Glycolysis of polyisocyanurate foams

Abstract

The present invention relates to a method for obtaining an isocyanate reactive substance from a polyisocyanurate material (a) wherein the polyisocyanurate material comprises isocyanurate structures and carboxylic ester structures and an organic phosphorous ester, wherein the method comprises mixing the polyisocyanurate material (a), at least one polyalcohol (b), at least one catalyst (c) at least one deamination agent (d) and at least one additive (e) to form a reac- tion mixture wherein the content of the polyisocyanurate material (a) in the reaction mixture is at least 10 % by weight, based on the total weight of components (a) to (e), and reacting the reac- tion mixture at temperatures of 130 to 280 °C, wherein the catalyst (c) comprises a tertiary amine catalyst, wherein the additive (e) is selected from the group consisting of (e-i) at least one alkali metal hydroxide, (e-ii) at least compound having at least one tertiary amine group, (e-iii) at least one carbonate and (e-iv) at least one lactame or mixtures of two or more additives (e), wherein, in case that at least one dihydric alkanolamine (e-ii) is used as additive (e), the dihydric alkanolamine (e-ii) also serves as polyalcohol (b) and no additional polyalcohol (b) is required, wherein the total content of active groups in compounds (e-i) (e-ii), (e-iii) and (e-iv) is at least 0.7 molar equivalents of the amount of the phosphorous ester present in the polyisocyanurate material and wherein the active group of the alkali metal hydroxide (e-i) is the OH group, the ac- tive group of the compound having at least one tertiary amine group (e-ii) is the tertiary amine group, the active group of the carbonate (e-iii) is the carbonate group and the active group of the lactame (e-iv) is the cyclic structure -N(H)-C(O)-. In addition, the present invention is di- rected to an isocyanate reactive substance, obtained from such a method, a polyurethane ob- tainable by reacting the isocyanate reactive substance and isocyanate and the use of the polyu- rethane as insulation material.

Description

[0001] Glycolysis of Polyisocyanurate foams

[0002] The present invention relates to a method for obtaining an isocyanate reactive substance from a polyisocyanurate material (a) wherein the polyisocyanurate material comprises isocyanurate structures and carboxylic ester structures and an organic phosphorous ester, wherein the method comprises mixing the polyisocyanurate material (a), at least one polyalcohol (b), at least one catalyst (c) at least one deamination agent (d) and at least one additive (e) to form a reaction mixture wherein the content of the polyisocyanurate material (a) in the reaction mixture is at least 10 % by weight, based on the total weight of components (a) to (e), and reacting the reaction mixture at temperatures of 130 to 280 °C, wherein the catalyst (c) comprises a tertiary amine catalyst, wherein the additive (e) is selected from the group consisting of (e-i) at least one alkali metal hydroxide, (e-ii) at least compound having at least one tertiary amine group, (e-iii) at least one carbonate and (e-iv) at least one lactame or mixtures of two or more additives (e), wherein, in case that at least one dihydric alkanolamine (e-ii) is used as additive (e), the dihydric alkanolamine (e-ii) also serves as polyalcohol (b) and no additional polyalcohol (b) is required, wherein the total content of active groups in compounds (e-i) (e-ii), (e-iii) and (e-iv) is at least 0.7 molar equivalents of the amount of the phosphorous ester present in the polyisocyanurate material and wherein the active group of the alkali metal hydroxide (e-i) is the OH group, the active group of the compound having at least one tertiary amine group (e-ii) is the tertiary amine group, the active group of the carbonate (e-iii) is the carbonate group and the active group of the lactame (e-iv) is the cyclic structure -N(H)-C(O)-. In addition, the present invention is directed to an isocyanate reactive substance, obtained from such a method, a polyurethane obtainable by reacting the isocyanate reactive substance and isocyanate and the use of the polyurethane as insulation material.

[0003] Polyurethane foams as flexible foams and rigid foams can be chemically degraded by the glycolysis process and can be used to produce recycled polyols. Numerous methods have been described in the patent literature. The glycolysis of polyisocyanurate foams (PI R foams) is more difficult.

[0004] PIR foams were developed about 30 years ago as an alternative to PUR foams in order to achieve rigid foams with improved flame retardancy due to the intrinsic flame retardancy of the isocyanurate structures. One of the main motivations of the work at that time was to be able to develop rigid foams that do not require any flame retardants at all. The PIR systems at that time were still foamed at very high index values of 400 and higher, as the primary goal was still to be able to develop PIR systems without the addition of flame retardants. This direction of development was later discarded, and the index was lowered in order to circumvent problems regarding excessive brittleness of the foams. However, this made it necessary to use additional flame retardants but in significantly smaller quantities than in classic PUR systems. As flame retardants mainly halogenated phosphorous esters were used as Tris(2-chlorisopropyl)phosphate (TCPP).

[0005] CN 104231304 discloses the glycolysis of PIR sytems by reaction with a alcoholytic agent and a heteropolyacid catalyst, which is a solid state catalyst, and, after the reaction is completed, addition of an alcohol amine compound. The use of a polyacid based solid state catalyst is not desirable sincethis results in a polyol comprising solid particles.

[0006] ES2277554 discloses the glycolysis of polyurethane- and / or polyisocyanurate foams in the presence of titan catalysts or alkali metal based catalysts. Nither in CN 104231304 nor in ES2277554 the recycling of a polyisocyanurate material comprises isocyanurate structures and carboxylic ester structures and comprising an organic phosphorous ester is disclosed.

[0007] The degradation of PIR systems is disclosed in EP 753535. This document discloses that in the glycolysis of PIR foams there is the problem of incomplete conversion and that black coke-like lumps remain, which make further processing impossible. EP 753535 proposes to carry out the reaction of the polyisocyanurates in the presence of polyols with an OH number of no more than 500 mg KOH / g and a molar mass of at least 450 g / mol. After the end of the reaction and cooling to 100 °C, NaOH is added in the examples to reduce the acid number.

[0008] DE 2304444 describes a process for the degradation of PIR foams in which mixtures of glycols such as DEG and dialkanolamines e.g. diethanolamine are used. The PIR foam described in Example 1 is obtained by reaction of PM DI and a mixture of an epoxy and a chlorinated aliphatic ester. They do not contain any other phosphorous based flame retardants such as TCPP or TEP. On page 4, in the third paragraph, it is pointed out that phosphorous-based polyols can lead to recycled polyols with high acid numbers and that this can be compensated, e.g. by further alkoxylation of the products.

[0009] DE 2902509 describes the use of metal catalysts for glycolysis of PUR and PIR rigid foams. These are Ti or Zr catalysts such as titanium(IV) butoxyde. These catalysts have advantages over previously described catalysts such as amines or alkali hydroxides since they have almost no effect on the intrinsic reactivity of the polyols obtained. The rigid foams used in the examples for glycolysis are declared as PUR foams and are not further specified.

[0010] During glycolysis the formation of hazardous amines, as aromatic amines, for example 2,2'- Methylenedianiline, 2,4'-Methylenedianiline and 4,4'-Methylenedianiline (MDA), is a common side reaction. Due to the hazard potential of these amines, the use of a so-called deamination agent is necessary to chemically bind the amines.

[0011] Today's PIR systems are manufactured at an index of 180 to 400 and also contain Phosphorous esters such as TCPP or TEP as flame retardants in proportions of 5-30% by weight. Polyetherols, preferably aromatic polyesterols are used as the main polyols, e.g. based on terephthalic acid or phthalic acid. Such PIR foams can not be degraded into a liquid polyol mixture at PIR- foam concentrations above 10 % by weight, there always remains a solid residue. Therefore, it was object of the present invention to provide a method for obtaining an isocyanate reactive substance from a polyisocyanurate material (a) wherein the polyisocyanurate material comprises isocyanurate structures and carboxylic ester structures and an organic phosphorous ester where no solid residue remains. It was further object of the present invention to provide an isocyanate reactive substance, obtained from degradation of such a polyisocyanurate material and a polyurethane obtainable by reacting the isocyanate reactive substance and isocyanate.

