EP3894460A1 - Pur-/pir-hartschaumstoffen enthaltend polyesterpolyole mit reduzierter funktionalität - Google Patents
Pur-/pir-hartschaumstoffen enthaltend polyesterpolyole mit reduzierter funktionalitätInfo
- Publication number
- EP3894460A1 EP3894460A1 EP19816701.7A EP19816701A EP3894460A1 EP 3894460 A1 EP3894460 A1 EP 3894460A1 EP 19816701 A EP19816701 A EP 19816701A EP 3894460 A1 EP3894460 A1 EP 3894460A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- pes
- polyol
- pur
- octanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
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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
- C08G18/28—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
- C08G18/4236—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
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- C—CHEMISTRY; METALLURGY
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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
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- C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
- C08G18/168—Organic compounds
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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
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/22—Catalysts containing metal compounds
- C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
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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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/50—Polyesters chemically modified by esterification by monohydric alcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
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- C08G2101/00—Manufacture of cellular products
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- C08G2110/0058—≥50 and <150kg/m3
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- C08G2110/00—Foam properties
- C08G2110/0075—Foam properties prepared with an isocyanate index of 60 or lower
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- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08J2205/10—Rigid foams
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
Definitions
- the invention relates to a process for the production of polyester polyols containing monooie and their use, in particular for the production of rigid polyurethane / polyisocyanurate foams (hereinafter also called rigid PUR / PIR foams) with improved fire behavior.
- rigid polyurethane / polyisocyanurate foams hereinafter also called rigid PUR / PIR foams
- Rigid PUR / PIR foams are mainly produced today based on aromatic polyester polyols, since these have a positive effect on the flame retardancy of the rigid PUR / PIR foams and the thermal conductivity.
- the raw materials used in the production of the aromatic polyester polyols are primarily phthalic acid, terephthalic acid and isophthalic acid or their anhydrides.
- polyether polyols and sometimes also aliphatic polyester polyols are occasionally used to improve the solubility behavior of pentanes compared to the aromatic polyester polyols or to reduce the brittleness of the isocyanurate-containing PUR / PIR rigid foams.
- polyester-based PUR / PIR rigid foams are enjoying increasing demand.
- a quantitatively significant polyester polyol is made up of technical glutaric acid (mixture of 70 - 80% glutaric acid, also containing adipic acid and / or succinic acid) and ethylene glycol.
- polyester polyols It is also known from the prior art to use monofunctional components, e.g. monofunctional acids to be used in the synthesis of the polyester in order to lower the average functionality of the resulting polyester polyols (see, for example, EP 1219653 A [0012] and WO 97/48747).
- monofunctional building blocks are monobasic unsaturated fatty acids, explicitly mentioned only the monofunctional oleic acid.
- the functionality of the polyester polyols it is stated that they should be in the range between 1.8 and 8, preferably> 2.
- EP 1 924 356 B1 also discloses producing rigid PUR / PIR foams with polyester films which have functionalities of 1.5-5 and, in addition to polyfunctional alcohols and carboxylic acids, name hydrophobic substances as further starting materials.
- the hydrophobic substances are water-insoluble substances which contain a non-polar organic radical and have at least one reactive group selected from hydroxy, carboxylic acid, carboxylic acid esters or mixtures thereof.
- the equivalent weight of the hydrophobic materials is between 130 and 1000 g / mol.
- fatty acids such as stearic acid, oleic acid, palmitic acid, fauric acid or finoleic acid, as well as fats and Oils such as castor oil, corn oil, sunflower oil, soybean oil, coconut oil, olive oil or tall oil.
- the proportion of the hydrophobic substances in the total monomer content of the polyester alcohol is preferably 1 to 30 mol%, particularly preferably 4 to 15 mol%.
- EP 1 942 356 B1 generally only states that they should be prepared by esterification of the starting products.
