Glycolysis of polyisocyanurate foams

Abstract

This invention relates to a method for obtaining isocyanate reactive substances from a polyisocyanurate material (a), wherein the polyisocyanurate material comprises an isocyanurate structure, a carboxylic acid ester structure, and an organophosphorus ester, wherein the method comprises mixing the polyisocyanurate material (a), at least one polyol (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 a temperature of 130°C to 280°C, wherein the catalyst (c) comprises a tertiary amine catalyst, and wherein the additive (e) is selected from the group consisting of: (e-i) at least one alkali metal hydroxide, (e-ii) a compound having at least one tertiary amine group, (e-i) a tertiary amine group, (e-ii) a tertiary amine group, and a tertiary amine group. ii) a mixture of at least one carbonate and (e-iv) at least one lactam or two or more additives (e), wherein when at least one dialkanolamine (e-ii) is used as additive (e), the dialkanolamine (e-ii) is also used as a polyol (b) and no additional polyol (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 phosphite present in the polyisocyanurate material, and wherein the active group of the alkali metal hydroxide (e-i) is an OH group, the active group of the compound (e-ii) having at least one tertiary amine group is a tertiary amine group, the active group of the carbonate (e-iii) is a carbonate group, and the active group of the lactam (e-iv) is a cyclic structure -N(H)-C(O)-. Furthermore, the present invention relates to isocyanate reactive substances obtained by this method, polyurethanes that can be obtained by reacting isocyanate reactive substances with isocyanates, and the use of polyurethanes as insulating materials.

Description

[0001] This invention relates to a method for obtaining isocyanate reactive substances from a polyisocyanurate material (a), wherein the polyisocyanurate material comprises an isocyanurate structure, a carboxylic acid ester structure, and an organophosphorus ester, wherein the method comprises mixing the polyisocyanurate material (a), at least one polyol (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 a temperature of 130°C to 280°C, wherein the catalyst (c) comprises a tertiary amine catalyst, and wherein the additive (e) is selected from the group consisting of: (e-i) at least one alkali metal hydroxide, (e-ii) a compound having at least one tertiary amine group, (e-i ... ii) a mixture of at least one carbonate and (e-iv) at least one lactam or two or more additives (e), wherein when at least one dialkanolamine (e-ii) is used as additive (e), the dialkanolamine (e-ii) is also used as a polyol (b) and no additional polyol (b) is required, wherein the total content of active groups in compounds (ei), (e-ii), (e-iii) and (e-iv) is at least 0.7 molar equivalents of the amount of phosphite present in the polyisocyanurate material, and wherein the active group of the alkali metal hydroxide (ei) is an OH group, the active group of compound (e-ii) having at least one tertiary amine group is a tertiary amine group, the active group of the carbonate (e-iii) is a carbonate group, and the active group of the lactam (e-iv) is a cyclic structure -N(H)-C(O)-. Furthermore, the present invention relates to isocyanate reactive substances obtained by this method, polyurethane obtained by reacting isocyanate reactive substances with isocyanates, and the use of polyurethane as an insulating material.

[0002] Polyurethane foams, both flexible and rigid, can be chemically degraded via glycolysis and can be used to prepare recycled polyols. Many methods have been described in patent literature. Glycolysis of polyisocyanurate foam (PIR foam) is more difficult.

[0003] PIR foam was developed approximately 30 years ago as a replacement for PUR foam, with the aim of achieving a rigid foam with improved flame retardancy due to the inherent flame retardancy of the isocyanurate structure. One of the main motivations for the work at that time was to develop a rigid foam that did not require any flame retardants at all. The PIR system at that time still foamed at very high index values ​​of 400 and above, as the primary goal remained the development of a PIR system without added flame retardants. This development direction was subsequently abandoned, and the index was lowered to circumvent concerns about excessive brittleness of the foam. However, this necessitated the use of additional flame retardants, but in significantly smaller amounts than in classic PUR systems. Halogenated phosphates, primarily tris(2-chloroisopropyl) phosphate (TCPP), were used as the main flame retardant.

[0004] CN 104231304 discloses a method for glycolysis in a PIR system by reacting with an alcoholysis agent and a heteropolyacid catalyst (which is a solid catalyst) and then adding an alkanolamine compound after the reaction is complete. Using a solid catalyst based on a polyacid is not desirable because it produces polyols containing solid particles.

[0005] ES2277554 discloses the glycolysis of polyurethane and / or polyisocyanurate foams in the presence of a titanium catalyst or an alkali metal-based catalyst. Neither CN 104231304 nor ES2277554 discloses the recycling of polyisocyanurate materials containing isocyanurate and carboxylic ester structures and containing organophosphorus esters.

[0006] EP 753535 discloses the degradation of the PIR system. This document reveals the problem of incomplete conversion during the glycolysis of PIR foam, and the presence of black, charred clumps that prevent further processing. EP 753535 proposes carrying out the reaction of polyisocyanurate in the presence of a polyol with an OH value not exceeding 500 mg KOH / g and a molar mass of at least 450 g / mol. In the examples, NaOH is added to lower the acid value after the reaction is complete and cooled to 100°C.

[0007] DE 2304444 describes a process for degrading PIR foam, in which a mixture of ethylene glycol such as DEG and dialkylamines such as diethanolamine is used. The PIR foam described in Example 1 is obtained by reacting PMDI with a mixture of epoxy and chlorinated aliphatic esters. They do not contain any other phosphorus-based flame retardants, such as TCPP or TEP. It is noted in paragraph 3 on page 4 that phosphorus-based polyols can produce recycled polyols with high acid values, and this can be compensated, for example, by further alkoxylation of the product.

[0008] DE 2902509 describes the use of metal catalysts for the glycolysis of PUR and PIR rigid foams. These are titanium or zirconium catalysts, such as titanium(IV)butoxy. These catalysts have advantages over previously described catalysts such as amines or alkali metal hydroxides because they have little effect on the inherent reactivity of the resulting polyol. In the examples, the rigid foam used for glycolysis is referred to as PUR foam, and no further details are provided.

[0009] During glycolysis, the formation of harmful amines such as aromatic amines, including 2,2'-methylenediphenylamine, 2,4'-methylenediphenylamine, and 4,4'-methylenediphenylamine (MDA), is a common side reaction. Due to the potential dangers of these amines, so-called deaminating agents must be used to chemically bind them.

[0010] Current PIR systems are prepared with an index of 180 to 400 and also contain 5% to 30% by weight of phospholipids such as TCPP or TEP as flame retardants. Polyether alcohols (preferably aromatic polyester alcohols) are used as the main polyols, such as polyols based on terephthalic acid or phthalic acid. When the PIR foam concentration is higher than 10% by weight, such PIR foams cannot degrade into liquid polyol mixtures and always leave solid residues. Therefore, an object of the present invention is to provide a method for obtaining isocyanate reactive substances from polyisocyanurate materials (a), wherein the polyisocyanurate material comprises isocyanurate structures and carboxylic acid ester structures as well as organophosphorus esters, wherein no solid residues remain. Another object of the present invention is to provide an isocyanate reactive substance obtained by degradation of such polyisocyanurate material, and a polyurethane that can be obtained by reacting the isocyanate reactive substance with isocyanates.

