic carboxylic acids with divalent alcohols such as Texanol ester alcohols, for example 2,2,4-trimethyl-l,3-pentanediol diisobutyrate (TXIB) or 2,2,4-trimethyl-l,3-pentanediol dibenzoate; diesters of oligoalkylene glycols and alkylcarboxylic acids, for example triethylene glycol dihexanoate or tetraethylene glycol diheptanoate and analogous compounds, can also be used as plasticizers.
  • divalent alcohols such as Texanol ester alcohols, for example 2,2,4-trimethyl-l,3-pentanediol diisobutyrate (TXIB) or 2,2,4-trimethyl-l,3-pentanediol dibenzoate
  • diesters of oligoalkylene glycols and alkylcarboxylic acids for example triethylene glycol di
  • plasticizers are esters of the abovementioned alcohols with phosphoric acid.
  • Phosphoric esters of halogenated alcohols e.g. trichloro ethyl phosphate
  • a flame-retardant effect can be achieved together with the plasticizing effect.
  • mixed esters of the abovementioned alcohols and carboxylic acids are also possible.
  • the plasticizers can also be polymeric plasticizers, e.g. polyesters of adipic, sebacic and/or phthalic acid.
  • alkylsulfonic esters of phenol e.g. phenyl paraffmsulfonate
  • aromatic sulfonamides e.g. ethyltoluene sulfonamide
  • Polyethers for example triethylene glycol dimethyl ether, can also be used as plasticizers.
  • the plasticizer is preferably used in an amount of from 0.05 to 7.5% by weight, particularly preferably from 0.25 to 5% by weight, based on the total weight of the rigid polyurethane foam.
  • the addition of plasticizer enables the mechanical properties of the rigid polyurethane foam to be improved further, in particular at low temperatures.
  • fillers in particular reinforcing fillers, are the known, customary organic and inorganic fillers, reinforcing materials, etc.
  • inorganic fillers such as siliceous minerals, for example sheet silicates such as antigorite, serpentine, hornblendes, amphiboles, chrisotile, talc
  • metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide, zinc sulfide and also glass and others.
  • kaolin China clay
  • Possible organic fillers are, for example: carbon, melamine, rosin, cyclopentadienyl resins and graft polymers and also cellulose fibers, polyamide, polyacrylonitrile, polyurethane and polyester fibers based on aromatic and/or aliphatic dicarboxylic esters and in particular carbon fibers.
  • the inorganic and organic fillers can be used either individually or as mixtures and are advantageously incorporated into the reaction mixture in amounts of from 0.5 to 30% by weight, preferably from 1 to 15% by weight, based on the weight of the rigid polyurethane foam.
  • reinforcing material it is possible to use all materials which give the rigid polyurethane foam an even greater mechanical stability.
  • Such reinforcing materials are, for example, glass fibers, glass fiber mats or carbon fiber mats, preferably glass fiber mats, for example Unifilio® U801 or U809 from Owens Corning Vetrotex.
  • the proportion of reinforcing material is preferably from 5 to 15 percent by weight, based on the total weight of the rigid polyurethane foam.
  • the invention further provides an insulating material for liquefied natural gas tanks, in particular for liquefied natural gas tanks on board ships, which comprises a rigid polyurethane foam according to the invention.
  • the present invention provides a process for producing the rigid polyurethane foam according to the present invention, which comprises reacting
  • the rigid polyurethane foam of the invention is preferably produced continuously on a belt.
  • all components except isocyanate compounds (b), for example compounds (a), blowing agent (c), catalyst (d), foam stabilizer (e) and additives (f) are preferably mixed to form a polyol component.
  • These are subsequently mixed with the isocyanate compounds (b), preferably in a low-pressure mixing apparatus, a high-pressure mixing apparatus at a pressure of less than 100 bar or a high-pressure machine.
  • all components can also each be introduced individually into the mixing apparatus.
  • the reaction mixture obtained in this way is subsequently placed on the reinforcing material, preferably the glass fiber mats, which are preferably continuously rolled off from a plurality of drums (for example 4-10, preferably 6, 7 or 8) onto the belt and there form an appropriate number of layers.
  • the number of layers can be freely chosen and on the desired degree of foam reinforcement and on the foam height produced.
  • the foam obtained is then preferably cured on the belt to such an extent that it can be cut into pieces without damage. This can be carried out at elevated temperatures, for example during passage through an oven.
  • the foam pieces obtained are then preferably stored further in order to attain full mechanical strength.
  • the rigid polyurethane foam obtained is subsequently processed further to produce insulation panels.
  • the pieces of the rigid polyurethane foam of the invention which are obtained are cut to size and preferably adhesively bonded to plywood sheets and resin-impregnated glass fiber mats.
  • These polyurethane foam elements are then provided with further auxiliaries such as iron plates, screws and threads in order to produce the finished insulation elements which are then used directly in the production of the insulation barrier of the liquefied natural gas tank.
  • auxiliaries such as iron plates, screws and threads
  • All components for example compounds (a) having groups which are reactive toward isocyanate, isocyanates (b), physical blowing agents (c), catalysts (d), foam stabilizers (e) and further additives (f) are preferably reacted in such amounts that the isocyanate index is in the range from 100 to 400, preferably 100 to 200, particularly preferably 110 to 150.
  • the isocyanate index is, for the purposes of the invention, the stoichiometric ratio of isocyanate groups to groups which are reactive toward isocyanate multiplied by 100.
  • Groups which are reactive toward isocyanate are in this case all isocyanate-reactive groups comprised in the reaction mixture.
  • Rigid polyurethane foams according to the invention are preferably used for insulation purposes.
  • Rigid polyurethane foams according to the invention are particularly preferably used for the insulation of liquefied natural gas tanks, in particular on board ships (LNG carriers). They are mechanically stable, have a low thermal conductivity, display excellent foam properties, for example without holes or cracks, have good mechanical properties such as shear strengths, compressive strengths and an excellent Young's modulus, all even at low temperatures, and have a uniform distribution of the layers of reinforcing materials.
  • Lambda values were determined in accordance with ASTM C518-04 to evaluate the thermal property.
  • Prepolymer was prepared by dropwise adding a certain amount of chain extender/crosslinker (according to the desired NCO content) at a speed of 1.5 ml/min into lOOOg MDI, PMDI or the mixture of MDI/PMDI at 40 °C. The temperature increased to 60 to 70 °C during the reaction. The mixture was reacted for another 1 hour after all the chain extender/crosslinker was added into the isocyanate. The resulting prepolymer was taken out and measured the NCO content and viscosity.
  • the polyester polyols, polyether polyols and chain extender were stirred with catalyst, foam stabilizer and blowing agent as shown in tables below, the resulted mixture was subsequently mixed with the isocyanates or prepolymer as shown in tables below, immediately after mixing, the final mixture was poured into a 25cm*25cm*25cm open mold, and foamed to give the rigid polyurethane foam.
  • the gel time was in each case set to around 400 seconds by adapting the amount of catalyst. After curing for 24 h, the test specimens were cut in order to determine the thermal conductivity and compressive strength of the foam.
  • the NCO content of prepolymer, Lambda values and compressive strength are also shown in the following tables. All parts are in weight.