- polyester polyols by using monooils. This would broaden the possible raw material base, so that e.g. waste products from other syntheses can also be used.
- polyester polyols with number-average hydroxy functionalities which are between 1.0 and 2.0
- F (OH) number-average hydroxy functionalities
- the Monooie due to their low boiling point or due to their water vapor volatility, often during a classic esterification reaction, i.e. when applying vacuum, e.g. 200 mbar or also 100 mbar or also 10 mbar, and / or at high temperatures, e.g. 180 to 220 ° C, completely or partially discharged in a non-reproducible manner (see, for example, WO 2010/139395 A), with the result that the functionality of the resulting polyester polyol cannot be set reproducibly.
- vacuum e.g. 200 mbar or also 100 mbar or also 10 mbar
- high temperatures e.g. 180 to 220 ° C
- polyester polyols containing monooie in particular polyester polyols containing monooie with number-average hydroxyl functionalities 1.00 ⁇ F (OH) ⁇ 2.00, to be available with which it is possible from the prior art the problems resulting from technology can be overcome and the polyols can be prepared reproducibly.
- the object was achieved by a multi-stage process for the preparation of a polyester polyol PES-B with a number-average OH functionality of> 1.00, preferably with a number-average OH functionality of> 1.00 to ⁇ 2.00, containing the steps a) complete reaction of at least one carboxyl compound selected from the group consisting of i) polyfunctional, preferably difunctional, carboxylic acids and ii) polyfunctional, preferably difunctional, hydroxy-reactive carboxylic acid derivatives selected from the group consisting of carboxylic acid chlorides, carboxylic acid alkyl esters, hydroxy-functional carboxylic acids, factones and carboxylic acid anhydrides with at least one polyol containing 2-8 hydroxyl groups, preferably 2-3 hydroxyl groups, particularly preferably 2 - 2.5 and especially 2 hydroxyl groups, to a polyester polyol PES-A, in which step a) the ratio of the molar amount of hydroxyl groups [n (OH) a ] to molar amount of carboxy
- carboxylic anhydrides having two carboxyl end groups lactones each having one hydroxyl and one carboxyl end group, and alkyl esters of dicarboxylic acids having two carboxyl end groups are included in the balance sheet. Further details for determining the theoretical hydroxyl number are explained in more detail below.
- step b) subsequent reaction of the polyester polyol PES-A obtained in step a) with a monofunctional alcohol (monool) to give the PES-B, the ratio of the molar sum of the hydroxyl groups of all of the reactant molecules used in steps a) and b) to the molar sum of the carboxyl-equivalent groups used: n (OH) E duct / n (Carboxy) E duct > 1.
- carboxyl end groups mean those functional groups of carboxylic acids and carboxylic acid derivatives which are used in an esterification reaction with a hydroxy group can react.
- a polyester polyol PES-A is produced from the carboxy-functional component and the polyol by means of a complete esterification reaction.
- “Complete esterification reaction” in the sense of this application means that the esterification reaction is only terminated when the acid number of the polyester polyol A ⁇ 3 mg KOH / g (preferably ⁇ 1.5 mg KOH / g). The acid number can be determined according to DIN EN ISO 2114 (June 2002).
- the ratio of the starting materials in stage a) is chosen such that the theoretical hydroxyl number corresponds to the desired hydroxyl number of the polyester PES-A when the components are completely esterified.
- the procedure is known in such a way that at least the starting materials difunctional organic acid and difunctional alcohol are initially introduced and reacted by heating.
- the polyester polyols are made without the use of a solvent.
- the discharge of the water of reaction in the solvent-free variant is preferably supported by applying a negative pressure, in particular towards the end of the esterification.
- pressures from 1 to 500 mbar are used.
- esterification is also possible above 500 mbar.
- the discharge of the water of reaction can also be supported by passing an inert gas, such as nitrogen or argon.
- an inert gas such as nitrogen or argon.