[0012] The object is solved by a method for obtaining an isocyanate reactive substance from a polyisocyanurate material (a) wherein the polyisocyanurate material comprises isocyanurate structures and carboxylic ester structures and an organic phosphorous ester, wherein the method comprises mixing the polyisocyanurate material (a), at least one polyalcohol (b), at least one catalyst (c), at least one deamination agent (d) and at least one additive (e) to form a reaction mixture wherein the content of the polyisocyanurate material (a) in the reaction mixture is at least 10 % by weight, based on the total weight of components (a) to (e), and reacting the reaction mixture at temperatures of 130 to 280 °C, wherein the catalyst (c) comprises a tertiary amine catalyst, wherein the additive (e) is selected from the group consisting of (e-i) at least one alkali metal hydroxide, (e-ii) at least compound having at least one tertiary amine group, (e-iii) at least one carbonate and (e-iv) at least one lactame or mixtures of two or more additives (e), wherein, in case that at least one dihydric alkanolamine (e-ii) is used as additive (e), the dihydric alkanolamine (e-ii) also serves as polyalcohol (b) and no additional polyalcohol (b) is required, wherein the total content of active groups in compounds (e-i) (e-ii), (e-iii) and (e-iv) is at least 0.7 molar equivalents of the amount of the phosphorous ester present in the polyisocyanurate material and wherein the active group of the alkali metal hydroxide (e-i) is the OH group, the active group of the compound having at least one tertiary amine group (e-ii) is the tertiary amine group, the active group of the carbonate (e-iii) is the carbonate group and the active group of the lactame (e-iv) is the cyclic structure -N(H)-C(O)-.

[0013] The isocyanate reactive substance obtained according to the present invention can be reacted with polyisocyanate to form polyurethane materials such as polyurethanes or polyisocyanurates.

[0014] Polyisocyanurate material (a) according to the present invention comprises isocyanurate structures and carboxylic ester structures and an organic phosphorous ester. Such isocyanurates are commonly used when a flame-retardant insulation foam is required, for example as insulation materials for the insulation of buildings.

[0015] The isocyanurate structures are usually obtained by reacting isocyanates and isocyanate reactive materials at an isocyanate index of at least 160, preferably 180 to 400, more preferred 190 to 350 and especially preferred 200 to 320 in presence of a trimerization catalyst. The isocyanate index is the ratio of isocyanate groups to isocyanate-reactive groups multiplied by 100. An isocyanate index of 100 corresponds to an equimolar ratio of the isocyanate groups used and isocyanate reactive groups used.

[0016] The isocyanurate structures can be detected via IR spectroscopy. The IR spectrum of a polyisocyanurate material (a) according to the present invention shows a ratio of the height of the isocyanurate oscillation band at approximately 1410 cm-1to the aromatic oscillation band at approx. 1600 cm-1of at least 0.5, preferably at least 1 , more preferably at least 2 and especially preferred at least 4. In a preferred embodiment the ratio of the isocyanurate oscillation band to the aromatic oscillation band is at most 7, more preferably at most 6. Preferably foam samples for the IR spectroscopy measurement are taken from the core of the foam to be tested.

[0017] Suitable isocyanates are the aliphatic, cycloaliphatic, araliphatic and preferably the aromatic polyvalent isocyanates known in technology. Such polyfunctional isocyanates are known and can be produced using known methods. In particular, the polyfunctional isocyanates can also be used as mixtures, so that isocyanate component in this case contains various polyfunctional isocyanates. Polyisocyanate is a polyfunctional isocyanate with two (hereinafter also referred to as diisocyanates) or more than two isocyanate groups per molecule.

[0018] In particular, the isocyanates are selected from the group consisting of alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical, such as 1 ,12-dodecanediisocyanate, 2- ethyltetramethylene diisocyanate-1 ,4, 2-methylpentamethylene diisocyanate-1 ,5, tetramethylene diisocyanate-1 ,4 and preferably hexamethylene diisocyanate-1 ,6; cycloaliphatic diisocyanates such as cyclohexane-1 ,3- and 1 ,4-diisocyanate and any mixtures of these isomers, 1-iso- cyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (I PDI), 2,4- and 2,6-hexahydrotoluene diisocyanate and the corresponding mixtures of isomers, 4,4’-, 2,2’- and 2,4’-dicyclohexylme- thane diisocyanate and the corresponding mixtures of isomers, and preferably aromatic polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate and the corresponding isomer mixtures, 4,4’-, 2,4’- and 2,2’-diphenylmethane diisocyanate and the corresponding mixtures of isomers, mixtures of 4,4’- and 2,4’-diphenylmethane diisocyanates, polyphenylpolymethene polyisocyanates, mixtures of 4,4’, 2,4’- and 2,2’-diphenylmethane diisocyanates and poly-phenylpolyeth- ylene polyisocyanates (crude MDI) and mixtures of crude MDI and toluene diisocyanates.

[0019] Particularly suitable are 2,2’-, 2,4’- or 4,4’-diphenylmethane diisocyanate (MDI) and mixtures of two or three of these isomers or mixtures of diphenylmethandiisocyanate and higher homologues (polymer MDI or pMDI), 1 ,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), 3,3’-dimethyldiphenyl diisocyanate, 1 ,2-diphenylethane diisocyanate and / or p-phenylene diisocyanate (PPDI). Such polyisocyanates are disclosed in the “Polyurethane Handbook”, Hanser / Gardener publications, 2ndedition 1993, chapter 3.2. Especially preferred is MDI or pMDI, such as Lupranate® M20 or Lupranate® M50, sold by BASF.

[0020] The carboxylic ester structures in the polyisocyanurate material (a) can be obtained by reacting of polyesterols with polyisocyanate. The isocyanate reactive component for the production of the polyisocyanurate material (a) thus comprises polyester polyols, often in combination with polyether polyols. Suitable polyester polyols can be prepared from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aromatic, or mixtures of aromatic and aliphatic dicarboxylic acids and polyhydric alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.

[0021] In particular, the following dicarboxylic acids may be considered: succinic acid, glutaric acid, adipic acid, cork acid, azelaic acid, sebacic acid, decandicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually as well as in a mixture. Instead of the free dicarboxylic acids, the corresponding dicarboxylic acid derivatives, such as dicarboxylic acid esters of alcohols with 1 to 4 carbon atoms or dicarboxylic acid anhydrides, can also be used. As aromatic dicarboxylic acids or acid derivatives, phthalic acid, phthalic anhydride, terephthalic acid and / or isophthalic acid are preferably used in a mixture or alone. Dicarboxylic acid mixtures of succinic, glutaric and adipic acids in proportions of, for example, 20 to 35 : 35 to 50 : 20 to 32 parts by weight, and in particular adipic acid are preferably used as aliphatic dicarboxylic acids. Particular preference is given to polyester polyols obtained by using exclusively aromatic dicarboxylic acid or its derivatives as acid component. Preferably used as an aromatic dicarboxylic acid, at least a compound selected from the group consisting of terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate (PET), phthalic acid, phthalic anhydride (PSA) and isophthalic acid or mixtures of at least two of these dicarboxylic acids, especially preferred at least one compound from the group consisting of terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate (PET) and phthalic anhydride (PSA) and in particular phthalic acid and / or Phthalic anhydride is used. In a preferred embodiment the aromatic carboxylic acids can be obtained from recycled material or production waste.

[0022] Examples of dihydric and polyhydric alcohols, in particular diols, are: monoethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1 ,2- or 1 ,3-propanediol, dipropylene glycol, polypropylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,10-decanediol, glycerol, trimethylolpropane and pentaerythritol, as well as alkoxylates of the same starters. Preferably used are monoethylene glycol, diethylene glycol, triethylene glycol, 1 ,2- or 1 ,3-pro- panediol, dipropylene glycol, as well as ethoxylates of the same starters, for example ethoxylated glycerol, or mixtures of at least one of the mentioned diols. In particular, monoethylene glycol, diethylene glycol, glycerol, as well as ethoxylates of these starters, or mixtures of at least two of the mentioned diols in particular diethylene glycol are used.