[0011] The objective is to achieve this by a method for obtaining isocyanate reactive substances from a polyisocyanurate material (a), wherein the polyisocyanurate material comprises an isocyanurate structure, a carboxylic acid ester structure, and an organophosphorus ester, wherein the method comprises mixing the polyisocyanurate material (a), at least one polyol (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 a temperature of 130°C to 280°C, wherein the catalyst (c) comprises a tertiary amine catalyst, and wherein the additive (e) is selected from the group consisting of: (e1) at least one alkali metal hydroxide, (e-ii) a compound having at least one tertiary amine group, (e... -iii) a mixture of at least one carbonate and (e-iv) at least one lactam or two or more additives (e), wherein when at least one dialkanolamine (e-ii) is used as additive (e), the dialkanolamine (e-ii) is also used as a polyol (b) and no additional polyol (b) is required, wherein the total content of active groups in compounds (ei), (e-ii), (e-iii) and (e-iv) is at least 0.7 molar equivalents of the amount of phospholipid present in the polyisocyanurate material, and wherein the active group of the alkali metal hydroxide (ei) is an OH group, the active group of compound (e-ii) having at least one tertiary amine group is a tertiary amine group, the active group of the carbonate (e-iii) is a carbonate group, and the active group of the lactam (e-iv) is a cyclic structure -N(H)-C(O)-.

[0012] The isocyanate reactive substances obtained according to the present invention can react with polyisocyanates to form polyurethane materials, such as polyurethane or polyisocyanurate.

[0013] The polyisocyanurate material (a) according to the present invention comprises an isocyanurate structure, a carboxylic acid ester structure, and an organophosphorus ester. This isocyanurate is typically used when flame-retardant insulating foam is required, for example, as an insulating material for building insulation.

[0014] Isocyanurate structures are typically obtained by reacting isocyanates and isocyanate reactive materials at an isocyanate index of at least 160, preferably 180 to 400, more preferably 190 to 350, and particularly preferably 200 to 320, in the presence of a trimerizing 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 isocyanate groups to isocyanate reactive groups used.

[0015] The isocyanurate structure can be detected by IR spectroscopy. The IR spectrum of the polyisocyanurate material (a) according to the present invention is shown at approximately 1410 cm⁻¹. -1 The isocyanurate oscillation band at approximately 1600 cm⁻¹ -1 The height ratio of the aromatic oscillation bands is at least 0.5, preferably at least 1, more preferably at least 2, and particularly preferably 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, the foam sample used for IR spectroscopy measurements is taken from the core of the foam to be tested.

[0016] Suitable isocyanates are aliphatic, alicyclic, and aryliphatic isocyanates, and preferably aromatic polyvalent isocyanates known in the art. Such polyfunctional isocyanates are known and can be prepared using known methods. In particular, polyfunctional isocyanates can also be used as mixtures, such that the isocyanate component contains various polyfunctional isocyanates in this case. A polyisocyanate is a polyfunctional isocyanate having two isocyanate groups per molecule (hereinafter also referred to as diisocyanate) or more than two isocyanate groups.

[0017] Specifically, the isocyanate is selected from the group consisting of: alkylene diisocyanates having 4 to 12 carbon atoms in an alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene-1,4-diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate, and preferably hexamethylene-1,6-diisocyanate; alicyclic diisocyanates, such as cyclohexane-1,3-diisocyanate and cyclohexane-1,4-diisocyanate and any mixture of these isomers, 1-isocyano-3,3,5-trimethyl-5-isocyanomethylcyclohexane (IPDI), hexahydrotoluene-2,4-diisocyanate and hexahydrotoluene-2,6-diisocyanate and corresponding mixtures of isomers, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,2'- Diisocyanates and dicyclohexylmethane-2,4'-diisocyanates and mixtures of their respective isomers; and preferred aromatic polyisocyanates, such as toluene-2,4-diisocyanates and toluene-2,6-diisocyanates and mixtures of their respective isomers, diphenylmethane-4,4'-diisocyanates, diphenylmethane-2,4'-diisocyanates and diphenylmethane-2,2'-diisocyanates and mixtures of their respective isomers, mixtures of diphenylmethane-4,4'-diisocyanates and diphenylmethane-2,4'-diisocyanates, polyphenylmethylene polyisocyanates, diphenylmethane-4,4'-diisocyanates, diphenylmethane-2,4'-diisocyanates and mixtures of diphenylmethane-2,2'-diisocyanates, and polyphenylmethylene polyisocyanates (crude MDI), and mixtures of crude MDI and toluene diisocyanates.

[0018] Particularly suitable are diphenylmethane-2,2'-diisocyanate, diphenylmethane-2,4'-diisocyanate, and diphenylmethane-4,4'-diisocyanate (MDI), and mixtures of two or three of these isomers, or mixtures of diphenylmethane diisocyanate and higher homologues (polymeric MDI or pMDI), naphthylene-1,5-diisocyanate (NDI), toluene-2,4-diisocyanate and / or toluene-2,6-diisocyanate (TDI), dimethyl diphenyl-3,3'-diisocyanate, diphenylethane-1,2-diisocyanate, and / or p-phenylene diisocyanate (PPDI). Such polyisocyanates are disclosed in the "Polyurethane Handbook," Hanser / Gardener publications, 2nd edition, 1993, Chapter 3.2. Particularly preferred are MDI or pMDI, such as Lupranate sold by BASF. ® M20 or Lupranate ® M50.

[0019] The carboxylic acid ester structure in polyisocyanurate material (a) can be obtained by reacting polyester alcohol with polyisocyanate. Therefore, the isocyanate reactive component used to produce polyisocyanurate material (a) comprises a polyester polyol, typically in combination with a polyether polyol. Suitable polyester polyols can be prepared from organic dicarboxylic acids (preferably aromatic dicarboxylic acids or mixtures of aromatic and aliphatic dicarboxylic acids) having 2 to 12 carbon atoms and polyols (preferably diols) having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.

[0020] In particular, the following dicarboxylic acids may be considered: succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid. Dicarboxylic acids can be used alone or in mixtures. Corresponding dicarboxylic acid derivatives may also be used instead of free dicarboxylic acids, such as dicarboxylic acid esters or dicarboxylic acid anhydrides of alcohols having 1 to 4 carbon atoms. As aromatic dicarboxylic acids or acid derivatives, phthalic acid, phthalic anhydride, terephthalic acid, and / or isophthalic acid are preferably used in mixtures or alone. A mixture of dicarboxylic acids of succinic acid, glutaric acid, and adipic acid is preferred as an aliphatic dicarboxylic acid, with a ratio of, for example, 20-35:35-50:20-32 parts by weight, and adipic acid is particularly preferred as an aliphatic dicarboxylic acid. Polyester polyols obtained by using only aromatic dicarboxylic acids or their derivatives as the acid component are particularly preferred. Preferably, at least one compound selected from the group consisting of terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate (PET), phthalic acid, phthalic anhydride (PSA), and isophthalic acid, or a mixture of at least two of these dicarboxylic acids, is particularly preferred. Especially preferred is at least one compound selected from the group consisting of terephthalic acid, dimethyl terephthalate (DMT), polyethylene terephthalate (PET), and phthalic anhydride (PSA), and particularly phthalic acid and / or phthalic anhydride. In a preferred embodiment, the aromatic carboxylic acid may be obtained from recycled materials or production waste.