- the esterification can also be carried out with the addition of a solvent, in particular a water-carrying solvent (azeotropic esterification), such as benzene, toluene or dioxane.
- a solvent in particular a water-carrying solvent (azeotropic esterification), such as benzene, toluene or dioxane.
- the actual hydroxyl number of the polyester polyol obtained is then determined, e.g. by means of DIN 53240 (December 1971). If there are deviations from the theoretically calculated hydroxyl number as a result of unintentional discharge of diol, the hydroxyl number can be adjusted to the pre-calculated value by adding the same, in a variant at this point subsequent diol by applying an elevated temperature, e.g. is esterified in the range of 160 to 240 ° C over a longer period of 12 to 4 hours, for example 170 ° C and 10 hours or 180 ° C and 6 hours or 200 ° C and 5 hours without applying a vacuum, so that with respect to the Oligomer distribution there is a Schulz-Flory distribution. If the deviation was very large, the hydroxyl number and also the acid number and further addition of diol can be determined again until the measured hydroxyl number of the PES-A corresponds to the desired hydroxyl number.
- the theoretically calculated hydroxyl number of the PES-A is determined from the polyester formulation by balancing the hydroxyl end groups n (OH) a used and the carboxyl end groups or carboxyl-equivalent groups n (carboxy) a used , as defined above.
- carboxylic anhydrides having two carboxyl end groups, lactones each having one hydroxyl and one carboxyl end group, and alkyl esters of dicarboxylic acids having two carboxyl end groups are included in the balance sheet.
- the hydroxyl number of the polyester PES-B can then be read out in an analogous manner
- n (OH) pEs-B n (OH) educt - n (carboxy) educt
- the carboxyl compounds used in step a) are selected from the group consisting of i) polyfunctional, preferably difunctional, carboxylic acids and ii) polyfunctional, preferably difunctional, hydroxy-reactive carboxylic acid derivatives e.g. Carboxylic acid chlorides, carboxylic acid alkyl esters, hydroxy-functional carboxylic acids, lactones and carboxylic acid anhydrides. In particular, the free acids or their anhydrides are used.
- the latter are particularly preferably combined with ethylene glycol and / or diethylene glycol.
- the monool is in the same way by applying an elevated temperature, for example in the range from 160 ° to 240 ° C. over a longer period of 12 to 4 hours, for example 170 ° C. and 10 hours or 180 ° C. and esterified for 6 hours or 200 ° C. and 5 hours without applying a vacuum, and thus obtain the polyester polyol PES-B with the desired functionality and hydroxyl number.
- Stage b) is particularly preferably carried out without solvent and / or entrainer.
- This second stage ensures that the monooie, which in a classical one-stage esterification due to their partly low boiling point but also due to their volatility in water vapor, possibly also due to azeotrope formation with diols during a classic esterification reaction, ie when applying Vacuum, for example 200 mbar or even 100 mbar or also 10 mbar, would be completely or partially discharged in a non-reproducible manner, can be fully implemented.
- the polyester polyol PES-B is obtained, which has a lower number-average molecular weight and a lower functionality than the polyester polyol PES-A. It is essential that the second stage takes place without applying a vacuum, so that no starting material is carried out. The functionality of the polyester polyol PES-B can therefore be safely set using this two-stage synthesis process.
- Monooies which are suitable for step b) above are therefore those whose boiling point at normal pressure is at least 125 ° C., preferably at least 140 ° C., and very particularly preferably at least 165 ° C.
- the monooie are preferably selected from the group consisting of 1-octanol, 2-octanol, 3-octanol, 4-octanol, 2-ethyl-1-hexanol, cis- 2-hexen-1-ol, citronellol, 1-decanol , 1-dodecanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, 1-tetracosanol, preference being given to saturated alcohols with primary hydroxyl groups and less than 12 carbon atoms, and also benzyl alcohol.