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Abstract

La présente invention concerne une mousse rigide de polyuréthane obtenue par la réaction a) de composés comprenant des groupes qui sont réactifs vis-à-vis des isocyanates avec b) un prépolymère d'isocyanate aromatique présentant une teneur en NCO comprise entre 25 % et 33 % en poids, en présence de c) un ou plusieurs agents gonflants physiques. Les composés (a) présentant des groupes qui sont réactifs vis-à-vis des isocyanates comprennent (a1) 45 à 80 % en poids, sur la base du poids total de composés (a), d'un polyesterpolyol aromatique présentant une fonctionnalité inférieure à 3 et un indice d'hydroxyle de 250 mg de KOH/g ou plus, (a2) 20 à 55 % en poids, sur la base du poids total des composés a), d'un polyétherpolyol présentant une fonctionnalité de 3 ou plus et un indice d'hydroxyle de 350 mg de KOH/g ou plus et (a3) 0 à 10 % en poids, sur la base du poids total des composés a), d'un agent d'allongement de chaîne et/ou d'un agent de réticulation.
PCT/EP2016/072527 2015-09-23 2016-09-22 Mousses rigides de polyuréthane présentant une propriété isolante et propriété mécanique améliorées WO2017050887A1 (fr)

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US11767407B1 (en) 2022-04-21 2023-09-26 Covestro Llc HCFO-containing polyurethane foam-forming compositions, related foams and methods for their production
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KR102252902B1 (ko) * 2019-03-28 2021-05-14 한국조선해양 주식회사 발포 조성물과 이의 발포체를 포함하는 단열재, 액화가스 저장탱크 및 선박
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