[0021] Examples of diols and polyols, particularly 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 alkoxylated derivatives of the same starting material. Monoethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol or 1,3-propanediol, dipropylene glycol, and ethoxylated derivatives of the same starting material, such as ethoxylated glycerol, or mixtures of at least one of the diols are preferred. In particular, monoethylene glycol, diethylene glycol, glycerol, and ethoxylated derivatives of these starting materials, or mixtures of at least two of the diols, especially diethylene glycol, are used.

[0022] Polyester polyols can be prepared without a catalyst or preferably in the presence of an esterification catalyst, preferably in an inert gas atmosphere such as nitrogen in the melt, at a temperature of 150°C to 280°C, preferably 180°C to 260°C, and appropriately under reduced pressure, until a desired acid value of preferably less than 10, more preferably less than 2 is achieved. For example, catalysts in the form of metals, metal oxides, or metal salts, such as iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium, and tin, can be considered as catalysts.

[0023] In order to produce polyester polyols, organic polycarboxylic acids and / or derivatives are advantageously polycondensed with polyols at a molar ratio of 1:1 to 2.2, preferably 1:1.05 to 2.1, and especially preferably 1:1.1 to 2.0.

[0024] The resulting polyester polyols typically have a number-average molecular weight of 200 g / mol to 3000 g / mol, preferably 300 g / mol to 1000 g / mol, and particularly 400 g / mol to 800 g / mol. Preferably, based on the total amount of polyols in the polyurethane foam, the amount of aromatic polyester alcohol is greater than 70% by weight, preferably greater than 80% by weight, and particularly preferably greater than 90% by weight to 100% by weight. The amount of aromatic esters in the polyisocyanurate material can be determined from its degradation products, for example, after glycolysis.

[0025] Suitable trimerization catalysts include those compounds used to accelerate and promote the trimerization of isocyanates. Useful trimerization catalysts include alkali metal phenolates, alkali metal carboxylates, and alkoxides. Phenates can also be called benzene oxides. Exemplary alkali metals include lithium, sodium, potassium, rubidium, cesium, and francium. Exemplary phenolate ligands may include p-nonylphenolate, p-octylphenolate, p-tert-butylphenolate, and various alkylphenol formaldehyde resins. Preferred alkali metal phenolates include potassium p-nonylphenolate, sodium p-nonylphenolate, and lithium p-nonylphenolate. Alkali metal phenolates, such as potassium p-nonylphenolate, can be formed by the reaction of p-nonylphenol and potassium hydroxide, preferably in toluene or ethyl acetate. Useful alkali metal carboxylates may include potassium carboxylate, sodium carboxylate, and lithium carboxylate, 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 salt derivatives, such as the catalyst TOYOCAT available from Tosoh. ™ TRX, or certain tertiary nitrogen derivatives, such as POLYCAT available from Air Products. ™ 41.

[0026] The amount of catalyst can vary depending on the catalyst's activity. Generally, the proportion of trimer catalyst will fall within the range of about 0.01 parts to about 15 parts per 100 parts of isocyanate reactive component.

[0027] Organophosphates are typically added as flame retardants. Examples of organophosphates are chlorinated phosphates, such as tri-(2-chloroethyl)-phosphate. , Esters, tri-(2-chloropropyl) phosphate (TCPP), tri-(1,3-dichloropropyl) phosphate, tricresyl phosphate, tri-(2,3-dibromopropyl) phosphate, tetra-(2-chloroethyl)-ethylene diphosphate, dimethyl methylphosphonate, and diethylaminomethylphosphonate. Diethyl phosphonate (DEEP), triethyl phosphate (TEP), dimethyl propyl phosphonate (DMPP), and diphenyltoluene phosphate (DPK) can also be used as organophosphates. In a preferred embodiment of the invention, the polyisocyanurate material comprises a phosphate ester selected from the group consisting of triethyl phosphate (TEP) and trichlorophenyl phosphate (TCPP).

[0028] Furthermore, polyisocyanurate materials (a) may contain suitable catalysts, blowing agents, and additives known in the art. Examples of catalysts, blowing agents, and suitable additives are mentioned in the "Polyurethane Handbook," Hanser / Gardener publications, 2nd edition, 1993.

[0029] Based on the total weight of the reaction mixture according to the invention, the amount of polyisocyanurate material (a) is at least 10% by weight, preferably 15% to 80% by weight, more preferably 20% to 60% by weight, and especially preferably 25% to 50% by weight.

[0030] Any diol can be used as the polyol (b). Preferably, the suitable polyol (b) is liquid at 40°C. Examples of polyols, preferably 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, pentaerythritol, and alkoxylated derivatives of the same starting material. Monoethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol or 1,3-propanediol, dipropylene glycol, and ethoxylated derivatives of the same starting material, such as ethoxylated glycerol, or mixtures of at least one of the diols are preferred. In particular, monoethylene glycol, diethylene glycol, glycerol, and ethoxylated derivatives of these starting materials, or mixtures of at least two of the glycols, are used, with diethylene glycol being particularly preferred. Ethylene glycols having a primary alcohol, such as ethoxylated trimethylolpropane, ethoxylated glycerol, or triethylene glycol, as well as mixtures of ethylene glycol and natural oils, are especially preferred.

[0031] Any catalyst known for the production of polyurethane from isocyanates and isocyanate reactive compounds can be used as catalyst (c), provided that catalyst (c) contains a tertiary amine catalyst. Besides tertiary amine catalysts, known catalysts can be used for the production of polyesters and the transesterification of polyesters. 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 do not contain isocyanate reactive groups such as -OH, -NH-, 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-methylmorpholine, N-ethylmorpholine and N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazolium, 1-azabicyclo[3.3.0]octane, and preferably 1,4-diazabicyclo[2.2.2]octane and dimethylcyclohexylamine, most preferably dimethylcyclohexylamine. In addition to tertiary amine catalysts, organometallic compounds, preferably organotin compounds, such as tin(II) salts of organic carboxylic acids, such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate, and tin(II) laurate, and dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, zinc(II) acetate, dibutyltin maleate, and dioctyltin diacetate; and titanium alkoxides, such as tetrabutyl orthotitanate; and bismuth carboxylic acids, such as bismuth neodecanoate(III), bismuth 2-ethylhexanoate, and bismuth octoate; or mixtures thereof. In a preferred embodiment, in addition to at least one tertiary amine catalyst, catalyst (c) is selected from the group consisting of at least one tin catalyst, at least one titanium catalyst, or a combination of at least two of these catalysts.

[0032] For example, based on the weight of components (a), (b), (c), and (d), catalyst (c) may be used as a catalyst at a concentration of 0.01 wt% to 10 wt%, particularly 0.5 wt% to 8 wt%, or individually as a combination of catalysts. In a preferred embodiment, based on the total weight of components (a), (b), (c), and (d), the content of the tertiary amine catalyst is 0.01 wt% to 10 wt%, more preferably 0.5 wt% to 8 wt%, and even more preferably 1 wt% to 5 wt%.

[0033] Deaminating agents (d) are compounds that, when added to a mixture of alcohols and aromatic amines, preferentially react with the aromatic amines even in the presence of excess alcohol. These include fatty acids, isocyanates, glycidyl ethers, or epoxidized natural oils.