- reaction products of the above-mentioned monooies, as well as of shorter-chain monooies such as e.g. 1-hexanol, 1-butanol, 1-propanol with alkylene oxides, preferably with ethylene oxide.
- the number-average functionality of the polyester polyol PES-B obtained can be calculated by calculation as follows: The molar amounts of all of the reactant molecules [n (reactant]) involved in the process, all reactive hydroxyl groups [n (OH) reactant ] and the reactive carboxyl groups [n (carboxy ) Educt ] of the educts used in step a) or step b) is calculated.
- the number-average functionality F (OH) PES B of the polyester PES-B results as follows:
- Catalysts can be used for both process steps.
- all catalysts known for the production of polyesters can be used as catalysts. These are, for example, tin salts, e.g. Tin dichloride, titanates, e.g. Tetrabutyl titanate or strong acids e.g. p-toluenesulfonic acid.
- the polyester polyols can also be prepared without the use of catalysts.
- the hydroxyl number and thus also the number-average molar mass can be determined via the end group titration according to DIN 53240 (December 1971).
- the acid number can be determined according to DIN EN ISO 2114 (June 2002).
- F (OH) relates to the hydroxyl end groups. Acid end groups are not taken into account.
- F (OH) is defined as the number of OH end groups divided by the number of molecules in an ensemble.
- F (OH) normally results from the recipe with which the polyester polyol is made, as stated above, but can in principle also alternatively be determined by ⁇ -NMR or other colligative methods.
- Monocarboxylic acids and their derivatives can also be added to the carboxylic acid (derivative) mixture C used in stage a).
- bio-based starting materials and / or their derivatives such as.
- the polyester polyol PES-B produced by the process according to the invention can be aliphatic or also ar-aliphatic.
- the proportion of aromatic groups can be 0 to 50% by weight, in particular 0 to ⁇ 50% by weight, in each case based on the starting materials, in particular mixtures of glutaric acid, succinic acid, adipic acid and / or phthalic acid as well as ethylene glycol are used. If aromatic groups are present, their proportion is> 0 to 50% by weight.
- the proportion of aromatics in the ester is calculated from the ester formulation by relating the amount of aromatic compound, for example phthalic anhydride or isophthalic acid, to the amount of ester obtained.
- the polyester polyols PES-B containing monooie can be produced reproducibly with the process according to the invention, since the full implementation of the monool is ensured due to the two-stage process.
- "Reproducible" in the sense of this application means that the functionalities and hydroxyl numbers can be set reproducibly in the technical sense - e.g. in a range of +/- 10%, preferably in a range of +/- 5%.
- the polyester polyols PES-B have e.g. Hydroxyl numbers from 150 to 300 mg KOH / g, preferably from 160 to 260, on and e.g.
- Number-average functionalities from ⁇ 2.00, in particular 1.00 to 1.90, preferably from 1.20 to 1.80 and very particularly preferably from 1.30 to 1.79.
- Such polyester polyols cannot be produced in a reproducible manner using the classic one-step synthesis process.
- the polyester polyol PES-B has 60 to 100 mol% of primary hydroxyl groups; the process is also suitable for the production of polyester polyols with less than 60 mol% primary hydroxyl groups.
- the invention relates to the use of the polyester polyols PES-B according to the invention in the production of rigid polyurethane foam products, such as, for example, polyurethane insulation boards, metal composite elements, polyurethane block foam, polyurethane spray foam, polyurethane local foams or even in one - or multi-component assembly foam or as an adhesive raw material.
- the invention further relates to a reaction system for producing rigid PUR / PIR foams, comprising the following components:
- the organic polyisocyanate component A) to components B) and optionally C) being used in such a ratio to one another that there is an index of 100 to 500, in particular 180 to 450 and the reaction system is characterized in that the polyol component B) comprises at least one polyester polyol PES-B according to the invention.
- index or index The molar ratio of all NCO groups of component A) to all NCO reactive groups in the reaction system, in the present case of components B) and C), is referred to by index or index.
