TW201339192A - Preparing rigid polyurethane foams - Google Patents

Abstract

The present invention relates to a process for preparing rigid polyurethane foams or rigid polyisocyanurate foams by using certain polyetherester polyols (B) based on aromatic dicarboxylic acids, optionally further polyester polyols (C), which differ from those of component (B), and polyether polyols (D), wherein the mass ratio of total components (B) and optionally (C) to component (D) is less than 1.6. The present invention also relates to the rigid foams thus obtainable and to their use for producing sandwich elements having rigid or flexible outer layers. The present invention further relates to the underlying polyol components.

Description

Preparation of rigid polyurethane foam

The present invention relates to a polyester polyol C) by using certain polyether ester polyols based on aromatic dicarboxylic acid, B), and optionally other polyether ester polyols different from component B) Polyether polyol D) for the preparation of rigid polyurethane foams or rigid polyisocyanurate foams, wherein the total amount and composition of component B) and optionally C) D) The mass ratio is less than 1.6. The invention also relates to rigid foams obtainable thereby and to the use thereof for producing sandwich elements having a rigid or flexible outer layer. The invention further relates to the underlying polyol component.

By using a polyisocyanate with a compound having a relatively high molecular weight of at least two reactive hydrogen atoms, in particular a polyether polyol produced by polymerization of an alkylene oxide or a polyester polyol produced by polycondensation of an alcohol with a dicarboxylic acid Reacting in the presence of a polyurethane catalyst, a chain extender and/or a crosslinking agent, a blowing agent, and other auxiliaries and additives to produce a rigid polyurethane foam is known and described In a number of patents and literature publications.

More specifically, it is known from the prior art that a polyester polyol obtained by using an aromatic dicarboxylic acid and/or an aliphatic dicarboxylic acid and an alkylene glycol and/or an alkyl triol or an ether diol as a polycondensate is used. . WO 2010/115532 A1 describes the preparation of polyester polyols from terephthalic acid and oligomeric alkylene oxides, which are said to provide products with improved flame retardancy. Fatty acids or fatty acid derivatives are not used in this reference. Low functional alcohols are used as starters.

When a rigid polyurethane (PU) foam is produced using a polyester polyol based on an aromatic carboxylic acid or a derivative thereof (for example, terephthalic acid or phthalic anhydride), the polyester polyol High viscosity often has a significant adverse effect because, therefore, a blend with polyester The increase in viscosity and thus the mixing of the polyol component with the isocyanate is significantly more difficult.

Furthermore, in certain systems for making rigid PU foams, such as when glycerin is used as the relatively high functionality alcohol component, problems with unsatisfactory dimensional stability may occur, ie, The foam product is significantly deformed after the pressure section after removal from the mold or when processed by the two-belt process.

For all systems, the behavior of rigid PU foams during fire has not been satisfactorily resolved. For example, when trimethylolpropane (TMP) is used as the relatively high functionality polyester component, toxic compounds are formed upon ignition.

A general problem in the manufacture of rigid PU foams is surface defects, especially at the interface with the outer layer of metal. These foam surface defects result in the formation of a non-uniform metal surface in the sandwich component, and thus often result in the product being visually unacceptable. Improvements in the surface of the foam reduce the frequency of occurrence of such surface defects and thereby cause visual improvements in the surface of the sandwich component.

Rigid PU foams often exhibit a high degree of brittleness when cut, with a large amount of dust escaping and high sensitivity on one part of the foam, and also during sawing, especially with a metallic outer layer and a polyamine group. The sawing of the composite component of the formate or polyisocyanurate foam core results in the formation of cracks in the foam.

It is generally additionally desirable to provide a system with very high self-reactivity in order to minimize the use of the catalyst.

The rigid PU foams of the prior art and/or their constituents are unsatisfactory in terms of some aspects relating to their profile with respect to the properties mentioned above. It is an object of the invention to improve the form relating to the properties mentioned above.

More specifically, it is an object of the present invention to provide a rigid PU foam having a low brittleness. Another object of the present invention is to provide a polyol component having high self-reactivity.

In addition, the compounds used and the blends prepared therefrom should have a lower viscosity to provide good meterability and miscibility in the preparation of rigid PU foams. In addition, the solubility of the foaming agent, such as the solubility of pentane in the polyol component, should also be good.

Another object is to improve the dimensional stability of rigid PU foams. The formation of toxic compounds should be minimal during fire. In addition, the formation of surface defects should be reduced.

For the selection (constitution) of the components, the materials used should be obtainable at very low cost and inconvenience (i.e., especially with minimal processing and purification steps).

It has been found that this object is achieved by a process for preparing a rigid polyurethane foam or a rigid polyisocyanurate foam which comprises the reaction of: A) at least one polyisocyanate, B) at least one polyether ester polyol obtainable by esterification of: b1) 10 mol% to 70 mol% dicarboxylic acid composition, the composition comprising: b11) with the dicarboxylic acid The composition is from 50 mol% to 100 mol% of one or more aromatic dicarboxylic acids or derivatives thereof, b12) from 0 mol% to 50 mol% of one or more aliphatic dicarboxylic acids based on the dicarboxylic acid composition b1) Or a derivative thereof, b2) 2 mol% to 30 mol% of one or more fatty acid or fatty acid derivatives, b3) 10 mol% to 70 mol% of one or more aliphatic or cycloaliphatic groups having 2 to 18 carbon atoms An alcohol or an alkoxylate thereof, b4) 2 mol% to 50 mol% of a polyether polyol having a functionality of not less than 2 prepared by alkoxylation of a polyol having a functionality greater than 2, all in components From the total of b1) to b4), wherein the components b1) to b4) are 100 mol% in total, and C) other polyester polyols which are different from the polyester polyol of component B), as the case may be, D )Polyether polyol , E) a flame retardant as the case may be, F) one or more foaming agents, G) catalysts, and H) other auxiliaries or additives used as appropriate, wherein the mass ratio of component B) and optionally C) to component D) is less than 1.6.

The present invention also provides a polyol component comprising the above-mentioned components B) to H), wherein the mass ratio of the component B) and optionally C) to the component D) is less than 1.6 .

The present invention further provides a rigid polyurethane foam and a rigid polyisocyanurate foam obtainable by the method of the present invention, and a sandwich member thereof for producing a rigid or flexible outer layer. use.

The invention will now be more specifically illustrated. Combinations of the preferred embodiments are beyond the scope of the invention. This is especially the case for the embodiments of the individual components A) to H) which have been characterized as preferred. The examples set forth below with respect to components B) to H) apply not only to the process of the invention and to the rigid foams obtainable thereby, but also to the polyol component of the invention.

Component B

In the context of the present invention, the term "polyester polyol" is synonymous with "polyesterol" and the term "polyether polyol" is synonymous with "polyetherol".

Component b11) preferably comprises at least one compound selected from the group consisting of terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate (PET), phthalic acid , phthalic anhydride (PA) and isophthalic acid. Component b11) more preferably comprises at least one compound selected from the group consisting of terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate (PET) and phthalic acid. Anhydride (PA). Component b11) even more preferably comprises phthalic anhydride, dimethyl terephthalate (DMT), terephthalic acid or a mixture thereof. The aromatic dicarboxylic acid or its derivative in component b11) is preferably selected from the above The aromatic dicarboxylic acids and dicarboxylic acid derivatives mentioned are mentioned, in particular selected from terephthalic acid and/or dimethyl terephthalate (DMT). The terephthalic acid and/or DMT in component b11) gives the polyetherester B) particularly good fire protection properties. Terephthalic acid is especially preferred because the formation of destructive elimination products can be avoided as compared to DMT.