[0023] Polyester polyols may be produced catalyst-free or preferably in the presence of esterification catalysts, preferably in an atmosphere of inert gas such as nitrogen in the melt at temperatures of 150 to 280 °C, preferably 180 to 260 °C, where appropriate under reduced pressure up to the desired acid number of preferred than 10, more preferred less than 2. For example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium, and tin catalysts in the form of metals, metal oxides or metal salts can be considered as catalysts.

[0024] For the production of polyester polyols the organic polycarboxylic acids and / or derivatives and polyhydric alcohols are advantageously polycondensed in the molar ratio of 1 : 1 to 2.2, preferably 1 : 1.05 to 2.1 and especially preferably 1 : 1.1 to 2.0.

[0025] The polyester polyols obtained generally have a number average molecular weight of 200 to 3000, preferably 300 to 1000 and in particular 400 to 800 g / mol. Preferably, the amount of aromatic polyesterols is more than 70 % by weight, preferably more than 80 % by weight and especially preferred more than 90 to 100 % by weight, based on the total amount of polyols in the polyurethane foam. The amount of aromatic esters in the polyisocyanurate material can be determined from its degradation products, for example after glycolysis.

[0026] Suitable trimerization catalysts include those compounds employed to expedite and facilitate the trimerization of isocyanates. Useful trimerization catalysts include alkali metal phenolates, alkali metal carboxylates, and alkoxides. The phenolates may also be referred to as phenoxides. Exemplary alkali metals include lithium, sodium, potassium, rubidium, cesium, and francium. Exemplary phenolate ligands may include p-nonyphenolate, p-octylphenolate, p-tertbutylpheno- late, and various alkylphenol-formaldehydes. Preferred alkali metal phenolates include potassium, sodium, and lithium p-nonylphenolate. Alkali metal phenolates, such as potassium p- nonylphenoxide, can be formed from the reaction of p-nonylphenol and potassium hydroxide, preferably within toluene or ethyl acetate. Useful alkali metal carboxylates may include potassium, sodium, and lithium carboxylates, such as salts of 2-ethylhexanoic acid, acetic acid, propionic acid, butyric acid, and combinations thereof. Also suitable as trimerization catalysts are certain quaternary ammonium-based derivatives, such as TOYOCAT™ TRX, a catalyst available from Tosoh, or certain tertiary nitrogen derivatives, such as POLYCAT™ 41 , available from Air Products.

[0027] The amount of catalyst used can vary based on the activity of the catalyst. Generally, the proportions of trimer catalyst will fall within a range of about 0.01 to about 15 parts per 100 parts of the isocyanate reactive component.

[0028] Organic phosphorous esters are usually added as flame retardants. Examples for organic phosphorous esters are chlorinated phosphates such as tris-(2-chloroethyl)-,phosphate, tris-(2-chlo- ropropyl)phosphate (TCPP), tris(1 ,3-dichloropropyl)phosphate, tricresyl phosphate, tris-(2,3-di- bromopropyl)phosphate, tetrakis-(2-chloroethyl)-ethylene diphosphate, dimethylmethanphos- phonate and diethanol-aminomethylphosphonic acid diethyl ester. Diethylethane phosphonate (DEEP), triethyl phosphate (TEP), di methyl propyl phosphonate (DMPP), diphenylcresyl phosphate (DPK) can be used as organic phosphorous esters as well. In a preferred embodiment of the present invention the polyisocyanurate material comprises Phosphourous esters selected from the group of triethylphosphate (TEP) and Trichlor phenyle phosphate (TCPP).

[0029] In addition, the polyisocyanurate material (a) may comprise suitable catalysts, blowing agents and additives known in the field. Examples of catalysts, blowing agents and suitable additives are mentioned in the “Polyurethane Handbook”, Hanser / Gardener publications, 2nd edition 1993.

[0030] The amount of the polyisocyanurate material (a), based on the total weight of the reaction mixture according to the invention is at least 10 % by weight, preferably 15 to 80 % by weight, more preferred 20 to 60 % by weight and especially preferred 25 to 50 % by weight.

[0031] As polyalcohol (b) any at least dihydric alcohol can be applied. Preferably suitable polyalcohols (b) are liquid at 40 °C. Examples of polyhydric, preferably dihydric alcohols are monoethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1 ,2- or 1 ,3-propanediol, dipropylene glycol, polypropylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,10-dec- anediol, glycerol, trimethylolpropane, pentaerythritol, , as well as alkoxylates of the same starters. Preferably used are monoethylene glycol, diethylene glycol, triethylene glycol, 1 ,2- or 1 ,3- propanediol, dipropylene glycol, , as well as ethoxylates of the same starters, for example ethoxylated glycerol, or mixtures of at least one of the mentioned diols. In particular, monoethylene glycol, diethylene glycol, glycerol, as well as ethoxylates of these starters, or mixtures of at least two of the mentioned diols and in particular diethylene glycol is used. Especially preferred are glycols having primary alcohols as ethoxylated trimethylolpropane, ethoxylated glycerol or triethyleneglycol as well as mixtures of glycols and natural oils.

[0032] As catalyst (c) any catalyst known for the production of polyurethanes from isocyanates and isocyanate reactive compounds can be used with the provision, that the catalyst (c) comprises a tertiary amine catalyst. In addition to tertiary amine catalysts, the known catalysts can be used for the production of polyesters and their transesterification. These are metal catalysts such as titanium catalysts, as described in "Modern Polyesters: Chemistry and Technology of Polyesters and Copolyesters", Chapter 2, Wiley, 2003, ISBN 0-471-49856-4. These catalysts are free of isocyanate reactive groups as -OH groups, -NH- groups or -NH2 groups. Typical tertiary amine catalysts include amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, aliphatic tertiary amines, such as triethylamine, tributylamine, dimethylbenzylamine, N-methyl-, N-ethyl- and N- cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanedia- mine, N,N,N',N'-tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1 ,2-dimethylimidazole, 1- azabicyclo[3.3.0]octane and preferably 1 ,4-diazabicyclo[2.2.2]octane and dimethylcyclohexylamine, most preferred dimethylcyclohexylamine. In addition to tertiary amine catalysts it is also possible to use organic metal compounds, preferably organic tin compounds, for example tin(ll) salts of organic carboxylic acids, e.g. tin(ll) acetate, tin(ll) octoate, tin(ll) ethylhexanoate and tin(ll) laurate, and the dialkyltin(IV) salts of organic carboxylic acids, e.g. dibutyltin diacetate, dibutyltin dilaurate, zinc(ll) acetate, dibutyltin maleate and dioctyltin diacetate, and the titanium alkoxides, e.g. tetrabutyl orthotitanate, and also bismuth carboxylates, such as bismuth(lll) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate, or mixtures thereof.. In a preferred embodiment catalyst (c), in addition to at least one tertiary amine catalyst, is selected from the group consisting of at least one tin catalyst, at least one titan catalystor combinations of at least two of these catalysts.

[0033] Catalysts (c) can be used by way of example at a concentration of from 0.01 to 10% by weight, in particular from 0.5 to 8% by weight, as catalyst or, respectively, catalyst combination, based on the weight of components (a), (b), (c) and (d). In a preferred embodiment, the content of tertiary amine catalyst, based on the total weight of the of components (a), (b), (c) and (d), is 0.01 to 10 % by weight, more preferred 0.5 to 8 % by weight even more preferred 1 to 5 % by weight. Deamination agents (d) are compounds which, when added to mixtures of alcohols and aromatic amines, react preferentially with the aromatic amines, even if there is an excess of alcohol. These include such as fatty acids, isocyanates, glycidyl ethers or epoxidized native oils.

[0034] For example, stearic acid, palmitic acid, dodecanoic acid, erucaic acid, linoleic acid, linolenic acid, oleic acid or mixtures of fatty acids can be used as fatty acids. Fatty acids and their use for deamination are described, for example, in DE 102009026898.