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

[0035] Isocyanates used for deamination are preferably those having only secondary or tertiary or secondary and tertiary aliphatic bonds in the form of isocyanate groups, such as bis-1,3-(2-isocyanopropyl)benzene. Isocyanates and their use in deamination are described, for example, in EP899292.

[0036] Any compound containing an epoxy group can be used as glycidyl ether (d), preferably a compound containing one or two epoxy groups in the molecule. Monofunctional glycidyl ethers of general formula (i) have proven to be particularly suitable:

[0037]

[0038] Wherein R = phenyl, cyclohexyl, methylcyclohexyl, benzyl, isopropyl, isobutyl, or a methyl- and / or ethyl-branched hydrocarbon chain having 5 to 10 carbon atoms in the straight chain, and / or a group of general formula (ii):

[0039]

[0040] Where A represents an alkyl residue having 1 to 8 carbon atoms, n is 3 to 12, and m is 1 to 6.

[0041] Compounds according to formula (iii) are particularly preferred as bifunctional glycidyl ethers:

[0042]

[0043] Wherein R' = diphenylmethylene, 2,2-diphenylpropylene (bisphenol A), an unbranched hydrocarbon chain having 4 to 10 carbon atoms, or a methyl and / or ethyl branched hydrocarbon chain having 4 to 8 carbon atoms in a straight chain. Glycidyl ethers and their use for deamination are disclosed, for example, in EP592952.

[0044] Epoxidized natural fatty oils are those products obtained from at least one, preferably at least three, unsaturated natural oils (e.g., soybean, flax, castor, and all kinds of nuts). The term "unsaturated" refers to carbon-carbon double bonds. Glycidyl ethers and their use for deamination are disclosed, for example, in EP718349.

[0045] Glycidyl ether is preferably used as a deamination agent (d). The preferred glycidyl ether is a nonfunctional epoxy resin, such as 2-ethylhexyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, tolyl glycidyl ether, or a monofunctional glycidyl ether based on 2-ethylhexanol (Epilox P13-16, LEUNA-Harze GmbH), C12-C14 alcohol (Epilox P 13-18, LEUNA-Harze GmbH), or C13-C15 alcohol (Epilox P 13-19, LEUNA-Harze GmbH).

[0046] The amount of deamination agent (d) added to the reaction mixture is preferably from 0% to 40% by weight, more preferably from 5% to 30% by weight, and particularly preferably from 10% to 20% by weight, each based on the total weight of the polyisocyanurate material (a).

[0047] Additive (e) is selected from the group consisting of: (ei) at least one alkali metal hydroxide, (e-ii) a compound having at least one tertiary amine group, (e-iii) at least one carbonate, and (e-iv) at least one lactam, or a mixture of two or more additives (e).

[0048] Examples of alkali metal hydroxides (ei) are lithium hydroxide, sodium hydroxide, and potassium hydroxide.

[0049] Examples of compounds having at least one tertiary amine group (e-ii) are alkanolamines having a tertiary nitrogen atom, such as triethanolamine, methyldiethanolamine, and dimethylethanolamine. Methyldiethanolamine is particularly preferred. When the alkanolamine is at least a dialkylolamine, it can also be used as a polyol (b). This means that if at least a dialkylolamine (e-ii) is used as an additive (e), then the alkanolamine (e-ii) also functions as a polyol (b), and no additional polyol (b) is required. Furthermore, the alkanolamine can act as a tertiary amine catalyst (c). This means that if at least a dialkylolamine (e-ii) is used as an additive (e), no additional tertiary amine catalyst is necessary. In a preferred embodiment, the at least dialkylolamine (e-ii) is used in conjunction with a tertiary amine catalyst.

[0050] Examples of carbonates (e-iii) are carbonates and bicarbonates of alkali metals and alkaline earth metals, such as sodium carbonate, potassium carbonate, sodium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate, talc, and hydrotalcite. Sodium carbonate or hydrotalcite, for example, is particularly preferred as an additive (e-iii).

[0051] In the context of this invention, "lactam" (e-iv) should be understood to mean a substituted cyclic amide. In this case, the amide bond is located in the ring, and preferably only one amide group is present in the ring. Examples of lactams according to the invention are β-propiolactam, 2-pyrrolidone, N-methylpyrrolidone, γ-butyrolactam, δ-valerolactam (2-piperidinone), and ε-lactam (ε-caprolactam). ε-caprolactam is particularly preferred. Preferably, the additive (e) is selected from carbonates (e-iii) and / or lactams (e-iv), especially preferably from carbonates (e-iii).

[0052] The total content of active groups in compounds (ei), (e-ii), (e-iii) and (e-iv) is at least 0.7 molar equivalents of the amount of phospholipid present in the polyisocyanurate material, wherein the active group of the alkali metal hydroxide (ei) is an OH group, the active group of compound (e-ii) having at least one tertiary amine group is a tertiary amine group, the active group of carbonate (e-iii) is a carbonate group, and the active group of lactam (e-iv) is a cyclic structure -N(H)-C(O)-.

[0053] In a preferred embodiment, the content of at least one alkali metal hydroxide is less than 4 molar equivalents, preferably less than 3 molar equivalents, and particularly preferably less than 1.5 molar equivalents, of the amount of phospholipids present in the polyisocyanurate material (a). Also preferably, the sum of the active groups of (ei) the alkali metal hydroxide, (e-ii) the compound having at least one tertiary amine group, and (e-iv) at least one lactam tertiary amine compound (e-ii) is less than 10 molar equivalents, more preferably less than 4 molar equivalents, more preferably less than 3 molar equivalents, and particularly preferably less than 1.5 molar equivalents, of the amount of phospholipids present in the polyisocyanurate material (a). The amount of phospholipids present in the polyisocyanurate material (a) can be determined by extraction (e.g., using dichloromethane as a solvent) and subsequent gas chromatography or P-NMR or elemental analysis.

[0054] Polyisocyanurate material (a), polyol (b), catalyst (c), deaminating agent (d), and additive (e) are mixed to form a reaction mixture, wherein the content of polyisocyanurate material (a) in the reaction mixture is at least 10% by weight based on the total weight of components (a) to (e), and the reaction mixture is reacted at a temperature of 130°C to 280°C, preferably 160°C to 250°C, and particularly preferably 180°C to 220°C. In one embodiment of the invention, the polyisocyanurate material (a) comprises a tertiary amine catalyst (c). In this case, when added to the polyol (b), catalyst (c), deaminating agent (d), and additive (e), no additional catalyst (c) is required to form the reaction mixture according to the invention.

[0055] The resulting isocyanate reactive material can be further purified by filtration. Therefore, insoluble components, such as unreacted carbonates, can be separated by filtration. Furthermore, volatile substances can be separated by distillation. The resulting isocyanate reactive material can react with common isocyanates to form novel polyurethanes or polyisocyanurates. Common ingredients can be used to prepare polyurethanes / polyisocyanurates. Depending on the properties of the polymer to be obtained, additional isocyanate reactive compounds, foaming agents, known catalysts, and known additives may be added. In a preferred embodiment, the polyurethane obtained from the isocyanate reactive compound according to the invention is a rigid polyurethane foam or a rigid polyisocyanurate foam, particularly preferred as an insulating material, for example, for buildings, cooling devices, and water heaters, especially for buildings.