The ratio of the aliphatic dicarboxylic acid or the aliphatic dicarboxylic acid derivative (component b12)) contained in the dicarboxylic acid composition b1) is generally in the range of 0 mol% to 30 mol% and preferably 0 mol. From % to 10 mol%. The dicarboxylic acid composition b1) is particularly preferably free of any aliphatic dicarboxylic acid or a derivative thereof and thus to some extent consists of 100 mol% of one or more aromatic dicarboxylic acids or derivatives thereof, in which case The above mentioned are preferred.

The amount of component b2) is preferably in the range of from 3 mol% to 20 mol% and more preferably in the range of from 5 mol% to 18 mol%.

The amount of the component b3) is preferably in the range of 20 mol% to 60 mol%, more preferably in the range of 25 mol% to 55 mol%, and even more preferably in the range of 30 mol% to 45 mol%.

The amount of component b4) is preferably in the range of 2 mol% to 40 mol%, more preferably in the range of 2 mol% to 35 mol%, and even more preferably in the range of 15 mol% to 25 mol%.

In one embodiment of the invention, the fatty acid or fatty acid derivative b2) consists of a fatty acid or a mixture of fatty acids, one or more fatty acid or a mixture of fatty acid glycerides, and/or one or more fatty acid monoesters (for example, biodiesel or fatty acid methyl esters) Composition b2) more preferably composed of a fatty acid or a mixture of fatty acids and/or one or more fatty acid monoesters; component b2) even more preferably consists of a fatty acid or a mixture of fatty acids and/or biodiesel; and component b2) even More preferably consists of a mixture of fatty acids or fatty acids.

In a preferred embodiment of the invention, the fatty acid or fatty acid derivative b2) is selected from the group consisting of castor oil, polyhydroxy fatty acid, ricinoleic acid, stearic acid, hydroxy modified oil, grape seed oil, Black cumin oil, pumpkin kernel oil, borage seed oil, large Soybean oil, wheat germ oil, rapeseed oil, sunflower oil, peanut oil, apricot kernel oil, pistachio oil, almond oil, olive oil, macadamia nut oil, avocado oil, sea buckthorn oil, sesame oil, Hemp seed oil, hazelnut oil, primrose oil, wild rose oil, safflower oil, walnut oil, tallow (such as beef tallow), fatty acids, fatty acids modified with hydroxyl, biodiesel, fatty acid methyl esters, and based on Nutmeg oleic acid, palmitoleic acid, oleic acid, isooleic acid, petroselinic acid, oleic acid, sinapic acid, nervonic acid, linoleic acid, α- and γ-linolenic acid, stearidonic acid , fatty acids of arachidonic acid, timnodonic acid, salmon acid and cervonic acid, and mixed fatty acids.

In a particularly preferred embodiment of the invention, the fatty acid or fatty acid derivative b2) is oleic acid, biodiesel, soybean oil, rapeseed oil or tallow, more preferably oleic acid biodiesel, soybean oil, rapeseed oil or tallow Even better is oleic acid or biodiesel, and even more preferably oleic acid. Fatty acids or fatty acid derivatives are generally used to improve the solubility of foaming agents in the manufacture of rigid polyurethane foams.

Component b2) is particularly preferably free of any triglycerides, in particular no oil or fat. As mentioned above, glycerol released by triglyceride by esterification/transesterification has a detrimental effect on the dimensional stability of rigid foams. Thus, preferred fatty acids and fatty acid derivatives in the case of component b2) are the fatty acid itself as well as the alkyl monoesters of fatty acid alkyl monoesters and fatty acid mixtures, especially the fatty acids themselves and/or biodiesel.

The aliphatic or cycloaliphatic diol b3) is preferably selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentane Alcohol, 1,6-hexanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol and alkoxylates thereof. The aliphatic diol b3) is particularly preferably monoethylene glycol or diethylene glycol, especially diethylene glycol.

It is preferred to use the polyether polyol b4) having a functionality greater than 2, which is prepared by alkoxylating a polyol having a functionality of not less than 3.

According to the invention, the functionality of the polyether polyol b4) is greater than 2. Its functionality is not small It is 2.7 and especially not less than 2.9. In general, the functionality is no more than 6, preferably no more than 5 and more preferably no more than 4.

In one embodiment of the invention, the polyether polyol b4) can be obtained by reacting a polyol having a functionality greater than 2 with ethylene oxide and/or propylene oxide, preferably with ethylene oxide.

In another preferred embodiment, the poly is obtained by alkoxylating a polyol selected from the group consisting of sorbitol, pentaerythritol, trimethylolpropane, glycerin, polyglycerol, and mixtures thereof. Ether polyol b4).

In a particularly preferred embodiment, the polyether polyol b4) can be obtained by alkoxylation with ethylene oxide to provide improved fire barrier properties to the rigid polyurethane foam.

In a preferred embodiment of the invention, component b4) is anion which is formed by the use of at least one starter molecule by the action of propylene oxide or ethylene oxide, preferably ethylene oxide, in the presence of an alkoxylation catalyst. Prepared by polymerization, such as an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; or an alkali metal alkoxide such as sodium methoxide, sodium ethoxide, potassium ethoxide or potassium isopropoxide; Amine alkoxylation catalysts such as dimethylethanolamine (DMEOA), imidazole and imidazole derivatives; and mixtures thereof. KOH and amine alkoxylation catalysts are preferred alkoxylation catalysts. Since the polyether is first neutralized when KOH is used as the alkoxylation catalyst and the potassium salt product produced must be removed before the polyether can be used as component b4) in the esterification, it is preferred to use an amine. Alkoxylation catalyst. Preferred amine alkoxylation catalysts are selected from the group consisting of dimethylethanolamine (DMEOA), imidazole and imidazole derivatives, and mixtures thereof, more preferably imidazole.

In an advantageous embodiment of the invention, the polyether polyol b4) consists of the reaction product of glycerol with ethylene oxide and/or propylene oxide, preferably with ethylene oxide. Therefore, the storage stability of component B) is particularly high.

In another advantageous embodiment of the invention, the polyether polyol b4) consists of the reaction product of trimethylolpropane with ethylene oxide and/or propylene oxide, preferably with ethylene oxide. another Furthermore, the result is that the storage stability of component B) is especially improved.

The OH number of the polyether polyol b4) is preferably in the range of 150 to 1250 mg KOH/g, preferably in the range of 300 to 950 mg KOH/g, and more preferably in the range of 500 to 800 mg KOH/g. Inside.

In a particularly preferred embodiment of the invention, the polyether polyol b4) consists of trimethylolpropane or glycerol, preferably the reaction product of glycerol and ethylene oxide, and the OH number of the polyether polyol b4) In the range of 500 to 650 mg KOH/g, and using KOH or imidazole, imidazole is preferably used as the alkoxylation catalyst.

In a particularly preferred embodiment of the invention, the polyether polyol b4) consists of trimethylolpropane or glycerol, preferably the reaction product of glycerol and ethylene oxide, and the OH number of the polyether polyol b4) In the range of 500 to 650 mg KOH/g, imidazole is used as the alkoxylation catalyst, and the aliphatic or cycloaliphatic diol b3) is diethylene glycol, and the fatty acid or fatty acid derivative is oleic acid.

The amount of component b4) used per kg of the polyetherester polyol B) is preferably not less than 200 mmol, more preferably not less than 400 mmol, even more preferably not less than 600 mmol, even more preferably not less than 800 mmol, and most preferably Not less than 1000 mmol.