[0035] Isocyanates for deamination are preferably those that have exclusively secondary or tertiary or secondary and tertiary aliphatic bound Isocyanate groups, for example bis-1 ,3(2-isocyanatopro- pyl)benzene. Isocyanates and their use for deamination are described, for example, in EP899292.

[0036] As glycidyl ethers (d) any compound comprising epoxide groups preferably compounds containing one or two epoxy groups in the molecule can be used. The monofunctional glycidyl ethers of the general formula (i) proved to be particularly suitable:

[0037] Wherein R = Phenyl, Cyclohexyl, Methylcyclohexyl, Benzyl, i-Propyl, i-Butyl or methyl- and / or ethyl-branched hydrocarbon chains having 5 to 10 carbon atoms in the straight chain and / or a group of the general formula (ii):

[0038] Wherein A stands for an alkyl residue having 1 bis 8 carbon atoms, n is 3 to 12 and m is 1 to 6.

[0039] As difunctional glycidyl ethers compounds according to formula (iii) are especially preferred: wherein R' = diphenylmethylene, 2,2-diphenylpropylene (bisphenol A}, unbranched hydrocarbon chains with 4 to 10 carbon atoms or methyl and / or ethyl branched hydrocarbon chains with 4 to 8 carbon atoms in the straight chain. Glycidylethers and their use for deamination are for example disclosed in EP592952. Epoxidized native fatty oils are those products that are obtained from at least single, preferably at least triple unsaturated natural oils, e.g. from soy, flax, castor and nuts of all kinds. The term "unsaturated" refers to a carbon-carbon double bond. Glycidylethers and their use for deamination are for example disclosed in EP718349.

[0040] As deamination agents (d) preferably glycidylethers are used. Preferred glycidylethers are non- ofunctional epoxy resins, such as 2-ethylhexyl glycidyl ether, isopropyl glycidyl ether, butyl glyc- idyl ether, cresyl glycidyl ether or monofunctional glycidyl ethers based on 2-ethylhexanol (Epilox P13-16, LEUNA-Harze GmbH), C12-C14 alcohols (Epilox P 13-18, LEUNA-Harze GmbH) or C13-C15 alcohols (Epilox P 13-19, LEUNA-Harze GmbH).

[0041] The amount of the deamination agent (d) added to the reaction mixture preferably is 0 to 40 % by weight, more preferred 5 to 30 wt.-% and especially preferred 10 to 20 % by weight, each based on the total weight of the polyisocyanurate material (a)

[0042] The additive (e) is selected from the group consisting of (e-i) at least one alkali metal hydroxide, (e-ii) at least compound having at least one tertiary amine group, (e-iii) at least one carbonate and (e-iv) at least one lactame or mixtures of two or more additives (e).

[0043] Examples for alkali metal hydroxides (e-i) are lithium hydroxide, sodium hydroxide and potassium hydroxide.

[0044] Examples for compounds having at least one tertiary amine group (e-ii) are alkanolamines with tertiary nitrogen atom as triethanolamine, methyldiethanolamin and dimethylethanolamine. Especially preferred is methyl-diethanolamine. In case that the alkanolamine is at least a dihydric alkanolamine, the alkanolamine can also function as polyol (b). This means that if an at least dihydric alkanolamine (e-ii) is used as additive (e), the alkanolamine (e-ii) also serves as polyalcohol (b) and no additional polyalcohol (b) is required. Further, the Alkanolamine can act as tertiary amine catalyst (c). This means that if an at least dihydric alkanolamine (e-ii) is used as additive (e), no additional tertiary amine catalyst has to be present. In a preferred embodiment, the at least dihydric alkanolamine (e-ii) is used together with an tertiary amine catalyst.

[0045] Examples of carbonates (e-iii) are alkali and alcali earth carbonates and hydrogencarbonates as sodium carbonate, potassium carbonate, sodium hydorgencarbonate, calcim carbonate, calcium hydogencarbonate, magnesium carbonate, magnesium hydrogencarbonate, talcite and hydrotalcite. Especially preferred as additive (e-iii) is sodium carbonate or hydrotalcite, for example.

[0046] In the context of the invention, "lactam" (e-iv) is understood to mean cyclic amides which may be substituted. In this case the amide bond is situated in the ring, and preferably there is only one amide group in the ring. Examples of lactam according to the invention are p-propiolactam, 2-pyrrolidone, N-methylpyrrolidone, y-butyrolactam, 5-valerolactam (2-piperidone) and e-lactam (e-caprolactam). Particular preference is given to using e-caprolactam. are Preferably the additive (e) is selected from carbonates (e-iii) and / or lactames (e-iv), especially preferred from ccarbonates (e-iii).

[0047] The total content of active groups in compounds (e-i) (e-ii), (e-iii) and (e-iv) is at least 0.7 molar equivalents of the amount of the phosphorous ester present in the polyisocyanurate material wherein the active group of the alkali metal hydroxide (e-i) is the OH group, the active group of the compound having at least one tertiary amine group (e-ii) is the tertiary amine group, the active group of the carbonate (e-iii) is the carbonate group and the active group of the lactame (e- iv) is the cyclic structure -N(H)-C(O)-.

[0048] In a preferred embodiment the content of the at least one alkali metal hydroxide is less than 4 molar equivalents of the amount of the phosphorous ester present in the polyisocyanurate material (a), preferably less than 3 molar equivalents and especially preferred less than 1 .5 molar equivalents. Preferably also the sum of active groups of (e-i) alkali metal hydroxide, (e-ii) at least compound having at least one tertiary amine group and (e-iv) at least one lactame tertiary amine compound (e-ii) is less than 10 molar equivalents of the amount of the phosphorous ester present in the polyisocyanurate material (a), more preferred less than 4 molar equivalents, more preferred less than 3 molar equivalents and especially preferred less than 1 .5 molar equivalents. The amount of the phosphorous ester present in the polyisocyanurate material (a) can be determined by extraction, for example with dichloromethane as solvent and subsequent gaschromatographic analysis or P-NMR or elementary analysis.

[0049] Polyisocyanurate material (a), a polyalcohol (b), a catalyst (c) a deamination agent (d) and an additive (e) are mixed to form a reaction mixture wherein the content of the polyisocyanurate material (a) in the reaction mixture is at least 10 % by weight, based on the total weight of components (a) to (e), and reacting the reaction mixture at temperatures of 130 to 280 °C, preferably 160 to 250 °C and especially preferred 180 to 220 °C. In one embodiment of the present invention, the polyisocyanurate material (a) comprises a tertiary amine catalyst (c). In this case, when added to the polyalcohol (b), the catalyst (c) the deamination agent (d) and the additive (e), it is not necessary to add additional catalyst (c) to form the reaction mixture according to the present invention.

[0050] The obtained isocyanate reactive substance may be further purified by filtration. So by filtration unsoluble components, as for example unreacted carbonates can be separated. In addition by distillation volatile substances might be separated. The obtained isocyanate reactive substance can be reacted with common isocyanates to form novel polyurethanes or polyisocyanurates. To produce Polyurethanes / polyisocyanurates common ingredients can be used. Depending on the properties of the polymer to be obtained additional isocyanate reactive compounds, bowing agents, commonly known catalysts and commonly known additives may be added. In a preferred embodiment the polyurethane obtained from the isocyanate reactive compound according to the present invention is a rigid polyurethane foam or a rigid polyisocyanurate foam, especially preferred an insulation material, for examples for buildings, cooling devices and water heaters, especially for buildings.