[0056] The present invention will be described below with reference to the embodiments:

[0057] For the glycolysis experiment, the polyisocyanurate material (a) used was a powder made from PIR foam. To prepare the foam, the following were used: a polyol 1 with an OH value of 240 composed of a polyester alcohol based on aromatic dicarboxylic acids and diethylene glycol; a polyol 2 with an OH value of 180 composed of a polyether alcohol based on ethylene oxide; a stabilizer composed of polyether siloxane from Evonik; a flame retardant composed of tri-(2-chloroisopropyl) phosphate; a blowing agent 1 composed of formic acid and water (mass ratio 85:15); a catalyst composed of a tertiary amine catalyst and potassium formate (PIR catalyst); a blowing agent 2 composed of n-pentane and isopentane in a mass ratio of 80:20; and an isocyanate composed of Lupronat M 50 from BASF.

[0058] Components substance Number of copies A Polyol 1 76,4 A Polyol 2 7,8 A Stabilizer 1 2,0 A Flame retardant 1 12,0 A Foaming agent 1 1,8 C catalyst 4,3 C Foaming agent 2 11,0 B Isocyanate 1 230,0

[0059] PIR foam boards are prepared by high-pressure mixing of components using aluminum foil as a cover layer on a dual-belt system. The mixing ratio between components A+C and B is 115.3:230. Corrected to a mixing ratio of 100 parts A+C, this is 100:199. This corresponds to an index of 335. The cover layer of the resulting PIR foam board is then removed, and the PIR foam is ground into powder using an ultrafine grinder (sieve aperture: 4 mm).

[0060] Glycolysis was carried out under a nitrogen atmosphere in a temperature-controlled 2-liter glass reaction vessel equipped with a stirrer, reflux condenser, and metering funnel, under a thermostatic jacket. The corresponding polyol (b) was heated to 210°C along with any catalyst (c), deaminator (d), and additive (e) used, and then PIR foam powder was added in portions, allowing the reaction mixture to remain stirred. After the last portion was added, stirring continued until a clear reaction product was obtained.

[0061] Comparative Example 1: Production of recycled polyols 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 adding two parts (corresponding to a total of 114 g of PIR foam powder), complete degradation could not be achieved (this corresponds to a theoretical PIR foam content of 13% by mass in the reaction mixture), and further addition of PIR powder was not possible due to the limited stirring capacity of the reaction mixture. On the other hand, a heterogeneous reaction mixture with swollen PIR foam particles was obtained, which did not undergo further degradation. Increasing the reaction temperature from 210 °C to 235 °C did not result in any change. This attempt ended in failure after 12 hours.

[0062] Example 2: Production of recycled polyols was carried out as described above. For this purpose, 1550 g of diethylene glycol and 7.5 g of sodium hydroxide were added and heated to 210°C. Complete degradation was achieved after the addition of six parts (corresponding to a total of 750 g of PIR foam powder). After a reaction time of 12 hours, a clear polyol with an OH value of 700, a PIR foam content of 32.5% by mass, and an MDA content of 540 ppm (360 ppm of 2,4'-MDA and 180 ppm of 4,4'-MDA) was obtained.

[0063] Example 3: Production of recycled polyols was carried out as described above. For this purpose, 880 g of diethylene glycol and 15 g of sodium hydroxide were added and heated to 210°C. Complete degradation was achieved after the addition of two parts (corresponding to a total of 600 g of PIR foam powder). After a reaction time of 2 hours and 40 minutes, a clear polyol with an OH value of 625, a rigid foam content of 40% by mass, and an MDA content of 4,370 ppm (810 ppm of 2,4'-MDA and 3,560 ppm of 4,4'-MDA) was obtained.

[0064] Example 4: Production of recycled polyols was carried out as described above. For this purpose, 420 g of diethylene glycol and 630 g of triethanolamine were added and heated to 210°C. Complete degradation was achieved after the addition of two parts (corresponding to a total of 450 g of PIR foam powder). After a reaction time of 6 hours and 45 minutes, a clear polyol with an OH value of 865, a rigid foam content of 30% by mass, and an MDA content of 2,590 ppm (350 ppm of 2,4'-MDA and 2,240 ppm of 4,4'-MDA) was obtained.

[0065] Example 5: Production of recycled polyols was carried out as described above. For this purpose, 750 g of N-methyldiethanolamine was added and heated to 210°C. Complete degradation was achieved after the addition of ten parts (corresponding to a total of 750 g of PIR foam powder). After a reaction time of 3 hours, a clear polyol with an OH value of 470, a rigid foam content of 50% by mass, and an MDA content of 21,700 ppm (5,400 ppm of 2,4'-MDA and 16,300 ppm of 4,4'-MDA) was obtained.

[0066] Example 6: Production of recycled polyols was carried out as described above. For this purpose, 750 g of N-methyldiethanolamine was added and heated to 160°C. Complete degradation was achieved after the addition of eleven parts (corresponding to a total of 750 g of PIR foam powder). After a reaction time of 4 hours and 10 minutes, a clear polyol with an OH value of 470, a rigid foam content of 50% by mass, and an MDA content of 12,400 ppm (2,600 ppm of 2,4'-MDA and 9,800 ppm of 4,4'-MDA) was obtained.

[0067] Example 7: Production of recycled polyols was carried out as described above. For this purpose, 750 g of N-methyldiethanolamine and 1.5 g of tetrabutyl orthotitanate were added and heated to 150°C. Complete degradation was achieved after the addition of nine parts (corresponding to a total of 750 g of PIR foam powder). After a reaction time of 6 hours, a clear polyol with an OH value of 470, a rigid foam content of 50% by mass, and an MDA content of 10,800 ppm (2,800 ppm of 2,4'-MDA and 8,000 ppm of 4,4'-MDA) was obtained.

[0068] Example 8: Production of recycled polyols was carried out as described above. For this purpose, 853 g of diethylene glycol, 46 g of N-methyldiethanolamine, and 1.5 g of tetrabutyl orthotitanate were added and heated to 210°C. Complete degradation was achieved after the addition of six parts (corresponding to a total of 600 g of PIR foam powder). After a reaction time of 6 hours and 10 minutes, a clear polyol with an OH value of 630, a rigid foam content of 40% by mass, and an MDA content of 2,170 ppm (360 ppm of 2,4'-MDA and 1,810 ppm of 4,4'-MDA) was obtained.

[0069] Example 9: Production of recycled polyol as described above. For this purpose, 860 g of diethylene glycol, 1.5 g of tetrabutyl titanate, and 60 g of hydrotalcite were added and heated to 210°C. Complete degradation was achieved after the addition of four parts (corresponding to a total of 600 g of PIR foam powder). After a reaction time of 4 hours and 25 minutes, a clear polyol with an OH value of 600, a rigid foam content of 39.5% by mass, and an MDA content of 1,580 ppm (380 ppm of 2,4'-MDA and 1,200 ppm of 4,4'-MDA) was obtained.