The number-weighted average functionality of the polyether ester polyol B) is preferably not less than 2, preferably more than 2, more preferably more than 2.2 and especially more than 2.3, so that the portion of the polyurethane prepared therefrom has Higher crosslink density, and thus better mechanical properties on portions of the polyurethane foam.

For the preparation of polyetherester polyols, the aliphatic and aromatic polycarboxylic acids and/or derivatives and polyols may advantageously be in the presence of a catalyst or preferably in the presence of an esterification catalyst, advantageously in an inert gas (for example, nitrogen). In an atmosphere, at a melting temperature of from 150 ° C to 280 ° C, preferably from 180 ° C to 260 ° C, the acid value required for polycondensation is optionally reduced under reduced pressure, and the acid value is advantageously less than 10, preferably less than 2 . In a preferred embodiment, the esterification mixture is at atmospheric pressure and then less than 500 mbar, preferably 40 to 400 millimeters at the temperatures mentioned above. The polycondensation is carried out under a pressure of Ba to form an acid value of 80 to 20, preferably 40 to 20. Possible esterification catalysts are, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts, which are in the form of metals, metal oxides or metal salts. However, the polycondensation can also be carried out in the liquid phase in the presence of a diluent and/or an entrainer such as benzene, toluene, xylene or chlorobenzene to distill off the condensation reaction as an azeotrope. water.

In order to prepare the polyether ester polyol, the organic polycarboxylic acid and/or the derivative and the polyol are advantageously in a molar ratio of from 1:1 to 2.2, preferably from 1:1.05 to 2.1 and particularly preferably from 1:1.1 to 2.0. Polycondensation is carried out.

The number average molecular weight of the resulting polyester polyol is generally in the range of from 300 to 3,000, preferably in the range of from 400 to 1,000, and especially in the range of from 450 to 800.

The proportion of the polyether ester polyol B) according to the invention is generally at least 10% by weight, preferably at least 20% by weight, and more preferably at least 25% by weight, based on the total of the components B) to H).

In order to produce a rigid polyurethane foam by the method of the present invention, in addition to the specific polyester polyol described above, constituent components known per se are also used, and with respect to the constituent components, the following may be provided. Details.

Component A

For the purposes of the present invention, polyisocyanates are understood to mean organic compounds which comprise at least two reactive isocyanate groups per molecule (ie a functionality of at least 2). When the polyisocyanate used or the mixture of two or more polyisocyanates does not have a single functionality, the quantity-weighted average functionality of component A) used is at least 2.

Aliphatic, cycloaliphatic, araliphatic polyfunctional isocyanates and preferably aromatic polyfunctional isocyanates known per se are conceivable for use as polyisocyanates A). Such polyfunctional isocyanates are known per se or can be obtained by methods known per se. More specifically, the polyfunctional isocyanate can also be used in the form of a mixture, in which case component A) will comprise various polyfunctional isocyanates. It is conceivable that the polyfunctional isocyanate used as the polyisocyanate has two (hereinafter referred to as diisocyanate) or more than two isocyanate groups per molecule.

Specific examples are: alkyl diisocyanates having 4 to 12 carbon atoms in an alkylene group, such as dodecyl 1,12-diisocyanate, 2-1,4-diisocyanate Ethyltetramethylene ester, 2-methylpentamethylene 1,5-diisocyanate, tetramethylene 1,4-diisocyanate, and preferably 1,6-diiso Hexamethylene cyanate; a cycloaliphatic diisocyanate such as cyclohexane 1,3-diisocyanate and cyclohexane 1,4-diisocyanate and any mixture of such isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), hexahydro-tolyl 2,4-diisocyanate and 2,6 - hexahydro-tolyl diisocyanate and a mixture of the corresponding isomers, dicyclohexylmethane 4,4'-diisocyanate, dicyclohexylmethane 2,2'-diisocyanate and 2, 4'-Dicyclohexylmethane diisocyanate and mixtures of corresponding isomers, and preferably aromatic polyisocyanates such as 2,4-diisocyanate tolyl and 2,6-diisocyanate Stretching tolyl ester and its corresponding isomer mixture, 4,4'-diphenylphenyl diisocyanate, 2,4'-diisocyanate diphenylmethane and 2,2'-diisocyanate Diphenylmethane a mixture of an ester and a corresponding isomer, a mixture of diphenylmethane 4,4'-diisocyanate and diphenylmethane 2,2'-diisocyanate, polyphenylpolymethylene polyisocyanate, Mixture of 4,4'-diphenylmethane diisocyanate, diphenylmethane 2,4'-diisocyanate and diphenylmethane 2,2'-diisocyanate, and polyphenylene Polymethylene polyisocyanate (crude MDI), and a mixture of crude MDI and toluene diisocyanate.

Particularly suitable are 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and/or 4,4'-diphenylmethane diisocyanate. (MDI), 1,5-anthranyl diisocyanate (NDI), 2,4-tolyl diisocyanate and/or 2,6-streptyl diisocyanate (TDI) , 3,3'-dimethylbiphenyl diisocyanate, 1,2-diphenylethane diisocyanate and / or diphenyl isocyanate (PPDI), diisocyanate Trimethylene acid ester, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethyl diisocyanate and/or diiso) Octamethyl cyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutyl 1,4-diisocyanate, 1,5-diisocyanate Pentamethylene ester, 1,4-diisocyanate butyl ester, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophor) Keto diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane and/or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), diisocyanate 1,4-cyclohexane ester, 1-methyl-2,4-cyclohexane diisocyanate and/or 1-methyl-2,6-cyclohexane diisocyanate and diisocyanate Acid 4,4'-dicyclohexylmethane, 2,4'-dicyclohexylmethane diisocyanate and / or 2,2'-dicyclohexylmethane diisocyanate.

Modified polyisocyanates are also often used, i.e., products obtained by chemical reaction of an organic polyisocyanate and having at least two reactive isocyanate groups per molecule. Particular mention may be made of polyisocyanates comprising esters, ureas, biurets, ureaforms, carbodiimides, isocyanurates, uretdiones, urethanes and/or urethane groups. .

For the polyisocyanates used as component A), the following examples are preferred: i) based on toluene diisocyanate (TDI), especially 2,4-TDI or 2,6-TDI or 2,4-TDI a polyfunctional isocyanate of a mixture of 2,6-TDI; ii) based on diphenylmethane diisocyanate (MDI), especially 2,2'-MDI or 2,4'-MDI or 4,4'-MDI or Oligomeric MDI (also known as polyphenyl polymethylene isocyanate), or a mixture of two or three of the above mentioned diphenylmethane diisocyanates, or crude MDI (which is in the manufacture of MDI) Producing), or a polyfunctional isocyanate of at least one oligomer of MDI and at least one of the above mentioned low molecular weight MDI derivatives; iii) at least one aromatic isocyanate of example i) and at least one of example ii) A mixture of aromatic isocyanates.

It is especially preferred to use polymeric diphenylmethane diisocyanate as the polyisocyanate. The polymerized diphenylmethane diisocyanate (hereinafter referred to as polymeric MDI) is a mixture of a binuclear MDI and an oligomeric condensation product, and thus is a derivative of diphenylmethane diisocyanate (MDI). The polyisocyanate preferably also consists of a mixture of a monomeric aromatic diisocyanate and a polymeric MDI.

The polymeric MDI also comprises, in addition to the binuclear MDI, one or more polynuclear condensation products of MDI having a functionality greater than 2, especially 3 or 4 or 5. Polymeric MDI is known and is often referred to as polyphenyl polymethylene isocyanate, or as oligomeric MDI. Polymeric MDI is usually A mixture of MDI-based isocyanates having different functionalities. The polymeric MDI is typically used in the form of a mixture with the monomeric MDI.