[0051] The invention shall be elucidated hereinbelow with reference to examples:

[0052] For the glycolysis trials the polyisocyanurate material (a) used is a powder made of a PIR foam. To produce the foam, a polyol 1 consisting of a polyesterol based on aromatic dicarboxylic acids and diethylene glycol with an OH number of 240, a polyol 2 consisting of a polyetherol based on ethylene oxide with an OH number of 180, a stabilizer consisting of a polyether siloxane from Evonik, a flame retardant consisting of tris-(2-chloroisopropyl) phosphate, a blowing agent 1 consisting of formic acid and water (mass ratio 85:15), catalysts consisting of a tertiary amine catalyst and a potassium carboxylate (PIR catalyst), a blowing agent 2 consisting of n-pentane and iso-pentane with a mass ratio of 80:20, and an isocyanate consisting of Lupranat M 50 from BASF.

[0053] The PIR foam slabs were produced by high-pressure mixing of the components on a doublebelt system using aluminum foil as cover layers. The mixing ratio between A+C and B components was 115.3:230. The mixing ratio corrected to 100 parts A+C is 100:199. This corresponds to an index of 335. The cover layers of the PIR foam slabs obtained were then removed and the PIR foams were ground into a powder using a microfine grinder (hole diameter of the sieve: 4 mm).

[0054] The Glycolysis was carried out in a temperature-controlled 2-liter glass reaction vessel with a thermostatic jacket equipped with a stirrer, reflux condenser and dosing funnel in a nitrogen atmosphere. The corresponding polyalcohol (b) was heated to a temperature of 210 °C together with any catalysts (c), deamination agent (d) and additives (e) used and then the PIR foam powder was added in portions so that the reaction mixture could still be stirred. After adding the last portion, stirring continued until a clear reaction product was obtained.

[0055] Comparative example 1 : The production of the recycled polyol was carried out as described above. For this purpose, 750 g of diethylene glycol and 1 .5 g of 1 ,4-diazabicyclo[2.2.2]octane were added and heated to 210 °C. After the addition of two portions, which correspond to a total of 114 g of PIR foam powder, no complete degradation could be achieved (this corresponds to a theoretical content of PIR foam in the reaction mixture of 13% by mass) and a further dosage of PIR powder was not possible due to the limited stirring ability of the reaction mixture. On the other hand, a heterogeneous reaction mixture with swollen PIR foam particles is obtained, which are not further degraded. An increase in the reaction temperature from 210 °C to 235 °C did not lead to any change. The attempt was aborted unsuccessfully after 12 hours.

[0056] Example 2: The production of the recycled polyol was carried out as indicated above. For this purpose, 1550 g of diethylene glycol as well as 7.5 g of sodium hydroxide were added and heated to 210 °C. After the addition of six portions, which correspond to a total of 750 g of the PIR foam powder, a complete degradation could be achieved. After a reaction time of 12 h, a clear polyol with an OH number of 700, a PIR foam content of 32.5% by mass and an MDA content of 540 ppm (360 ppm 2,4’-MDA and 180 ppm 4,4’-MDA) was obtained.

[0057] Example 3: The production of the recycled polyol was carried out as indicated above. For this purpose, 880 g of diethylene glycol as well as 15 g of sodium hydroxide were added and heated to 210 °C. After the addition two portions, which correspond to a total of 600 g PIR foam powder, a complete degradation could be achieved. After a reaction time of 2 h and 40 minutes, a clear polyol with an OH number of 625, a rigid foam content of 40% by mass and an MDA content of 4,370 ppm (810 ppm 2,4’-MDA and 3,560 ppm 4,4’-MDA) was obtained.

[0058] Example 4: The production of the recycled polyol was carried out as indicated above. For this purpose, 420 g of diethylene glycol as well as 630 g of triethanolamine were added and heated to 210 °C. After the addition of two portions, which correspond to a total of 450 g PIR foam powder, a complete degradation could be achieved. After a reaction time of 6 h and 45 minutes, a clear polyol with an OH number of 865, a rigid foam content of 30% by mass and an MDA content of 2,590 ppm (350 ppm 2,4’-MDA and 2,240 ppm 4,4’-MDA) was obtained.

[0059] Example 5: The production of the recycled polyol was carried out as indicated above. For this purpose, 750 g N-methyldiethanolamine was added and heated to 210 °C. After the addition of ten portions, which correspond to a total of 750 g of PIR foam powder, a complete degradation could be achieved. After a reaction time of 3 hours, a clear polyol with an OH number of 470, a rigid foam content of 50% by mass and an MDA content of 21 ,700 ppm (5,400 ppm 2,4’-MDA and 16,300 ppm 4,4’-MDA) was obtained.

[0060] Example 6: The production of the recycled polyol was carried out as indicated above. For this purpose, 750 g N-methyldiethanolamine was added and heated to 160 °C. After the addition of eleven portions, which correspond to a total of 750 g of PIR foam powder, a complete degradation could be achieved. After a reaction time of 4 hours and 10 minutes, a clear polyol with an OH number of 470, a rigid foam content of 50% by mass and an MDA content of 12,400 ppm (2,600 ppm 2,4’-MDA and 9,800 ppm 4,4’-MDA) was obtained.

[0061] Example 7: The production of the recycled polyol was carried out as indicated above. For this purpose, 750 g N-methyldiethanolamine as well as 1 .5 g tetrabutyl orthotitanate were added and heated to 150 °C. After the addition of nine portions, which correspond to a total of 750 g of PI R foam powder, a complete degradation could be achieved. After a reaction time of 6 hours, a clear polyol with an OH number of 470, a rigid foam content of 50% by mass and an MDA content of 10,800 ppm (2,800 ppm 2,4’-MDA and 8,000 ppm 4,4’-MDA) was obtained.

[0062] Example 8: The production of the recycled polyol was carried out as indicated above. For this purpose, 853 g diethylene glycol, 46 g N-methyldiethanolamine as well as 1 .5 g tetrabutyl orthotitanate were added and heated to 210 °C. After the addition of six portions, which correspond to a total of 600 g of PI R foam powder, a complete degradation could be achieved. After a reaction time of 6 hours and 10 minutes, a clear polyol with an OH number of 630, a rigid foam content of 40% by mass and an MDA content of 2,170 ppm (360 ppm 2,4’-MDA and 1 ,810 ppm 4,4’-MDA) was obtained.

[0063] Example 9: The production of the recycled polyol was carried out as indicated above. For this purpose, 860 g of diethylene glycol, 1 .5 g of tetrabutyl orthotitanate as well as 60 g of hydrotalcite were added and heated to 210 °C. After the addition of four portions, which correspond to a total of 600 g of PI R foam powder, a complete degradation could be achieved. After a reaction time of 4 hours and 25 minutes, a clear polyol with an OH number of 600, a rigid foam content of 39.5% by mass and an MDA content of 1 ,580 ppm (380 ppm 2,4’-MDA and 1 ,200 ppm 4,4’-MDA) was obtained.

[0064] Example 10: The production of the recycled polyol was carried out as indicated above. For this purpose, 890 g of diethylene glycol, 1 .5 g of tetrabutyl orthotitanate and as well as 10.3 g of sodium carbonate were added and heated to 210 °C. After the addition of three portions, which correspond to a total of 600 g of PI R foam powder, a complete degradation could be achieved. After a reaction time of 4 hours and 5 minutes, a turbid polyol with an OH number of 625, a rigid foam content of 40% by mass and an MDA content of 1 ,890 ppm (490 ppm 2,4’-MDA and 1 ,400 ppm 4,4’-MDA) was obtained. The polyol could be freed from undissolved sodium carbonate by filtration, so that a clear polyol was obtained.

[0065] Example 11 : The production of the recycled polyol was carried out as indicated above. For this purpose, 991 g of tripropylene glycol as well as 95 g of hydrotalcite were added and heated to 220 °C. After the addition of seven portions, which correspond to a total of 504 g PI R foam powder, a complete degradation could be achieved. Following glycolysis, the temperature was lowered to 150 °C, 90 g of 2-ethyl hexyl glycidyl ether was added, and the reaction mixture was kept in this state for 30 minutes. After a reaction time of 6 hours and 30 minutes, a clear polyol with an OH number of 360, a rigid foam content of 30% by mass and an MDA content below the limit of quantification was obtained.