- the invention also relates to the use of the polyester polyols PES-B) according to the invention as or in the polyol component B) of a reaction system for the production of PUR / PIR rigid materials.
- Rigid PUR / PIR foams are understood to mean those rigid polyurethane foams which contain polyisocyanurate-modified urethane structures.
- Such a reaction system for PUR / PIR rigid foams is preferably suitable for the production of rigid polyurethane foam products, such as, for example, polyurethane insulation boards, metal composite elements, polyurethane block foam, polyurethane spray foam, polyurethane local foams or also in one or more component assembly foam or as an adhesive raw material.
- the organic polyisocyanate component is aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those described by W. Siefken in Justus Liebigs Annalen der Chemie 562, pp. 75-136, e.g. those of the formula
- n 2-4, preferably 2-3 and Q for an aliphatic hydrocarbon radical with 2-18, preferably 6-10 carbon atoms, a cycloaliphatic hydrocarbon radical with 4-15, preferably 5-10 carbon atoms, an aromatic Hydrocarbon residue with 6-15, preferably 6-13 carbon atoms or an araliphatic hydrocarbon residue with 8-15, is preferably 8-13 carbon atoms, such as polyisocyanates, which are described in DE-OS 2.832.253, pp. 10-11, suitable.
- Polyisocyanates which are technically easily accessible are normally preferred, such as 2,4- and 2,6-tolylene diisocyanate (TDI) and mixtures of these isomers.
- TDI 2,4- and 2,6-tolylene diisocyanate
- Polyphenylpolymethylene polyisocyanates such as e.g.
- polyisocyanates containing carbodiimide, urethane, allophanate, isocyanurate, urea or biuret groups modified polyisocyanates, especially those modified polyisocyanates derived from 2,4- and / or 2,6-tolylene diisocyanate and from 4,4'- and / or 2,4'-diphenylmethane diisocyanate.
- mixtures of isomers of diphenylmethane diisocyanate (MDI) and its oligomers are preferably used as the organic polyisocyanate component.
- MDI diphenylmethane diisocyanate
- oligomers preferably used as the organic polyisocyanate component.
- Such mixtures are generally referred to as "polymeric MDI” (pMDI).
- the polyol component contains at least one polyester polyol according to the invention and can also contain further polyol components.
- further polyol components at least one aliphatic polyester polyol can be used which, in addition to structural units derived from adipic acid, also contains structural units which are derived from glutaric acid, succinic acid and / or phthalic acid, preferably glutaric acid and / or succinic acid.
- the polyol component can contain further compounds with hydrogen atoms which are reactive toward isocyanate groups and which are not polyester polyols, for example polyether polyols or low-molecular chain extenders or crosslinking agents. These additives can improve the flowability of the reaction mixture and the emulsifiability of the blowing agent-containing formulation.
- Flame retardants can be added to polyol component B), preferably in an amount of 5 to 50% by weight, based on the total amount of compounds having hydrogen atoms reactive toward isocyanate groups in the polyol component, in particular 7 to 35% by weight, particularly preferably 12 to 25% by weight.
- Such flame retardants are known in principle to the person skilled in the art and are described, for example, in “Plastics Handbook”, Volume 7 “Polyurethanes”, Chapter 6.1. This can be, for example, bromine and chlorine-containing polyols or phosphorus compounds such as the esters of orthophosphoric acid and metaphosphoric acid, which also Halogen can be included. Flame retardants which are liquid at room temperature are preferably chosen.
- blowing agent and co-blowing agent are used as is necessary to achieve a dimensionally stable foam matrix and the desired bulk density.
- the proportion can be, for example, from 0 to 6.0% by weight of co-blowing agent and from 1.0 to 30.0% by weight of blowing agent, in each case based on 100% by weight of polyol component.
- the ratio of co-blowing agent to blowing agent can be from 20: 1 to 0: 100 as required.