The (average) functionality of the polyisocyanate comprising polymeric MDI can vary from about 2.2 to about 5, more preferably from 2.3 to 4, and even more preferably from 2.4 to 3.5. Such mixtures of MDI-based polyfunctional isocyanates having different functionalities are, in particular, the crude MDI obtained as an intermediate in the manufacture of MDI.

MDI-based polyfunctional isocyanates or mixtures of two or more polyfunctional isocyanates are known and are marketed, for example, by BASF Polyurethanes GmbH under the name Lupranat®.

The functionality of component A) is preferably at least 2, especially at least 2.2, and more preferably at least 2.4. The functionality of component A) is preferably in the range of from 2.2 to 4 and more preferably in the range of from 2.4 to 3.

The content of the isocyanate groups in component A) is preferably in the range of from 5 to 10 mmol/g, especially in the range of from 6 to 9 mmol/g and more preferably in the range of from 7 to 8.5 mmol/g. It is known to those skilled in the art that the isocyanate group content in milligrams per gram (mmol/g) and the so-called equivalent weight in grams per equivalent are reciprocal to each other. The isocyanate group content in mmol/g is obtained from the content in wt% according to ASTM D-5155-96A.

In a particularly preferred embodiment, component A) consists of at least one polyfunctional isocyanate selected from the group consisting of 4,4'-diphenylmethane diisocyanate and 2,4' diisocyanate. - Diphenylmethane ester, 2,2'-diphenylmethane diisocyanate and diphenylmethane diisocyanate. In the case of the preferred embodiment, component (a1) particularly preferably comprises diphenylmethane diisocyanate and has a functionality of at least 2.4.

The viscosity of component A) used can vary within wide limits. The viscosity of component A) is preferably in the range of 100 to 3000 mPa*s and more preferably in the range of 200 to 2500 mPa*s.

Component C

Unlike polyester polyol B), suitable polyester polyols C) can have from 2 to 12 carbons An organic dicarboxylic acid of an atom, preferably an aromatic dicarboxylic acid, or an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid, and a polyol having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms. It is preferably obtained as a mixture of diols.

Possible dicarboxylic acids are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decane dicarboxylic acid, maleic acid, fumaric acid, ortho-benzene Dicarboxylic acid, isophthalic acid and terephthalic acid. These dicarboxylic acids may be used singly or in a mixture with each other. Instead of the free dicarboxylic acid, it is also possible to use the corresponding dicarboxylic acid derivative, for example a dicarboxylic acid ester or a dicarboxylic acid anhydride of an alcohol having 1 to 4 carbon atoms. It is preferred to use phthalic acid, phthalic anhydride, terephthalic acid and/or isophthalic acid in the form of a mixture or as an aromatic dicarboxylic acid. It is preferred to use a mixture of succinic acid, glutaric acid and adipic acid dicarboxylic acid in a weight ratio of, for example, 20-35:35-50:20-32 and especially adipic acid as the aliphatic dicarboxylic acid. Examples of glycols and polyols, especially diols, are: ethylene glycol, diethylene glycol, 1,2-propylene glycol or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5- Pentandiol, 1,6-hexanediol, 1,10-nonanediol, glycerin, trimethylolpropane, and pentaerythritol. Preferably, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or a mixture of at least two of the aforementioned glycols is used. In particular, a mixture of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. Polyester polyols derived from lactones such as ε-caprolactone or hydroxycarboxylic acids such as ω-hydroxycaproic acid can also be used.

Bio-based starting materials and/or derivatives thereof are also suitable for the preparation of other polyester polyols C), such as castor oil, polyhydroxy fatty acids, ricinoleic acid, hydroxy-modified oils, grape seed oil, black Fennel oil, pumpkin kernel oil, borage seed oil, soybean oil, wheat germ oil, rapeseed oil, sunflower oil, peanut oil, apricot kernel oil, pistachio oil, almond oil, olive oil , Hawaiian nut oil, avocado oil, sea buckthorn oil, sesame oil, hemp seed oil, hazelnut oil, primrose oil, wild rose oil, safflower oil, walnut oil, fatty acid, fatty acid modified by hydroxyl, and based on myristic acid , palmitoleic acid, oleic acid, isooleic acid, petroselinic acid, oleic acid, sinapic acid, nervonic acid, linoleic acid, Fatty acid esters of α- and γ-linolenic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, salmonic acid and docosahexaenoic acid.

In general, the mass ratio of polyetherester polyol B) to polyester polyol C) is at least 0.1, preferably at least 0.25, more preferably at least 0.5, and especially at least 0.8. Preferably, the proportion of the polyether ester polyol B) in the total amount of the polyester polyols B) and C) is generally at least 25 wt%, preferably at least 50 wt%, more preferably at least 75 wt%. And especially 100 wt%. Other polyester polyols C) are not particularly reactive.

Component D

According to the invention, a rigid PU foam is prepared using a polyether polyol D). The polyether polyol D) can be obtained by known methods, for example, by using an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal alkoxide such as sodium methoxide, sodium ethoxide, potassium ethoxide or isopropyl alcohol. a potassium alkoxide) or an amine alkoxylation catalyst such as dimethylethanolamine (DMEOA), imidazole or an imidazole derivative, which comprises an average of 2 to 8 and preferably 2 to 6 reactive hydrogen atoms in a bonded form. At least one starter molecule or starter molecule mixture is anionically polymerized with one or more alkylene oxides having from 2 to 4 carbon atoms, or by using a Lewis acid such as antimony pentachloride, ether boron fluoride or clay ( Lewis acid) is obtained by cationic polymerization.

Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2-butylene oxide or 2,3-butylene oxide, styrene oxide, and preferably ethylene oxide and 1, 2-propylene oxide. The alkylene oxides can be used singly, in succession alternately or as a mixture. Preferred alkylene oxides are propylene oxide and ethylene oxide.

Possible starter molecules are, for example, water; organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid; aliphatic and aromatic groups having from 1 to 4 carbon atoms in the alkyl group, a diamine substituted with N-monoalkyl-, N,N-dialkyl- and N,N'-dialkyl, as the case may be, in the case of a monoalkyl or dialkyl substituted ethylenediamine, Diethyltriamine, triethylamine, 1,3-propyldiamine, 1,3-butylenediamine or 1,4-butylenediamine, 1,2-hexa Methyldiamine, 1,3-hexamethylenediamine, 1,4-hexamethylenediamine, 1,5-hexamethylene Diamine and 1,6-hexamethylenediamine, phenylenediamine, 2,3-tolyldiamine, 2,4-tolyldiamine and 2,6-tolyldiamine, And 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane and 2,2'-diaminodiphenylmethane. The di(primary amine), such as ethylenediamine, is especially preferred.

Other possible starting molecules are: alkanolamines such as ethanolamine, N-methylethanolamine and N-ethylethanolamine; dialkanolamines such as diethanolamine, N-methyldiethanolamine and N-ethyldiethanolamine; a trialkanolamine such as triethanolamine; and ammonia.

Preference is given to using diols or polyols (also known as "starters"), such as ethylene glycol, 1,2-propanediol and 1,3-propanediol, diethylene glycol (DEG), dipropylene glycol, 1 , 4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, and sucrose. It is especially preferred to use sucrose with DEG or sucrose with glycerol, especially a mixture of sucrose and glycerin starter.