[0066] Example 12: The production of the recycled polyol was carried out as indicated above. For this purpose, 715 g of diethylene glycol, 180 g of polyethylene glycol with a molar mass of 600 g / mol as well as 95 g of hydrotalcite were added and heated to 210 °C. After the addition of six portions, which correspond to a total of 720 g of PI R foam powder, a complete degradation could be achieved. After a reaction time of 5 hours and 20 minutes, a clear polyol with an OH number of 455, a rigid foam content of 40% by mass and an M DA content below the limit of quantification was obtained.

[0067] Example 13: The production of the recycled polyol was carried out as indicated above. For this purpose, 315 g of diethylene glycol, 575 g of tripropylene glycol as well as 100 g of hydrotalcite were added and heated to 220 °C. After the addition of five portions which correspond to a total of 720 g of PIR foam powder, a complete degradation could be achieved. Following glycolysis, the temperature was lowered to 150 °C, 90 g of 2-ethyl hexyl glycidyl ether was added, and the reaction mixture was kept in this state for 30 minutes. After a reaction time of 6 hours and 5 minutes, a clear polyol with an OH number of 385, a rigid foam content of 40% by mass and an MDA content below the limit of quantification was obtained.

[0068] Example 14: The production of the recycled polyol was carried out as indicated above. For this purpose, 1050 g polyethylene glycol with a molar mass of 600 g / mol as well as 100 g hydrotalcite were added and heated to 210 °C. After the addition of five portions, which correspond to a total of 360 g PIR foam powder, a complete degradation could be achieved. Following glycolysis, the temperature was lowered to 150 °C, 90 g of 2-ethyl hexyl glycidyl ether was added, and the reaction mixture was kept in this state for 30 minutes. After a reaction time of 5 hours and 25 minutes, a clear polyol with an OH number of 140, a rigid foam content of 22.5% by mass and an MDA content of 200 ppm (100 ppm 2,4’-MDA and 100 ppm 4,4’-MDA) was obtained.

[0069] Example 15: The production of the recycled polyol was carried out as indicated above. For this purpose, 249 g of dipropylene glycol, 746 g of tripropylene glycol, 30 g N-methyldiethanolamine, 9 g sodium carbonate as well as 3 g of sodium hydroxide were added and heated to 210 °C. After the addition of ten portions which correspond to a total of 720 g of PI R foam powder, a complete degradation could be achieved. Following glycolysis, the temperature was lowered to 150 °C, 90 g of 2-ethyl hexyl glycidyl ether was added, and the reaction mixture was kept in this state for 30 minutes. After a reaction time of 8 hours, a polyol with an OH number of 370, a rigid foam content of 40% by mass and an MDA content below the limit of quantification was obtained.

[0070] Example 16: The production of the recycled polyol was carried out as indicated above. For this purpose, 1095 g of dipropylene glycol as well as 12 g of sodium carbonate were added and heated to 210 °C. After the addition of seven portions which correspond to a total of 800 g of PIR foam powder, a complete degradation could be achieved. Following glycolysis, the temperature was lowered to 100 °C, 90 g of 2-ethyl hexyl glycidyl ether was added, and the reaction mixture was kept in this state for 30 minutes. After a reaction time of 5 hours and 40 minutes, a polyol with an OH number of 475, a rigid foam content of 40% by mass and an MDA content below the limit of quantification was obtained.

[0071] Example 17: The production of the recycled polyol was carried out as indicated above. For this purpose, 1098 g of tripropylene glycol as well as 12 g of sodium carbonate were added and heated to 210 °C. After the addition of six portions which correspond to a total of 720 g of PIR foam powder, a complete degradation could be achieved. Following glycolysis, the temperature was lowered to 100 °C, 90 g of 2-ethyl hexyl glycidyl ether was added, and the reaction mixture was kept in this state for 30 minutes. After a reaction time of 5 hours and 25 minutes, a polyol with an OH number of 350, a rigid foam content of 37.5% by mass and an MDA content below the limit of quantification was obtained.

[0072] Example 18: The production of the recycled polyol was carried out as indicated above. For this purpose, 500 g of dipropylene glycol, 500 g tripropylene glycol as well as 12 g of sodium carbonate were added and heated to 210 °C. After the addition of six portions which correspond to a total of 734 g of PIR foam powder, a complete degradation could be achieved. Following glycolysis, the temperature was lowered to 100 °C, 90 g of 2-ethyl hexyl glycidyl ether was added, and the reaction mixture was kept in this state for 30 minutes. After a reaction time of 5 hours and 25 minutes, a polyol with an OH number of 400, a rigid foam content of 40% by mass and an MDA content below the limit of quantification was obtained.

[0073] Example 19: The production of the recycled polyol was carried out as indicated above. For this purpose, 1320 g of a glycerol based polypropyleneglycol having a hydroxyl number of 400 mg KOH / g as well as 15 g of sodium carbonate were added and heated to 210 °C. After the addition of five portions which correspond to a total of 540 g of PIR foam powder, a complete degradation could be achieved. Following glycolysis, the temperature was lowered to 100 °C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was kept in this state for 30 minutes. After a reaction time of 6 hours and 40 minutes, a polyol with an OH number of 285, a rigid foam content of 27.5% by mass and an MDA content of 248 ppm (98 ppm 2,4’-MDA and 150 ppm 4,4’-MDA) was obtained.

[0074] Example 20: The production of the recycled polyol was carried out as indicated above. For this purpose, 798 g of 1 ,2-propanediol as well as 24 g of sodium carbonate were added and heated to 180 °C. After the addition of eleven portions which correspond to a total of 1115 g of PIR foam powder, a complete degradation could be achieved. Following glycolysis, the temperature was lowered to 100 °C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was kept in this state for 30 minutes. After a reaction time of 11 hours and 20 minutes, a polyol with an OH number of 595, a rigid foam content of 55% by mass and an MDA content of 6,400 ppm (1 ,000 ppm 2,4’-MDA and 5,400 ppm 4,4’-MDA) was obtained.

[0075] Example 21 : The production of the recycled polyol was carried out as indicated above. For this purpose, 798 g of monoethylene glycol as well as 21 g of sodium carbonate were added and heated to 180 °C. After the addition of eleven portions which correspond to a total of 1115 g of PIR foam powder, a complete degradation could be achieved. Following glycolysis, the temperature was lowered to 100 °C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was kept in this state for 30 minutes. After a reaction time of 11 hours and 50 minutes, a polyol with an OH number of 730, a rigid foam content of 55% by mass and an MDA content of 2,000 ppm (only 4,4’-MDA) was obtained. The recycled polyols were used as a component in the polyisocyanurate material (a) from which they were made. The following is a selection of examples in which the polyol 1 has been replaced with the corresponding recycled polyols. The mixing ratio has been left constant, so the index of the system changes.

[0076] The foams obtained are characterized in terms of their reactivity, hardening, thermal and mechanical properties as well as their fire behavior.

[0077] To assess the reactivity, start time, rise time and maximum core temperature are determined using a foam qualification system. The start time is defined as the time between the start of mixing and the beginning of the volume expansion of the reaction mixture by foaming. The rise time is defined as the period between the start of mixing and the end of volume expansion.

[0078] Cream time, tack-free time, needle height and free-foamed bulk density are also determined. The cream time is the time from the start of mixing to the time of the reaction process, at which threads can be pulled out of the foam mass with a rod. The tack-free time is defined as the time between the start of stirring and the time at which hardly any adhesive effect can be detected when touching the foam surface with a rod or similar. To determine the needle height, a needle or syringe cannula is inserted into the foam directly above the rim of the cup when the cream time is reached. After the end of the volume expansion of the foam, the distance traveled by the needle is measured. The core temperature is recorded with a thermocouple, which is pierced through a hole halfway up the cup height to the center of the cup as soon as the foam head has risen higher than half the cup height. The maximum core temperature is then output from the recorded data. In order to determine the free-foamed bulk density, a defined test specimen is cut from the material, the dimensions and weight of the specimen are determined, and the density is calculated.