[0070] Example 10: Production of recycled polyol was carried out as described above. For this purpose, 890 g of diethylene glycol, 1.5 g of tetrabutyl orthotitanate, and 10.3 g of sodium carbonate were added and heated to 210°C. Complete degradation was achieved after the addition of three parts (corresponding to a total of 600 g of PIR foam powder). After a reaction time of 4 hours and 5 minutes, a turbid polyol with an OH value of 625, a rigid foam content of 40% by mass, and an MDA content of 1,890 ppm (490 ppm of 2,4'-MDA and 1,400 ppm of 4,4'-MDA) was obtained. Undissolved sodium carbonate was removed from the polyol by filtration, resulting in a clear polyol.

[0071] Example 11: Production of recycled polyols was carried out as described above. For this purpose, 991 g of tripropylene glycol and 95 g of hydrotalcite were added and heated to 220°C. Complete degradation was achieved after the addition of seven parts (corresponding to a total of 504 g of PIR foam powder). Following glycolysis, the temperature was lowered to 150°C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was maintained at this state for 30 minutes. After a reaction time of 6 hours and 30 minutes, a clear polyol with an OH value of 360, a rigid foam content of 30% by mass, and an MDA content below the limit of quantitation was obtained.

[0072] Example 12: Production of recycled polyols was carried out as described above. For this purpose, 715 g of diethylene glycol, 180 g of polyethylene glycol with a molar mass of 600 g / mol, and 95 g of hydrotalcite were added and heated to 210°C. Complete degradation was achieved after the addition of six parts (corresponding to a total of 720 g of PIR foam powder). After a reaction time of 5 hours and 20 minutes, a clear polyol with an OH value of 455, a rigid foam content of 40% by mass, and an MDA content below the limit of quantitation was obtained.

[0073] Example 13: Production of recycled polyols was carried out as described above. For this purpose, 315 g of diethylene glycol, 575 g of tripropylene glycol, and 100 g of hydrotalcite were added and heated to 220°C. Complete degradation was achieved after the addition of five parts (corresponding to a total of 720 g of PIR foam powder). After glycolysis, the temperature was lowered to 150°C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was maintained at this state for 30 minutes. After a reaction time of 6 hours and 5 minutes, a clear polyol with an OH value of 385, a rigid foam content of 40% by mass, and an MDA content below the limit of quantitation was obtained.

[0074] Example 14: Production of recycled polyols was carried out as described above. For this purpose, 1050 g of polyethylene glycol (600 g / mol) and 100 g of hydrotalcite were added and heated to 210°C. Complete degradation was achieved after the addition of five parts (corresponding to a total of 360 g of PIR foam powder). After glycolysis, the temperature was lowered to 150°C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was maintained at this state for 30 minutes. After a reaction time of 5 hours and 25 minutes, a clear polyol with an OH value of 140, a rigid foam content of 22.5% by mass, and an MDA content of 200 ppm (100 ppm of 2,4'-MDA and 100 ppm of 4,4'-MDA) was obtained.

[0075] Example 15: Production of recycled polyols was carried out as described above. For this purpose, 249 g of dipropylene glycol, 746 g of tripropylene glycol, 30 g of N-methyldiethanolamine, 9 g of sodium carbonate, and 3 g of sodium hydroxide were added and heated to 210°C. Complete degradation was achieved after the addition of ten parts (corresponding to a total of 720 g of PIR foam powder). After glycolysis, the temperature was lowered to 150°C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was maintained at this state for 30 minutes. After a reaction time of 8 hours, a polyol with an OH value of 370, a rigid foam content of 40% by mass, and an MDA content below the limit of quantitation was obtained.

[0076] Example 16: Production of recycled polyols was carried out as described above. For this purpose, 1095 g of dipropylene glycol and 12 g of sodium carbonate were added and heated to 210°C. Complete degradation was achieved after the addition of seven parts (corresponding to a total of 800 g of PIR foam powder). After glycolysis, the temperature was lowered to 100°C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was maintained in this state for 30 minutes. After a reaction time of 5 hours and 40 minutes, a polyol with an OH value of 475, a rigid foam content of 40% by mass, and an MDA content below the limit of quantitation was obtained.

[0077] Example 17: Production of recycled polyols was carried out as described above. For this purpose, 1098 g of tripropylene glycol and 12 g of sodium carbonate were added and heated to 210°C. Complete degradation was achieved after the addition of six parts (corresponding to a total of 720 g of PIR foam powder). Following glycolysis, the temperature was lowered to 100°C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was maintained at this state for 30 minutes. After a reaction time of 5 hours and 25 minutes, a polyol with an OH value of 350, a rigid foam content of 37.5% by mass, and an MDA content below the limit of quantitation was obtained.

[0078] Example 18: Production of recycled polyols was carried out as described above. For this purpose, 500 g of dipropylene glycol, 500 g of tripropylene glycol, and 12 g of sodium carbonate were added and heated to 210°C. Complete degradation was achieved after the addition of six parts (corresponding to a total of 734 g of PIR foam powder). After glycolysis, the temperature was lowered to 100°C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was maintained in this state for 30 minutes. After a reaction time of 5 hours and 25 minutes, a polyol with an OH value of 400, a rigid foam content of 40% by mass, and an MDA content below the limit of quantitation was obtained.

[0079] Example 19: Production of recycled polyols was carried out as described above. For this purpose, 1320 g of glycerol-based polypropylene glycol with a hydroxyl value of 400 mg KOH / g and 15 g of sodium carbonate were added and heated to 210°C. Complete degradation was achieved after the addition of five parts (corresponding to a total of 540 g of PIR foam powder). After glycolysis, the temperature was lowered to 100°C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was maintained in this state for 30 minutes. After a reaction time of 6 hours and 40 minutes, a polyol with an OH value of 285, a rigid foam content of 27.5% by mass, and an MDA content of 248 ppm (98 ppm of 2,4'-MDA and 150 ppm of 4,4'-MDA) was obtained.

[0080] Example 20: Production of recycled polyols was carried out as described above. For this purpose, 798 g of 1,2-propanediol and 24 g of sodium carbonate were added and heated to 180°C. Complete degradation was achieved after the addition of eleven parts (corresponding to a total of 1115 g of PIR foam powder). After glycolysis, the temperature was lowered to 100°C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was maintained in this state for 30 minutes. After a reaction time of 11 hours and 20 minutes, a polyol with an OH value of 595, a rigid foam content of 55% by mass, and an MDA content of 6,400 ppm (1,000 ppm of 2,4'-MDA and 5,400 ppm of 4,4'-MDA) was obtained.

[0081] Example 21: Production of recycled polyols was carried out as described above. For this purpose, 798 g of monoethylene glycol and 21 g of sodium carbonate were added and heated to 180°C. Complete degradation was achieved after the addition of eleven parts (corresponding to a total of 1115 g of PIR foam powder). After glycolysis, the temperature was lowered to 100°C, 90 g of 2-ethylhexyl glycidyl ether was added, and the reaction mixture was maintained in this state for 30 minutes. After a reaction time of 11 hours and 50 minutes, a polyol with an OH value of 730, a rigid foam content of 55% by mass, and an MDA content of 2,000 ppm (4,4'-MDA only) was obtained.

[0082] Recycled polyols are used as components in polyisocyanurate materials (a) from which the polyols are prepared. The following are examples in which polyol 1 is replaced by a corresponding recycled polyol. The mixing ratio remains constant, thus altering the system's exponent.