The polyether polyol D), preferably a polyoxypropylene polyol and a polyoxyethylene polyol, has a functionality of preferably from 2 to 6, and especially from 2 to 5, and from 150 to 3,000, preferably from 200 to 2,000. In particular, the number average molecular weight is from 250 to 1000.

A preferred embodiment of the invention utilizes an alkoxylated diol, preferably an ethoxylated diol, such as polyethylene glycol, as part of the polyether polyol D).

In a preferred embodiment of the invention, the polyether alcohol component D) consists of a mixture of polyether alcohols in which some of the polyether alcohol component D) is based on propylene oxide. The (polyether alcohol component D1) is prepared and the remaining polyether alcohol component D) is prepared on the basis of ethylene oxide (polyether alcohol component D2).

In a preferred embodiment of the invention, the polyether alcohol component D1) has an average OH functionality of greater than 3, preferably greater than 3.5 and more preferably greater than 4, and greater than 300 mg KOH/g, preferably greater than 350 Mg KOH/g, more preferably greater than 400 mg KOH/g and especially OH number greater than 450 mg KOH/g.

In a preferred embodiment of the invention, the polyether alcohol component D1) has less than 6, An average OH functionality of less than 5.5 and more preferably less than 5, and an OH number of less than 600 mg KOH/g, preferably less than 550 mg KOH/g and more preferably less than 500 mg KOH/g.

In a preferred embodiment of the present invention, the proportion of the polyether alcohol component D1) in the total amount of the polyether alcohol component (D) is more than 65 wt%, preferably more than 70 wt%, more preferably more than 75. Wt%, especially greater than 80 wt% and especially greater than 85 wt%.

In a preferred embodiment of the invention, the polyether alcohol component D1) is not based on sorbitol.

In a preferred embodiment of the invention, the polyether alcohol component D1) is based on a polyether prepared from a mixture of propylene oxide and sucrose with glycerol or sucrose and DEG, preferably sucrose and glycerin.

In a preferred embodiment of the invention, the polyether alcohol component D2) is based on a polyether alcohol based on ethylene oxide and having an average OH functionality of no more than 3, preferably a polyether alcohol component D2. The functionality has a functionality equal to 2 and the polyether alcohol component D2) has an OH number of less than 400 mg KOH/g, preferably less than 300 mg KOH/g and more preferably less than 200 mg KOH/g.

In a particularly preferred embodiment of the invention, the polyether alcohol component D) consists of two polyethers, ie based on propylene oxide and a starter mixture of sucrose and glycerol and having an average OH of greater than 4 and less than 5 a polyether (polyether alcohol component D1) having a functionality and an OH number of more than 450 mg KOH/g and less than 500 mg KOH/g, and a polyethylene glycol having a OH number of less than 200 mg KOH/g (poly Ether alcohol component D2).

The proportion of the polyether polyol D) is generally in the range of from 25 wt% to 55 wt%, preferably from 29 wt% to 45 wt%, more preferably, based on the total of the components B) to H). It is in the range of 31 wt% to 43 wt%, more specifically in the range of 33 wt% to 42 wt%, and especially in the range of 35 wt% to 40 wt%.

According to the invention, the mass ratio of the total amount of components B) and C) to component D) is less than 1.6, in particular less than 1.5 or 1.4, preferably less than 1.3, more preferably less than 1.2, even more preferably less than 1.1, particularly preferably Less than 1 and optimally less than 0.8.

Furthermore, according to the invention, the mass ratio of the total amount of components B) and C) to component D) is more than 0.1, in particular more than 0.2, preferably more than 0.4, more preferably more than 0.5 and most preferably more than 0.6.

Component E

A flame retardant known from the prior art can generally be used as the flame retardant E). Suitable flame retardants are, for example, brominated esters, brominated ethers (Ixol) or brominated alcohols (such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol), and chlorinated phosphates (such as , ginseng (2-chloroethyl) phosphate, ginseng (2-chloropropyl) phosphate (TCPP), ginseng (1,3-dichloropropyl) phosphate), tricresyl phosphate, ginseng (2, 3-dibromopropyl)phosphate, bis(2-chloroethyl)ethylidene diphosphate, dimethyl methanephosphonate, diethyl diethanolamine methylphosphonate, and commercially available halogen-containing flame retardant A polyol. By means of other phosphates or phosphonates, diethyl ethanephosphonate (DEEP), triethyl phosphate (TEP), dimethyl propyl phosphonate (DMPP), toluene diphenyl phosphate (DPK) can be used. ) as a liquid flame retardant.

In order to prepare a rigid polyurethane foam flame retardant, in addition to the flame retardant mentioned above, inorganic or organic flame retardants such as red phosphorus, a formulation containing red phosphorus, and hydrated alumina may also be used. , antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives (such as melamine), or a mixture of at least two flame retardants, such as ammonium polyphosphate and melamine and optionally Corn starch, or ammonium polyphosphate, melamine, expandable graphite, and optionally aromatic polyester.

Preferred flame retardants do not have isocyanate reactive groups. These flame retardants are preferably liquid at room temperature. Especially preferred are TCPP, DEEP, TEP, DMPP and DPK, especially TCPP.

The proportion of the flame retardant E), based on the components B) to H), is generally in the range of 10 wt% to 40 wt%, preferably in the range of 15 wt% to 30 wt% and more preferably 20 wt%. Up to 25 wt%.

Component F

The foaming agent F) for producing a rigid polyurethane foam preferably comprises water, formic acid And mixtures thereof. The foaming agents react with the isocyanate groups to form carbon dioxide and form carbon dioxide and carbon monoxide in the case of formate. In addition, physical blowing agents such as low boiling hydrocarbons can be used. Suitable physical blowing agents are those which are inert to the polyisocyanate A) and which have a boiling point below 100 ° C, preferably below 50 ° C at atmospheric pressure, and thus are vaporized under conditions of exothermic addition polymerization. Examples of such liquids which may preferably be used are alkanes such as heptane, hexane, n-pentane and isopentane, preferably n-pentane and isopentane, n-butane and isobutane and propane. a mixture; a cycloalkane such as cyclopentane and/or cyclohexane; an ether such as furan, dimethyl ether and diethyl ether; a ketone such as acetone and methyl ethyl ketone; an alkyl carboxylate such as methyl formate , dimethyl oxalate and ethyl acetate; and halogenated hydrocarbons such as dichloromethane, dichloromonofluoromethane, difluoromethane, trifluoromethane, difluoroethane, tetrafluoroethane, chlorodifluoroethane, 1 , 1-dichloro-2,2,2-trifluoroethane, 2,2-dichloro-2-fluoroethane and heptafluoropropane. Mixtures of such low boiling liquids with one another and/or with other substituted or unsubstituted hydrocarbons may also be used. Organic carboxylic acids such as formic acid, acetic acid, oxalic acid, ricinoleic acid and carboxyl-containing compounds are also suitable.

Preferably, no formic acid or any halogenated hydrocarbon is used as the blowing agent. Preference is given to using water, any pentane isomer and mixtures of water and pentane isomers.

The blowing agent is completely or partially dissolved in the polyol component (i.e., B+C+D+E+F+G+H) or introduced via a static mixer just prior to foaming the polyol component. Water or formic acid is usually completely or partially dissolved in the polyol component, and a physical blowing agent such as pentane and any remaining chemical blowing agents are introduced "on the line".

The polyol component is mixed in situ with pentane, some chemical blowing agents that may be present, and all or some of the catalyst. Auxiliaries and additives as well as flame retardants have been included in the polyol blend.