[0079] The determination of the surface hardening is carried out with a universal testing machine. In this case, the foam surface is pressed in by 1 cm with the test stamp at fixed times and the force occurring is determined.

[0080] The measurement of thermal conductivity is carried out using a heat flow meter. The measurements are carried out at ambient pressure, an average temperature of 10 °C and a temperature difference between the measuring plates of 10 K.

[0081] The compressive strength in 3 spatial directions is also determined with a universal testing machine according to DIN EN ISO 844 and is corrected to a density of 38 kg / m3.

[0082] As a result of the characterization of the fire behavior according to class E at 15 s edge flame, the flame height is given.

[0083] Foam reference: The reference system is the original system without using any recycling polyols. As stated above the mixing ratio between A+C and B components was 100:199, corresponding to an index of 335. The reactivity of the system is defined by a start time of 7 s, a cream time of 54 s, a rise time of 80 s, a tack-free time of 90 s, a needle height of 3.4 cm, a free-foamed bulk density of 42 kg / m3and a maximum core temperature of 167 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 74 N to 88 N, 102 N, 120 N, 131 N and finally 133 N. The thermal conductivity of the gained foam is 20.9 mW / (mxK), the compressive strength results in 0.171 N / mm2and the flame height gives 8.3 cm.

[0084] Foam Example 1 : 25 parts of polyol 1 were exchanged by the recycling polyol of example 8. Additionally, 1 .3 parts of PMDTA (pentamethyldiethylenetriamine) were added, and the isocyanate 1 amount was adjusted to 232 parts to keep the mixing ratio of 100:199. The resulting index is 258. The recycled content of the polyol component A is 10.0% by weight and the recycled content of the resulting foam is 2.9% by weight. The reactivity of the system is defined by a start time of 7 s, a cream time of 51 s, a rise time of 76 s, a tack-free time of 120 s, a needle height of 2.6 cm, a free-foamed bulk density of 43 kg / m3and a maximum core temperature of 152 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 26 N to 32 N, 41 N, 48 N, 48 N (crack formation) and finally 54 N. The thermal conductivity of the gained foam is 21 .0 mW / (mxK), the compressive strength results in 0.111 N / mm2and the flame height gives 12.7 cm.

[0085] Foam Example 2: 25 parts of polyol 1 were exchanged by the recycling polyol of example 11 . Additionally, 0.7 parts of PMDTA were added and the isocyanate 1 amount was adjusted to 231 parts to keep the mixing ratio of 100:199. The resulting index is 306. The recycled content of the polyol component A is 7.5% by weight and the recycled content of the resulting foam is 2.2% by weight. The reactivity of the system is defined by a start time of 6 s, a cream time of 53 s, a rise time of 72 s, a tack-free time of 105 s, a needle height of 2.6 cm, a free-foamed bulk density of 42 kg / m3and a maximum core temperature of 172 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 50 N to 58 N, 69 N, 83 N (crack formation), 92 N and finally 95 N. The thermal conductivity of the gained foam is 20.9 mVW(mxK), the compressive strength results in 0.171 N / mm2and the flame height gives 9.7 cm.

[0086] Foam Example 3: 50 parts of polyol 1 were exchanged by the recycling polyol of example 11 . Additionally, 1.3 parts of PMDTA were added and the isocyanate 1 amount was adjusted to 232 parts to keep the mixing ratio of 100:199. The resulting index is 283. The recycled content of the polyol component A is 15.0% by weight and the recycled content of the resulting foam is 4.3% by weight. The reactivity of the system is defined by a start time of 5 s, a cream time of 52 s, a rise time of 77 s, a tack-free time of 90 s, a needle height of 2.8 cm, a free-foamed bulk density of 42 kg / m3and a maximum core temperature of 156 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 40 N to 53 N, 68 N (crack formation), 75 N, 78 N and finally 81 N. The thermal conductivity of the gained foam is 20.9 mVW(mxK), the compressive strength results in 0.174 N / mm2and the flame height gives 11 .7 cm.

[0087] Foam Example 4: 25 parts of polyol 1 were exchanged by the recycling polyol of example 13. Additionally, 0.7 parts of PMDTA were added and the isocyanate 1 amount was adjusted to 231 parts to keep the mixing ratio of 100:199. The resulting index is 300. The recycled content of the polyol component A is 10.0% by weight and the recycled content of the resulting foam is 2.9% by weight. The reactivity of the system is defined by a start time of 7 s, a cream time of 54 s, a rise time of 79 s, a tack-free time of 105 s, a needle height of 2.7 cm, a free-foamed bulk density of 42 kg / m3and a maximum core temperature of 159 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 47 N to 56 N, 67 N, 82 N (crack formation), 80 N and finally 84 N. The thermal conductivity of the gained foam is 20.9 mW / (mxK), the compressive strength results in 0.161 N / mm2and the flame height gives 9.3 cm.

[0088] Foam Example 5: 50 parts of polyol 1 were exchanged by the recycling polyol of example 13. Additionally, 1.3 parts of PMDTA were added and the isocyanate 1 amount was adjusted to 232 parts to keep the mixing ratio of 100:199. The resulting index is 273. The recycled content of the polyol component A is 20.0% by weight and the recycled content of the resulting foam is 5.7% by weight. The reactivity of the system is defined by a start time of 6 s, a cream time of 55 s, a rise time of 87 s, a tack-free time of 105 s, a free-foamed bulk density of 43 kg / m3and a maximum core temperature of 153 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 17 N to 20 N, 31 N (crack formation), 41 N, 49 N and finally 55 N. The thermal conductivity of the gained foam is 27.1 mW / (mxK), the compressive strength results in 0.108 N / mm2and the flame height gives 8.7 cm.

[0089] Foam Example 6: 25 parts of polyol 1 were exchanged by the recycling polyol of example 14. Additionally, 0.2 parts of PMDTA were added and the mixing ratio of 100:199 was kept. The resulting index is 377. The recycled content of the polyol component A is 5.6% by weight and the recycled content of the resulting foam is 1.6% by weight. The reactivity of the system is defined by a start time of 6 s, a cream time of 53 s, a rise time of 75 s, a tack-free time of 120 s, a needle height of 3.1 cm, a free-foamed bulk density of 43 kg / m3and a maximum core temperature of 157 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 53 N to 61 N, 74 N, 84 N, 91 N and finally 99 N. The thermal conductivity of the gained foam is 20.7 mW / (mxK), the compressive strength results in 0.160 N / mm2and the flame height gives 9.0 cm.

[0090] Foam Example 7: 50 parts of polyol 1 were exchanged by the recycling polyol of example 14. Additionally, 0.4 parts of PMDTA were added and the mixing ratio of 100:199 was kept. The resulting index is 412. The recycled content of the polyol component A is 11 .3% by weight and the recycled content of the resulting foam is 3.3% by weight. The reactivity of the system is defined by a start time of 5 s, a cream time of 53 s, a rise time of 83 s, a tack-free time of 150 s, a needle height of 3.4 cm, a free-foamed bulk density of 45 kg / m3and a maximum core temperature of 152 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 38 N to 44 N, 55 N, 63 N, 71 N and finally 78 N (crack formation). The thermal conductivity of the gained foam is 26.0 mW / (mxK), the compressive strength results in 0.166 N / mm2and the flame height gives 5.7 cm.

[0091] Foam Example 8: 25 parts of polyol 1 were exchanged by the recycling polyol of example 15. Additionally, 0.5 parts of PMDTA were added and the mixing ratio of 100:199 was kept. The resulting index is 302. The recycled content of the polyol component A is 9.8% by weight and the recycled content of the resulting foam is 2.8% by weight. The reactivity of the system is defined by a start time of 7 s, a cream time of 54 s, a rise time of 81 s, a tack-free time of 120 s, a needle height of 3.0 cm, a free-foamed bulk density of 43 kg / m3and a maximum core temperature of 159 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 55 N to 63 N, 80 N, 93 N (crack formation), 101 N and finally 109 N. The thermal conductivity of the gained foam is 20.4 mW / (mxK), the compressive strength results in 0.182 N / mm2and the flame height gives 10.0 cm.