- Hydrocarbons e.g. the isomers of pentane, or hydrofluorocarbons, 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).
- HFC 245fa 1,1,1,3,3-pentafluoropropane
- HFC 365mfc 1,1,1,3,3-pentafluorobutane
- HFC 227ea heptafluoropropane
- Different classes of blowing agents can also be combined.
- n- or c-pentane with HFC 245fa in the ratio 75:25 (n- / c-pentane: HFC 245fa) achieve thermal conductivities, measured at 10 ° C, of less than 20 mW / mK.
- Water and / or formic acid can also be used as co-blowing agent, preferably in an amount of up to 6% by weight, preferably 0.5 to 4% by weight, based on the total amount of compounds with water atoms which are reactive toward isocyanate groups the polyol component.
- water cannot be used.
- Catalysts customary in polyurethane chemistry are advantageously added to the polyol component.
- the amine catalysts required for the production of a rigid PUR / PIR foam and the salts used as trimerization catalysts are used in such an amount that e.g.
- elements with flexible cover layers can be produced at 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 using the spray foam process with sufficient curing time. Batch production is also possible.
- catalysts examples include: triethylenediamine, N, N-dimethylcyclohexylamine, tetra methylenediamine, l-methyl-4-dimethylaminoethylpiperazine, triethylamine, tributylamine, dimethylbenzylamine, N, N ', N "-Tris- (dimcthylaminopropyl) hxxahydrotriazine, dimethylaminopropyl amide, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, dimethylpiperazine, 1, 2-dimethylimidazole, 1-azabicyclo [3.3] , Bis (dimethylaminopropyl) urea, N-methylmorpholine, N-e
- Foam stabilizers can also be added to the polyol component, for which purpose polyether siloxanes are particularly suitable. These compounds are generally constructed in such a way that a copolymer of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane radical. Such substances are available on the market, for example, under the name Struksilon 8031 from Schill and Seilacher or TEGOSTAB® B 8443 from Evonik. Silicone-free stabilizers, such as the product LK 443 from Air Products, can also be used.
- the weight ratio of components A) and B) to one another is from 100: 150 to 100: 300, in particular from 100: 180 to 100: 250.
- polyester polyols PES-B produced by the process according to the invention are particularly well suited for use in PUR-PIR rigid foam formulations.
- the PUR / PIR rigid foams produced with the polyester polyols have a combination of good fire protection properties and mechanical properties.
- Another object of the invention is a process for the production of rigid PUR / PIR foams, in which components A) and B) and optionally C) of a reaction system according to the invention are mixed with one another and allowed to react.
- the PUR / PIR rigid foams according to the invention are typically produced by the one-step process known to the person skilled in the art, in which the reaction components are reacted with one another continuously or discontinuously and then either manually or with the aid of mechanical equipment in a high-pressure or low-pressure process after discharge Conveyor belt or be brought into suitable forms for curing. Examples are in US-A 2,764,565, in G. Oertel (ed.) "Kunststoff-Handbuch", Volume VII, Carl Hanser Verlag, 3rd edition, Kunststoff 1993, p. 267 ff., And in K. Uhlig ( Ed.) "Polyurethane Taschenbuch", Carl Hanser Verlag, 2nd edition, Vienna 2001, pp. 83-102.
- the invention also relates to a rigid foam which can be obtained by mixing and reacting components A) and B) and, if appropriate, C) of a reaction system according to the invention.
- a rigid foam can be used in various fields of application, especially as an insulating material. Examples from the construction industry are wall insulation, pipe shells or pipe half-shells, roof insulation, wall elements and floor panels.
- the rigid foam can be in the form of an insulation board or as a composite element with flexible or non-flexible cover layers and have a density of 25 to 65 kg / m 3 , in particular 30 to 45 kg / m 3 .