The blowing agent or the foamer mixture is used in an amount ranging from 1 wt% to 30 wt%, preferably from 3 wt% to 15 wt%, and more preferably from the total of the components B) to H). Preferably in the range of 5 wt% to 10 wt%.

When water is used as the foaming agent, it is preferably added to the polyol component in an amount of from 0.2 wt% to 10 wt% (based on component B) (B+C+D+E+F+G+H) )in. The addition of water can be carried out in combination with the use of other such blowing agents. It is preferred to use a combination of water and pentane.

Component G

Catalysts G) for the preparation of rigid polyurethane foams are, in particular, compounds which substantially accelerate the reaction of the compounds comprising the reactive hydrogen atoms, in particular the hydroxyl groups, B) to H) with the polyisocyanate A).

It is preferred to use a basic polyurethane catalyst such as a tertiary amine such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N,N, N',N'-tetramethyldiaminodiethyl ether, bis(dimethylamino-propyl)urea, N-methylmorpholine or N-ethylmorpholine, N-cyclohexyl-morpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N,N-tetramethylbutanediamine, N,N,N,N-tetramethylhexane-1,6 -diamine, pentamethyldiethylideneamine, bis(2-dimethylaminoethyl)ether, dimethyl-piperazine, N-dimethylaminoethylpiperidine, 1,2 - dimethylimidazole, 1-azabicyclo-[2.2.0]octane, 1,4-diazabicyclo[2.2.2]octane (Dabco), and alkanolamine compounds such as triethanolamine, three Isopropanolamine, N-methyldiethanolamine and N-ethyldiethanolamine, dimethylaminoethanol, 2-(N,N-dimethylaminoethoxy)ethanol, N,N',N "-Sentyl (dialkylamino-alkyl)hexahydrotriazine, such as N, N', N"-paraxyl (dimethylaminopropyl)-s-hexahydrotriazine, and tri-ethyl Diamine. However, metal salts such as iron (II) chloride, zinc chloride, lead octoate, and preferably tin salts such as tin dioctoate, tin diethylhexanoate and dibutyltin dilaurate, and especially tertiary amines Mixtures with organotin salts are also suitable.

Other possible catalysts are: anthraquinones such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; alkali metal hydroxides , such as sodium hydroxide; and alkali metal alkoxides such as sodium methoxide and potassium isopropoxide; alkali metal carboxylates and alkali metal salts of long chain fatty acids having 10 to 20 carbon atoms and optionally OH pendant groups. It is preferred to use 0.001 parts by weight based on 100 parts by weight of component B) (ie, calculated) 10 parts by weight of catalyst or catalyst combination. It is also possible to carry out the reaction without catalysis. In this case, the catalytic activity of the polyol starting from the amine is utilized.

When an excess of polyisocyanate is used during foaming, other suitable catalysts for the tertiary polymerization of the excess NCO groups are: an isocyanurate-based catalyst, such as ammonium alone or in combination with a tertiary amine. An ionic or alkali metal salt, in particular an ammonium or alkali metal carboxylate. The formation of isocyanurate produces a fire resistant PIR foam which is preferably used in industrial rigid foams, for example as a heat insulating sheet or sandwich element in construction and construction.

In a preferred embodiment of the invention, one of the components G) is partly composed of a carboxylate, in particular an alkali metal carboxylate.

Further information on the above mentioned and other starting materials can be found in the technical literature, for example Kunststoffhandbuch, Volume VII, Polyurethane, Carl Hanser Verlag Munich, Vienna, No. 1, 2nd edition and 3rd edition, 1966, 1983 and 1993.

Component H

Further auxiliaries and/or additives H) may optionally be added to the reaction mixture for the production of rigid polyurethane foams. Mention may be made, for example, of surface active substances, foam stabilizers, cell regulators, fillers, dyes, pigments, hydrolysis inhibitors, fungistatic substances and bacteriostatic substances.

Possible surface active substances are, for example, compounds which can be used to promote homogenization of the starting materials, and which can also be adapted to adjust the cell structure of the polymer. Mention may be made, for example, of emulsifiers, such as castor oil sulfates or sodium salts of fatty acids, and salts of fatty acids with amines (for example diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate), sulfonic acids a salt (for example an alkali metal or ammonium salt of dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid) and a ricinoleate; a foam stabilizer such as a siloxane-oxyalkylene copolymer and Other organic polyoxane, ethoxylated alkyl phenol, ethoxylated fatty alcohol, paraffin oil, castor oil or ricinoleate, Turkey red oil and peanut oil; and cell regulator Such as paraffin wax, fatty alcohol and dimethyl polyoxyalkylene. Polyalkylene oxide and fluoroalkane groups as side groups The above oligoacrylates are also suitable for improving the emulsification, cell structure and/or stabilizing the foam. The amount of the surface active material is usually from 0.01 part by weight to 10 parts by weight based on 100 parts by weight of the component B) (that is, calculated).

For the purposes of the present invention, fillers, especially reinforcing fillers, are conventional organic and inorganic fillers, reinforcing materials, weighting agents, auxiliaries for improving the abrasive behavior of paints, coating compositions, etc., such materials Known for itself. Specific examples are: inorganic fillers, such as cerium-containing minerals, such as layered cerium salts, such as lobular serpentine, serpentine, hornblende, amphibole, chrysotile and 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 and zinc sulfide, and glass. It is preferred to use kaolin (porcelain), aluminum silicate, and a coprecipitate of barium sulfate and aluminum citrate, as well as natural and synthetic fiber minerals (such as asbestos), metal fibers and especially glass fibers of various lengths. A coating of a certain size is applied. Possible organic fillers are, for example, carbon, melamine, rosin, cyclopentadienyl resins and graft polymers, as well as cellulose fibers, polyamines, polyacrylonitriles, polyurethanes, based on aromatics and / or polyester fibers of aliphatic dicarboxylates and especially carbon fibers.

The inorganic and organic fillers may be used singly or in the form of a mixture, and are preferably added in an amount of from 0.5% by weight to 50% by weight, preferably from 1% by weight to 40% by weight, based on the weight of the components A) to H). The content of the natural, synthetic fiber mat, non-woven fabric and woven fabric may be up to a value of up to 80% by weight based on the weight of components A) to H).

Additional information on other conventional auxiliaries and additives mentioned above can be found in the technical literature, such as JHSaunders and KCFrisch's monograph "High Polymers" Volume XVI, Polyurethanes, Parts 1 and 2, Interscience Publishers 1962 and 1964, or Kunststoff-Handbuch, Polyurethane, Vol. VII, Hanser-Verlag, Munich, Vienna, 1st and 2nd editions, 1966 and 1983.

The invention further provides a polyol component comprising: 10 wt% to 50 wt% polyether ester polyol B), 0 wt% to 30 wt% other polyester polyol C), 25 wt% to 55 wt% polyether polyol D), 10 wt% to 40 wt % flame retardant E), 1 wt% to 30 wt% foaming agent F), 0.5 wt% to 10 wt% catalyst G), and 0 wt% to 20 wt%, especially 0.5 wt% to 20 wt% other help And additives H), each as defined above and each in terms of the total weight of components B) to H), wherein the wt% amounts to 100 wt%, and wherein the total amount and composition of components B) and C) The mass ratio of the fraction D) is less than 1.6.

The polyol component particularly preferably comprises: 25 wt% to 40 wt% polyether ester polyol B), 0 wt% other polyester polyol C), 29 wt% to 45 wt% polyether polyol D), 15 wt % to 30 wt% flame retardant E), 3 wt% to 15 wt% foaming agent F), 0.5 wt% to 10 wt% catalyst G), 0.5 wt% to 5 wt% other auxiliaries and additives H), Each is as defined above and each is based on the total weight of components B) to H), wherein the wt% amounts to 100 wt%, and wherein the mass ratio of the total amount of components B) and C) to component D) Less than 1.3.