[0083] The resulting foam is characterized by its reactivity, hardening, thermal and mechanical properties, and its combustion behavior.

[0084] To assess reactivity, a foam qualitative system was used to determine the onset time, rise time, and peak core temperature. Onset time was defined as the time between the start of mixing and the beginning of volume expansion of the reaction mixture due to foaming. Rise time was defined as the time between the start of mixing and the end of volume expansion.

[0085] The milky time, surface drying time, needle height, and free foam bulk density were also determined. Milky time is the time from the start of mixing to the reaction process, during which a thread can be pulled out of the foam material with a rod. Surface drying time is defined as the time between the start of stirring and when almost no adhesive effect is detectable when a rod or similar object touches the foam surface. To determine the needle height, when the milky time is reached, a needle or syringe cannula is inserted into the foam directly above the rim of the cup. After the foam volume expansion is complete, the distance traveled by the needle is measured. The core temperature is recorded using a thermocouple; once the foam head rises above half the cup height, the thermocouple passes through an opening half the cup height to reach the center of the cup. The maximum core temperature is then output from the recorded data. To determine the free foam bulk density, a defined sample is cut from the material, the sample size and weight are determined, and the density is calculated.

[0086] Surface hardening was determined using a universal testing machine. In this case, the foam surface was pressed 1 cm into the test mold at fixed intervals, and the resulting force was determined.

[0087] Thermal conductivity was measured using a heat flow meter. Measurements were performed under ambient pressure, at an average temperature of 10°C, and at a temperature difference of 10 K between the measuring plates.

[0088] The compressive strength in three spatial directions was also determined using a universal testing machine according to DIN EN ISO 844 and corrected to 38 kg / m. 3 The density.

[0089] The flame height is given as a result of characterization of the combustion behavior of Class E when ignited at the edge at 15s.

[0090] Foam Reference: The reference system is the original system without using any recycled polyols. As mentioned above, the mixing ratio between components A+C and B is 100:199, which corresponds to an index of 335. The reactivity of the system is measured by the onset time of 7 s, the milky time of 54 s, the rise time of 80 s, the surface drying time of 90 s, the needle height of 3.4 cm, and 42 kg / m³. 3 The free-floating bulk density and the maximum core temperature of 167°C were defined. After reaction times of 2.5 min, 3 min, 4 min, 5 min, 6 min, and 7 min, the surface hardening value increased from 74 N to 88 N, 102 N, 120 N, 131 N, and finally 133 N. The resulting foam had a thermal conductivity of 20.9 mW / (m×K) and a compressive strength of 0.171 N / mm.2 The obtained flame height was 8.3 cm.

[0091] Foam Example 1: 25 parts of polyol 1 were replaced with the recycled polyol from Example 8. Additionally, 1.3 parts of PMDTA (pentamethyldiethylenetriamine) were added, and the amount of isocyanate 1 was adjusted to 232 parts to maintain a mixing ratio of 100:199. The resulting index was 258. The recycled content of polyol component A was 10.0% by weight, and the recycled content of the resulting foam was 2.9% by weight. The reactivity of the system was measured by the onset time of 7 s, the milky time of 51 s, the rise time of 76 s, the surface drying time of 120 s, the needle height of 2.6 cm, and 43 kg / m³. 3 The free foaming bulk density and the maximum core temperature of 152°C were defined. After reaction times of 2.5 min, 3 min, 4 min, 5 min, 6 min, and 7 min, the surface hardening value developed from 26 N to 32 N, 41 N, 48 N, 48 N (crack formation), and finally 54 N. The resulting foam had a thermal conductivity of 21.0 mW / (m×K) and a compressive strength of 0.111 N / mm. 2 The obtained flame height was 12.7cm.

[0092] Foam Example 2: 25 parts of polyol 1 were replaced with the recycled polyol from Example 11. Additionally, 0.7 parts of PMDTA were added, and the amount of isocyanate 1 was adjusted to 231 parts to maintain a mixing ratio of 100:199. The resulting index was 306. The recycled content of polyol component A was 7.5% by weight, and the recycled content of the resulting foam was 2.2% by weight. The system reactivity was measured by the onset time of 6 s, the milky time of 53 s, the rise time of 72 s, the surface drying time of 105 s, the needle height of 2.6 cm, and 42 kg / m³. 3 The free-floating bulk density and the maximum core temperature of 172°C were defined. After reaction times of 2.5, 3, 4, 5, 6, and 7 minutes, the surface hardening values ​​developed from 50 N to 58 N, 69 N, 83 N (crack formation), 92 N, and finally 95 N. The resulting foam had a thermal conductivity of 20.9 mW / (m×K) and a compressive strength of 0.171 N / mm². 2 The obtained flame height was 9.7 cm.

[0093] Foam Example 3: 50 parts of polyol 1 were replaced with the recycled polyol from Example 11. Additionally, 1.3 parts of PMDTA were added, and the amount of isocyanate 1 was adjusted to 232 parts to maintain a mixing ratio of 100:199. The resulting index was 283. The recycled content of polyol component A was 15.0% by weight, and the recycled content of the resulting foam was 4.3% by weight. The system reactivity was measured by the onset time of 5 s, the milky time of 52 s, the rise time of 77 s, the surface drying time of 90 s, the needle height of 2.8 cm, and 42 kg / m³. 3 The free-floating bulk density and the maximum core temperature of 156°C were defined. After reaction times of 2.5 min, 3 min, 4 min, 5 min, 6 min, and 7 min, the surface hardening values ​​developed from 40 N to 53 N, 68 N (crack formation), 75 N, 78 N, and finally 81 N. The resulting foam had a thermal conductivity of 20.9 mW / (m×K) and a compressive strength of 0.174 N / mm. 2 The obtained flame height was 11.7cm.

[0094] Foam Example 4: 25 parts of polyol 1 were replaced with the recycled polyol from Example 13. Additionally, 0.7 parts of PMDTA were added, and the amount of isocyanate 1 was adjusted to 231 parts to maintain a mixing ratio of 100:199. The resulting index was 300. The recycled content of polyol component A was 10.0% by weight, and the recycled content of the resulting foam was 2.9% by weight. The system reactivity was measured by the onset time of 7 s, the milky time of 54 s, the rise time of 79 s, the surface drying time of 105 s, the needle height of 2.7 cm, and 42 kg / m³. 3 The free-floating bulk density and the maximum core temperature of 159°C were defined. After reaction times of 2.5 min, 3 min, 4 min, 5 min, 6 min, and 7 min, the surface hardening values ​​developed from 47 N to 56 N, 67 N, 82 N (crack formation), 80 N, and finally 84 N. The resulting foam had a thermal conductivity of 20.9 mW / (m×K) and a compressive strength of 0.161 N / mm. 2 The obtained flame height was 9.3 cm.

[0095] Foam Example 5: 50 parts of polyol 1 were replaced with the recycled polyol from Example 13. Additionally, 1.3 parts of PMDTA were added, and the amount of isocyanate 1 was adjusted to 232 parts to maintain a mixing ratio of 100:199. The resulting index was 273. The recycled content of polyol component A was 20.0% by weight, and the recycled content of the resulting foam was 5.7% by weight. The system reactivity was measured by the onset time of 6 s, the milky time of 55 s, the rise time of 87 s, the surface drying time of 105 s, and the reaction time of 43 kg / m³. 3The free-floating bulk density and the maximum core temperature of 153°C were defined. After reaction times of 2.5, 3, 4, 5, 6, and 7 minutes, the surface hardening values ​​developed from 17 N to 20 N, 31 N (crack formation), 41 N, 49 N, and finally 55 N. The resulting foam had a thermal conductivity of 27.1 mW / (m×K) and a compressive strength of 0.108 N / mm. 2 The obtained flame height was 8.7cm.