- the rigid foam can be in the form of block foam and have a density of 25 to 300 kg / m 3 , in particular 30 to 80 kg / m 3 .
- the invention also relates to the PUR / PIR rigid foams containing laminates according to the invention. These have a core of rigid PUR / PIR foam according to the invention and cover layers firmly connected to it.
- the cover layers can be flexible or rigid. Examples are paper cover layers, fleece cover layers, metal cover layers (e.g. steel, aluminum) and composite cover layers.
- the cover layers are decoiled from a roll and if necessary profiled, if necessary heated and if necessary corona treated in order to improve the foamability of the cover layers.
- a primer can also be applied to the lower top layer before applying the rigid polyisocyanurate foam system.
- TEP Levagard ® TEP Lanxess AG, flame retardant, triethyl phosphate
- Dynamic viscosity MCR 51 rheometer from Anton Paar in accordance with DIN 53019 with a CP 50-1 measuring cone, diameter 50 mm, angle 1 ° at shear rates of 25, 100, 200 and 500 s 1 .
- the polyester polyols according to the invention and not according to the invention show viscosity values which are independent of the shear rate.
- the mechanical properties were determined by means of a tensile test according to EN 1607 (DIN EN 14509) in the version from May 2013, whereby the force was applied perpendicular to the top layer, i.e. in the direction of foaming. This measurement results in the measurement parameters E-module (also called Young’s module).
- the fire properties were determined in accordance with DIN 4102-1 (May 1998 version), whereby the largest flame height and the destroyed sample length are given as measurement parameters for five individual samples.
- Start time The time that elapses from the start of mixing the main components to the visible start of foaming of the mixture.
- Setting time The setting time (“gel point tc") is determined by dipping a wooden stick into the reacting mixture and taking it out again. It characterizes the point in time from which the mixture hardens.
- the tc is the time at which threads can first be drawn between the wooden stick and the reacting mixture. The time measurement starts with the mixing of the foam components.
- Tack free time Shortly after setting time is reached with a wooden stick in short
- the foam surface is scanned at intervals. Starting from the start of the mixing, the adhesive free time is reached when the wooden stick detaches from the foam surface effortlessly, without adhering product.
- the functionality is calculated based on the functionality of the starting materials used.
- Viscosity 1000 mPas (25 ° C)
- Polyester polyol PES-B3 * a) 1661 g (12.40 mol, 51.91.) Were in a 4-liter four-necked flask equipped with mechanical stirrer, 50 cm packed column, thermometer, nitrogen inlet, as well as column head, distillation bridge and vacuum membrane pump % By weight) of technical glutaric acid, 381 g (3.13 mol, 11.93% by weight) of benzoic acid and 1157 g (18.65 mol, 36.20% by weight) of ethylene glycol and with nitrogen blanketing in the course of 60 min. heated to 200 ° C, water of reaction distilled off. After 5 For hours, the pressure was slowly reduced to 200 mbar in the course of 3 hours.
- the reaction was allowed to react for 40 hours under these conditions; the distillates were single phase and had a pH of 7.
- the OHZ was determined to be 154.4 mg KOH / g and the acid number was 1.4 mg KOH / g.
- Discharged ethylene glycol (42.4 g, 0.68 mol) was added and stirred in for a further 6 hours at 200 ° C. under normal pressure.
- Viscosity 1010 mPas (25 ° C)
- Polyester polyol PES-B4 a) In a 4-liter four-necked flask equipped with mechanical stirrer, 50 cm packed column, thermometer, nitrogen inlet, as well as column head, distillation bridge and vacuum membrane pump, 1680 g (12.54 mol) technical glutaric acid and 1045 g (16.83 mol) of ethylene glycol and with nitrogen blanketing in the course of 60 min. heated to 200 ° C, water of reaction distilled off. After 3 hours the pressure was slowly reduced to 30 mbar in the course of 3 hours. The reaction was allowed to continue for 24 hours under these conditions. The OHZ was determined to be 159.8 mg KOH / g and the acid number was 0.5 mg KOH / g.