[0092] Foam Example 9: 50 parts of polyol 1 were exchanged by the recycling polyol of example 15. Additionally, 1.8 parts of PMDTA were added and the isocyanate 1 amount was adjusted to 233 parts to keep the mixing ratio of 100:199. The resulting index is 274. The recycled content of the polyol component A is 19.5% by weight and the recycled content of the resulting foam is 5.6% by weight. The reactivity of the system is defined by a start time of 4 s, a cream time of 53 s, a rise time of 76 s, a tack-free time of 120 s, a needle height of 2.0 cm, a free-foamed bulk density of 43 kg / m3and a maximum core temperature of 153 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 51 N to 61 N, 80 N, 83 N (crack formation), 97 N and finally 98 N. The thermal conductivity of the gained foam is 20.6 mVW(mxK), the compressive strength results in 0.158 N / mm2and the flame height gives 10.0 cm.

[0093] Foam Example 10: Polyol 1 was completely exchanged by the recycling polyol of example 16. Additionally, the amount of blowing agent 1 was lowered to 1 .6 parts and 1 .6 parts of PMDTA were added and the isocyanate 1 amount was adjusted to 232 parts to keep the mixing ratio of 100:199. The resulting index is 214. The recycled content of the polyol component A is 30.1% by weight and the recycled content of the resulting foam is 8.8% by weight. The reactivity of the system is defined by a start time of 7 s, a cream time of 53 s, a rise time of 95 s, a tack-free time of 90 s, a needle height of 3.8 cm, a free-foamed bulk density of 43 kg / m3and a maximum core temperature of 158 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 43 N to 58 N, 87 N, 109 N, 110 N and finally 121 N. The thermal conductivity of the gained foam is 20.6 mVW(mxK).

[0094] Foam Example 11 : Polyol 1 was completely exchanged by the recycling polyol of example 17. Additionally, the amount of blowing agent 1 was raised to 2.1 parts and 1 .6 parts of PMDTA were added and the isocyanate 1 amount was adjusted to 233 parts to keep the mixing ratio of 100:199. The resulting index is 263. The recycled content of the polyol component A is 28.1% by weight and the recycled content of the resulting foam is 8.2% by weight. The reactivity of the system is defined by a start time of 7 s, a cream time of 55 s, a rise time of 82 s, a tack-free time of 90 s, a needle height of 2.7 cm, a free-foamed bulk density of 44 kg / m3and a maximum core temperature of 155 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 47 N to 58 N, 86 N, 100 N, 106 N and finally 107 N. The thermal conductivity of the gained foam is 21 .0 mVW(mxK).

[0095] Foam Example 12: Polyol 1 was completely exchanged by the recycling polyol of example 18. Additionally, the amount of blowing agent 1 was raised to 1.9 parts and 1.1 parts of PMDTA were added and the isocyanate 1 amount was adjusted to 232 parts to keep the mixing ratio of 100:199. The resulting index is 264. The recycled content of the polyol component A is 20.0% by weight and the recycled content of the resulting foam is 5.7% by weight. The reactivity of the system is defined by a start time of 7 s, a cream time of 56 s, a rise time of 97 s, a tack-free time of 94 s, a needle height of 3.7 cm, a free-foamed bulk density of 41 kg / m3and a maximum core temperature of 156 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7-minutes reaction time develop from 45 N to 59 N, 87 N, 103 N, 109 N and finally 117 N. The thermal conductivity of the gained foam is 21 .0 mWZ(mxK).

[0096] Foam Example 13: Polyol 1 was completely exchanged by the recycling polyol of example 19. Additionally, the amount of blowing agent 1 was raised to 1.9 parts and 1.05 parts of PMDTA were added and the isocyanate 1 amount was adjusted to 232 parts to keep the mixing ratio of 100:199. The resulting index is 315. The recycled content of the polyol component A is 13.7% by weight and the recycled content of the resulting foam is 3.9% by weight. The reactivity of the system is defined by a start time of 6 s, a cream time of 53 s, a rise time of 92 s, a tack-free time of 108 s, a needle height of 3.2 cm, a free-foamed bulk density of 44 kg / m3and a maximum core temperature of 156 °C. The values of surface hardening after 2.5-, 3-, 4-, 5-, 6- and 7- minutes reaction time develop from 50 N to 60 N , 83 N , 101 N , 110 N and finally 115 N . The thermal conductivity of the gained foam is 21.5 mW / (mxK).

Claims

Claims1 . Method for obtaining an isocyanate reactive substance from a polyisocyanurate material(a) wherein the polyisocyanurate material (a) comprises isocyanurate structures and carboxylic ester structures and an organic phosphorous ester, wherein the method comprises mixing the polyisocyanurate material (a), a polyalcohol (b), a catalyst (c) a deamination agent (d) and an additive (e) to form a reaction mixture wherein the content of the polyisocyanurate material (a) in the reaction mixture is at least 10 % by weight, based on the total weight of components (a) to (e), and reacting the reaction mixture at temperatures of 130 to 280 °C, wherein the catalyst (c) comprises a tertiary amine catalyst, wherein the additive (e) is selected from the group consisting of(e-i) at least one alkali metal hydroxide,(e-ii) at least one alkanolamine having at least one tertiary amine group,(e-iii) at least one carbonate (sodium carbonate, hydrotalcite) and(e-iv) at least one lactame or mixtures of two or more additives (e), wherein, in case that at least one dihydric alkanolamine (e-ii) is used as additive (e), the dihydric alkanolamine (e-ii) also serves as polyalcohol (b) and no additional polyalcohol(b) is required, wherein the total content of active groups in compounds (e-i) (e-ii), (e-iii) and (e-iv) is at least 0.7 molar equivalents of the amount of the phosphorous ester present in the polyisocyanurate material and wherein the active group of the alkali metal hydroxide (e-i) is the OH group, the active group of the compound having at least one tertiary amine group (e-ii) is the tertiary amine group, the active group of the carbonate (e-iii) is the carbonate group and the active group of the lactame (e-iv) is the cyclic structure comprising-N(H)-C(O)-.

2. Method according to claim 1 wherein the content of the at least one alkali metal hydroxide (e-i) is less than 4 molar equivalents of the amount of the phosphorous ester present in the polyisocyanurate material.

3. Method according to claim 1 or 2 wherein the phosphorous ester comprises Phos- phourous esters selected from the group of triethylphosphate (TEP) and Trichlor phenyle phosphate (TCPP).

4. Method according to any of claims 1 to 3 wherein a polyisocyanurate material (a) comprising a tertiary amine catalyst (c) is added to the reaction mixture.

5. Method according to any of claims 1 to 4 wherein the catalyst (c), in addition to the tertiary amine catalyst, is selected from the group consisting of at least one tin catalyst, at least one titan catalyst or combinations of at least two of these catalysts.

6. Method according to any of claims 1 to 5 wherein the IR spectrum of a polyisocyanurate material (a) shows a ratio of the height of the isocyanurate oscillation band at approximately 1410 cm-1to the aromatic oscillation band at approx. 1600 cm-1of at least 10.

7. Method according to any of claims 1 to 6 wherein the additive (e) comprises (e-ii) at least compound having at least one tertiary amine group, the at least compound having at least one tertiary amine group comprises at least one alkanolamine.

8. Method according to claim 7, wherein the alkanolamine is N-Methyl-Diethanolamine.

9. Method according to any of claims 1 to 6 wherein the additive (e) comprises (e-iii) at least one carboxylate.

10. Method according to any of claims 1 to 9 wherein the deamination agent (d) is a glycidyl ether.11 . Isocyanate reactive substance, obtainable by a method according to any of claims 1 to. 10.

12. Polyurethane obtainable by reacting an isocyanate reactive substance according to claims 11 with at least one polyisocyanate.

13. Polyurethane according to claim 12 wherein the polyurethane is a rigid polyurethane.

14. Use of the polyurethane according to claim 12 or 13 as insulation material.

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