The total amount of components B) and C) and the mass of component D) in the polyol component of the invention are preferably greater than 0.1, more particularly greater than 0.2, more preferably greater than 0.4, even more preferably greater than 0.5 and most preferably greater than 0.6. .

For the production of the rigid polyurethane foam of the invention, polyisocyanate A), the specific polyester polyol B) according to the invention, optionally other polyester polyols C), polyethers The alcohol D) and the other components E) to H) are such that all the reactivity of the NCO group on the polyisocyanate A) and the component B), optionally C) and D) to H) in the reaction The equivalent ratio of hydrogen atoms is in the range of 1 to 3.5:1, preferably in the range of 1 to 2.5:1, more preferably in the range of 1.1 to 2.1:1, even more preferably in the range of 1.2 to 2.0:1. In particular, it is mixed in an amount ranging from 1.3 to 1.9:1, more specifically in the range of from 1.4 to 1.8:1 and suitably in the range of from 1.4 to 1.7:1.

Preferably, the NCO group on the polyisocyanate A) and the component B), optionally C) and all of the reactive hydrogen atoms on D) to H) are more than 1.0:1, preferably greater than 1.1:1. More preferably, it is greater than 1.2:1, especially greater than 1.3:1 and especially greater than 1.4:1.

The following examples illustrate the invention.

The following polyester polyols (polyesterol 1, polyesterol 3 and polyesterol 5) and polyetherester polyols (polyesterol 2, polyesterol 4, polyesterol 6 and polyesterol 7) were used: Polyester alcohol 1 (comparative agent): an esterification product of terephthalic acid (34 mol%), oleic acid (9 mol%), diethylene glycol (40 mol%) and glycerol (17 mol%), which has The hydroxyl functionality of 2.3, the hydroxyl number of 244 mg KOH/g and the oleic acid content of 20% by weight in the polyester alcohol.

Polyesterol 2 (invention): terephthalic acid (31 mol%), oleic acid (8 mol%), diethylene glycol (43 mol%) prepared in the presence of imidazole as an alkoxylation catalyst and An esterification product of a polyether (18 mol%) based on glycerol and ethylene oxide and having an OH functionality of 3 and a hydroxyl number of 546 mg KOH/g. This polyether was not treated before it was used in the subsequent esterification reaction. The polyesterol has a hydroxyl functionality of 2.3, a hydroxyl number of 239 mg KOH/g, and an oleic acid content of 15% by weight in the polyester alcohol.

Polyester Alcohol 3 (comparative agent): ester of phthalic anhydride (30 mol%), oleic acid (12 mol%), diethylene glycol (40 mol%) and trimethylolpropane (18 mol%) A product having a hydroxyl functionality of 2.2, a hydroxyl number of 249 mg KOH/g, and an oleic acid content of 25% by weight in the polyester alcohol.

Polyesterol 4 (invention): Phthalic anhydride (25 mol%), oleic acid (15 mol) prepared in the presence of KOH as an alkoxylation catalyst and subsequently neutralized and removed the potassium salt formed %), an esterification product of diethylene glycol (37 mol%) and polyether (23 mol%) based on trimethylolpropane and ethylene oxide and having an OH functionality of 3 and 610 mg The number of hydroxyl groups of KOH/g. The polyesterol has a hydroxyl functionality of 2.2, a hydroxyl number of 244 mg KOH/g, and an oleic acid content of 24% by weight in the polyester alcohol.

Polyesterol 5 (comparative agent): an esterification product of terephthalic acid (35 mol%), oleic acid (7 mol%), diethylene glycol (40 mol%) and glycerol (18 mol%), which has The hydroxyl functionality of 2.5, the hydroxyl number of 256 mg KOH/g and the oleic acid content of 16% by weight in the polyester alcohol.

Polyester Alcohol 6 (Invention): terephthalic acid (29 mol%) and oleic acid (10 mol%) prepared in the presence of KOH as an alkoxylation catalyst and subsequently neutralized and removed the potassium salt formed. Esterification product of diethylene glycol (36 mol%) and polyether (25 mol%) based on glycerol and ethylene oxide and having 3 OH functionality and 535 mg KOH/g hydroxyl group number. The polyesterol has a hydroxyl functionality of 2.5, a hydroxyl number of 245 mg KOH/g, and an oleic acid content of 15% by weight in the polyester alcohol.

Polyester Alcohol 7 (Invention): terephthalic acid (29 mol%), oleic acid (10 mol%), diethylene glycol (36 mol%) prepared in the presence of imidazole as an alkoxylation catalyst and An esterified product of a polyether (25 mol%) based on glycerol and ethylene oxide and having an OH functionality of 3 and a hydroxyl number of 540 mg KOH/g. This polyether was not treated before it was used in the subsequent esterification reaction. The polyesterol has a hydroxyl functionality of 2.5, a hydroxyl number of 246 mg KOH/g, and an oleic acid content of 15% by weight in the polyester alcohol.

Determination of Curing and Brittleness of Rigid Polyurethane Foams

The curing was measured using a bolt test. For this purpose, the balls with a radius of 10 mm were used in a polystyrene beaker after mixing the components of the polyurethane foam for 2.5, 3, 4, 5, 6 and 7 minutes. The steel bolt of the cover was pressed to a depth of 10 mm in the formed mushroom-shaped foam. The maximum force (in N) required here is A measure of the solidification of the foam.

The brittleness of the rigid foam was determined by measuring the time when the surface of the rigid polyisocyanurate foam exhibited a visible damage zone in the bolt test. After the foaming, the brittleness was further determined subjectively by compressing the foam and classified according to the scale of 1 to 6, wherein 1 indicates a foam having almost no brittleness and 6 was a high-brittle foam.

Determination of the self-reactivity of the polyurethane system

The polyurethane system described below was adjusted to a single fiber time by varying the concentration of the polyurethane catalyst. When the system requires a lower catalyst concentration, this means that the system has a higher self-reactivity.

Measuring dimensional stability

The dimensional stability was determined by measuring the thickness of the element after foaming. For this purpose, a sandwich element having an aluminum foil of 0.05 mm thick as an outer layer material was produced in a two-belt method, and the thickness of the element was measured at the center of the element 5 minutes after manufacture. The closer the element thickness thus determined is to the gauge element thickness (170 mm in the case of the present invention), the better the dimensional stability.

Inventive Examples 1 and 2 and Comparative Examples 1 and 2

Manufacture of rigid polyurethane foams (variant 1): The isocyanate and isocyanate-reactive components are combined with the foaming agent, catalyst and all other additives in a polyol component ratio of isocyanate to 100: A constant mixing ratio of 180 is foamed.

Polyol component: 30 parts by weight of a polyesterol according to the present invention or a comparative example; 36.5 parts by weight of a polyether alcohol prepared by addition polymerization of propylene oxide to a sucrose/glycerin mixture as a starter molecule, having 490 mg OH/g OH number and 4.3 average functionality; 6 parts by weight of a polyether alcohol obtained from ethoxylated ethylene glycol having a hydroxyl functionality of 2 and a hydroxyl number of 190 mg KOH/g; 25 parts by weight of trichloroisopropyl phosphate (TCPP) as a flame retardant; and 2.5 parts by weight of a Niax polyoxyl L6635 stabilizer from Momentive; and an additive in a polyol component: 5.5 parts by weight of S 80:20 戊An alkane (composed of 80 wt% n-pentane and 20 wt% isopentane); about 2.2 parts by weight water; and 1.0 part by weight potassium acetate solution (47 wt% in ethylene glycol).