- Discharged ethylene glycol (74 g, 1.19 mol) was added and stirred in for a further 6 hours at 200 ° C. under normal pressure.
- the OHZ was determined to be 210.2 mg KOH / g and the acid number to 0.47 mg KOH / g. b) 227 g (1.43 mol) of 1-decanol were then added and the mixture was stirred at 200 ° C. for 6 hours under normal pressure.
- Viscosity 580 mPas (25 ° C)
- Polyester polyol PES-B6 * comparative example:
- Viscosity 540 mPas (25 ° C)
- Rigid PUR / PIR foams were produced on the basis of the aforementioned polyester polyols PES-B.
- the respective polyester polyol PES-B according to Table 2 was presented with the other polyols B1 and B-2, and mixed with the flame retardant, a foam stabilizer based on polyether siloxane, catalysts and n-pentane as blowing agent, the mixture thus obtained with polyisocyanate Al mixed and the mixture poured into a wooden box mold open to the top (30x30x10 cm 3 ) and reacted therein.
- Table 2 The formulations and results of the physical measurements on the samples obtained are shown in Table 2.
- Table 2 shows that PUR-PIR rigid foams based on the polyols PES-B4 according to the invention are significantly superior to the PUR-PIR rigid foam based on the non-inventive polyol PES-B 1 in terms of fire properties and are equivalent to the polyols PES-B2 and PES -B3 are.
- the essential difference between the polyol PES-B4 according to the invention and the polyol PES-B 1 not according to the invention consists only in the functionality of the polyester polyol used. All other recipe components are except for the amount of isocyanate identical in their amounts used, although different amounts of isocyanate were required in order to keep the key figures of all formulations at 300 also the same.
- PES-B4 is a good alternative to the well-known polyester polyols PES-B2 and PES-B3.
- the method according to the invention enables the reproducible production of the polyester polyol PES-B4 and enables the use of monoesters for the production of polyester polyols.
Abstract
Description
Claims
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EP18212596 | 2018-12-14 | ||
PCT/EP2019/084319 WO2020120431A1 (de) | 2018-12-14 | 2019-12-10 | Pur-/pir-hartschaumstoffen enthaltend polyesterpolyole mit reduzierter funktionalität |
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US2764565A (en) | 1951-12-24 | 1956-09-25 | Bayer Ag | Process and apparatus for the manufacture of polyurethane plastics |
DE2832253A1 (de) | 1978-07-22 | 1980-01-31 | Bayer Ag | Verfahren zur herstellung von formschaumstoffen |
JP3449833B2 (ja) * | 1995-07-21 | 2003-09-22 | 株式会社クラレ | ポリエステル系の可塑剤 |
DK0906353T3 (da) | 1996-06-18 | 2001-09-03 | Huntsman Int Llc | Stive isocyanuratmodificerede polyurethanskum |
EP1219653A1 (de) | 2000-12-29 | 2002-07-03 | Huntsman International Llc | Harte Polyurethan- oder urethanmodifizierte Polyisocyanurat-Schäume und Verfahren zu ihrer Herstellung |
DE102005041763A1 (de) * | 2005-09-01 | 2007-03-08 | Basf Ag | Polyisocyanurat Hartschaum und Verfahren zur Herstellung |
WO2007049478A1 (ja) | 2005-10-26 | 2007-05-03 | Central Glass Company, Limited | 近赤外線反射基板およびその基板を用いた近赤外線反射合わせガラス、近赤外線反射複層ガラス |
US9605106B2 (en) | 2009-05-30 | 2017-03-28 | Covestro Deutschland Ag | Polyester polyols made of isophthalic acid and/or terephthalic acid and oligoalkyl oxides |
-
2019
- 2019-12-10 EP EP19816701.7A patent/EP3894460A1/de not_active Withdrawn
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