Further, dimethylcyclohexylamine (DMCHA) for adjusting the fiber time is hereinafter also referred to as catalyst 1.

Isocyanate component: 180 parts by weight of Lupranat® M50 (polymeric methylene (diphenyl diisocyanate) (PMDI) having a viscosity of about 500 mPa*s at 25 ° C from BASF SE)

The components were mixed thoroughly using a laboratory stirrer. The foam density was adjusted to 41 +/- 1 g/L by changing the water content while keeping the pentane content constant at 5.5 parts. The fiber time was further adjusted to 45 +/- 1 second by varying the ratio of dimethylcyclohexylamine (DMCHA) (Catalyst 1).

The results are summarized in Table 1.

It is apparent that the polyester polyols 2 and 4 of the present invention reduce the brittleness of the heat insulating material and increase Add the system's self-reactivity and have no adverse effects on the foam curing.

Inventive Examples 3 and 4 and Comparative Example 3

Manufacture of rigid polyurethane foams (variant 2): the isocyanate and isocyanate-reactive components are made with the foaming agent, catalyst and all other additives at a constant polyol ratio of 100:160. Mixing ratio foaming.

Polyol component: 30 parts by weight of a polyesterol according to the present invention or a comparative example; 37 parts by weight of a polyether alcohol prepared by addition polymerization of propylene oxide to a sucrose/glycerin mixture as a starter molecule, having 490 mg OH/g OH number and 4.3 average functionality; 6 parts by weight of polyether alcohol obtained from ethoxylated ethylene glycol having a hydroxyl functionality of 2 and a hydroxyl number of 190 mg KOH/g; 25 parts by weight Trichloroisopropyl phosphate (TCPP) as a flame retardant; and 2 parts by weight of Niax polyoxyl L6635 stabilizer from Momentive; and an additive in the polyol component: 5.5 parts by weight of S 80:20 pentane; 1.8 parts by weight of water; and 1.2 parts by weight of potassium acetate solution (47 wt% in ethylene glycol).

In addition, about 0.9 parts by weight of dimethylcyclohexylamine (DMCHA) was used to adjust the fiber time.

Isocyanate component: 160 parts by weight of Lupranat® M50 was fabricated by a two-belt method to produce a 170 mm thick sandwich component. The foam density was adjusted to 38 +/- 1 g/L by changing the water content while keeping the pentane content constant at 5.5 parts. Further adjust the fiber time to 35 +/- 1 by changing the ratio of dimethylcyclohexylamine second.

The results are summarized in Table 2.

It is apparent that the polyester polyols 6 and 7 of the present invention improve the dimensional stability of the rigid polyurethane foam.

Claims (18)

A method of preparing a rigid polyurethane foam or rigid polyisocyanurate foam comprising the reaction of: A) at least one polyisocyanate, B) at least one polyether ester polyol , which can be obtained by esterification of the following: b1) 10 mol% to 70 mol% of a dicarboxylic acid composition comprising: b11) 50 mol% to the dicarboxylic acid composition 100 mol% of one or more aromatic dicarboxylic acids or derivatives thereof, b12) from 0 mol% to 50 mol% of one or more aliphatic dicarboxylic acids or derivatives thereof, based on the dicarboxylic acid composition b1) , b2) 2 mol% to 30 mol% of one or more fatty acid or fatty acid derivatives, b3) 10 mol% to 70 mol% of one or more aliphatic or cycloaliphatic diols having 2 to 18 carbon atoms or Alkoxylate, b4) 2 mol% to 50 mol% of a polyether polyol having a functionality of not less than 2 prepared by alkoxylation of a polyol having a functionality greater than 2, all based on component b1 ) to b4), wherein the components b1) to b4) are 100 mol% in total, and C) other polyester polyols which are different from the polyester polyol of component B), as the case may be, D ) polyether polyol, E) Flame retardants used in the case, F) one or more foaming agents, G) catalysts, and H) other auxiliaries or additives used as appropriate, The mass ratio of the total amount of component B) and optionally C) to component D) is less than 1.6. The method of claim 1, wherein the mass ratio of the total amount of components B) and C) to component D) is greater than 0.1. The method of claim 1 or 2, wherein the proportion of the polyether ester polyol B) in the total amount of the polyester polyols B) and C) is at least 25 wt%. The method of claim 1 or 2, wherein no other polyester polyol C) is reacted. The method of claim 1 or 2, wherein the polyether alcohol b4) has a functionality of >2. The method of claim 1 or 2, wherein the preparation is carried out by alkoxylating a polyol selected from the group consisting of sorbitol, pentaerythritol, trimethylolpropane, glycerin, polyglycerol, and mixtures thereof Polyether polyol b4). The method of claim 1 or 2, wherein the polyether alcohol b4) is prepared by alkoxylation with ethylene oxide. The method of claim 1 or 2, wherein the polyether polyol b4) is prepared by alkoxylation with ethylene oxide in the presence of an amine alkoxylation catalyst. The method of claim 1 or 2, wherein the component b11) comprises one or more compounds selected from the group consisting of terephthalic acid, dimethyl terephthalate, polyethylene terephthalate, Phthalic acid, phthalic anhydride and isophthalic acid. The method of claim 1 or 2, wherein the dicarboxylic acid composition b1) does not comprise an aliphatic dicarboxylic acid b12). The method of claim 1 or 2, wherein the fatty acid or fatty acid derivative b2) is selected from the group consisting of oleic acid and methyl oleate. The method of claim 1 or 2, wherein the aliphatic or cycloaliphatic diol b3) is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4- Butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-pentanediol and alkoxylates thereof. The method of claim 1 or 2, wherein the polyether alcohol component D) consists of a polyether alcohol mixture in which some polyether alcohol component D) is based on propylene oxide. The (polyether alcohol component D1) is prepared and the remaining polyether alcohol component D) is prepared on the basis of ethylene oxide (polyether alcohol component D2). The method of claim 1 or 2, wherein the polyether alcohol component D1) has an average OH functionality of greater than 3, preferably greater than 3.5 and more preferably greater than 4, and greater than 300 mg KOH/g, preferably greater than 350 mg KOH/g, more preferably greater than 400 mg KOH/g and especially more than 450 mg KOH/g OH number. The method of claim 1 or 2, wherein the polyether alcohol component D1) has an average OH functionality of less than 6, preferably less than 5.5 and more preferably less than 5, and less than 600 mg KOH/g, preferably less than 550 mg OH/g and more preferably less than 500 mg KOH/g OH number. A rigid polyurethane or polyisocyanurate foam obtainable by the method of any one of claims 1 to 15. A use of the rigid polyurethane or polyisocyanurate foam of claim 16 for the preparation of a sandwich element having a rigid or flexible outer layer. A polyol component comprising: 10 wt% to 50 wt% of polyester polyol B), 0 wt% to 30 wt% of other polyester polyols C), 25 wt% to 55 wt% of polyether Polyol D), 10 wt% to 40 wt% of flame retardant E), 1 wt% to 30 wt% of foaming agent F), 0.5 wt% to 10 wt% of catalyst G), and 0 wt% to 20 wt% of other auxiliaries and additives H), the components B) to H) being as defined in claims 1 to 15 and each of which is based on the total weight of components B) to H), wherein the wt % is up to 100 wt%, and wherein the mass ratio of the total amount of components B) and C) to component D) is less than 1.6.