[0096] Foam Example 6: 25 parts of polyol 1 were replaced with the recycled polyol from Example 14. Additionally, 0.2 parts of PMDTA were added, maintaining a mixing ratio of 100:199. The resulting index was 377. The recycled content of polyol component A was 5.6% by weight, and the recycled content of the resulting foam was 1.6% by weight. The system reactivity was measured by the onset time of 6 s, the milky time of 53 s, the rise time of 75 s, the surface drying time of 120 s, the needle height of 3.1 cm, and 43 kg / m³. 3 The free-floating bulk density and the maximum core temperature of 157°C were defined. After reaction times of 2.5 min, 3 min, 4 min, 5 min, 6 min, and 7 min, the surface hardening values ​​developed from 53 N to 61 N, 74 N, 84 N, 91 N, and finally 99 N. The resulting foam had a thermal conductivity of 20.7 mW / (m×K) and a compressive strength of 0.160 N / mm. 2 The obtained flame height was 9.0 cm.

[0097] Foam Example 7: 50 parts of polyol 1 were replaced with the recycled polyol from Example 14. Additionally, 0.4 parts of PMDTA were added, maintaining a mixing ratio of 100:199. The resulting index was 412. The recycled content of polyol component A was 11.3% by weight, and the recycled content of the resulting foam was 3.3% by weight. The reactivity of the system was defined as: onset time 5 s, milky time 53 s, rise time 83 s, surface drying time 150 s, needle height 3.4 cm, and 45 kg / m³. 3 The free-floating bulk density and the highest core temperature of 152℃ were obtained. After reaction times of 2.5 min, 3 min, 4 min, 5 min, 6 min, and 7 min, the surface hardening values ​​developed from 38 N to 44 N, 55 N, 63 N, 71 N, and finally 78 N (crack formation). The resulting foam had a thermal conductivity of 26.0 mW / (m×K) and a compressive strength of 0.166 N / mm. 2 The obtained flame height was 5.7cm.

[0098] Foam Example 8: 25 parts of polyol 1 were replaced with the recycled polyol from Example 15. Additionally, 0.5 parts of PMDTA were added, maintaining a mixing ratio of 100:199. The resulting index was 302. The recycled content of polyol component A was 9.8% by weight, and the recycled content of the resulting foam was 2.8% by weight. The system reactivity was measured by the onset time of 7 s, the milky time of 54 s, the rise time of 81 s, the surface drying time of 120 s, the needle height of 3.0 cm, and 43 kg / m³. 3 The free-floating bulk density and the maximum core temperature of 159°C were defined. After reaction times of 2.5, 3, 4, 5, 6, and 7 minutes, the surface hardening values ​​developed from 55 N to 63 N, 80 N, 93 N (crack formation), 101 N, and finally 109 N. The resulting foam had a thermal conductivity of 20.4 mW / (m×K) and a compressive strength of 0.182 N / mm. 2 The obtained flame height was 10.0 cm.

[0099] Foam Example 9: 50 parts of polyol 1 were replaced with the recycled polyol from Example 15. Additionally, 1.8 parts of PMDTA were added, and the amount of isocyanate 1 was adjusted to 233 parts to maintain a mixing ratio of 100:199. The resulting index was 274. The recycled content of polyol component A was 19.5% by weight, and the recycled content of the resulting foam was 5.6% by weight. The reactivity of the system was measured by the onset time of 4 s, the milky time of 53 s, the rise time of 76 s, the surface drying time of 120 s, the needle height of 2.0 cm, and 43 kg / m³. 3 The free-floating bulk density and the maximum core temperature of 153°C were defined. After reaction times of 2.5 min, 3 min, 4 min, 5 min, 6 min, and 7 min, the surface hardening values ​​developed from 51 N to 61 N, 80 N, 83 N (crack formation), 97 N, and finally 98 N. The resulting foam had a thermal conductivity of 20.6 mW / (m×K) and a compressive strength of 0.158 N / mm. 2 The obtained flame height was 10.0 cm.

[0100] Foam Example 10: Polyol 1 was completely replaced with the recycled polyol from Example 16. Additionally, the amount of blowing agent 1 was reduced to 1.6 parts, and 1.6 parts of PMDTA were added, while the amount of isocyanate 1 was adjusted to 232 parts to maintain a mixing ratio of 100:199. The resulting index was 214. The recycled content of polyol component A was 30.1% by weight, and the recycled content of the resulting foam was 8.8% by weight. The system reactivity was measured by the onset time of 7 s, the milky time of 53 s, the rise time of 95 s, the surface drying time of 90 s, the needle height of 3.8 cm, and 43 kg / m³. 3The free foaming bulk density and the maximum core temperature of 158°C were defined. After reaction times of 2.5 min, 3 min, 4 min, 5 min, 6 min, and 7 min, the surface hardening value increased from 43 N to 58 N, 87 N, 109 N, 110 N, and finally 121 N. The thermal conductivity of the resulting foam was 20.6 mW / (m×K).

[0101] Foam Example 11: Polyol 1 was completely replaced with the recycled polyol from Example 17. Additionally, the amount of blowing agent 1 was increased to 2.1 parts, and 1.6 parts of PMDTA were added, while the amount of isocyanate 1 was adjusted to 233 parts to maintain a mixing ratio of 100:199. The resulting index was 263. The recycled content of polyol component A was 28.1% by weight, and the recycled content of the resulting foam was 8.2% by weight. The system reactivity was measured by the onset time of 7 s, the milky time of 55 s, the rise time of 82 s, the surface drying time of 90 s, the needle height of 2.7 cm, and 44 kg / m³. 3 The free foaming bulk density and the maximum core temperature of 155°C were defined. After reaction times of 2.5 min, 3 min, 4 min, 5 min, 6 min, and 7 min, the surface hardening value developed from 47 N to 58 N, 86 N, 100 N, 106 N, and finally 107 N. The thermal conductivity of the resulting foam was 21.0 mW / (m×K).

[0102] Foam Example 12: Polyol 1 was completely replaced with the recycled polyol from Example 18. Additionally, the amount of blowing agent 1 was increased to 1.9 parts, and 1.1 parts of PMDTA were added, while the amount of isocyanate 1 was adjusted to 232 parts to maintain a mixing ratio of 100:199. The resulting index was 264. The recycled content of polyol component A was 20.0% by weight, and the recycled content of the resulting foam was 5.7% by weight. The system reactivity was measured by the onset time of 7 s, the milky time of 56 s, the rise time of 97 s, the surface drying time of 94 s, the needle height of 3.7 cm, and 41 kg / m³. 3 The free foaming bulk density and the maximum core temperature of 156°C were defined. After reaction times of 2.5 min, 3 min, 4 min, 5 min, 6 min, and 7 min, the surface hardening value developed from 45 N to 59 N, 87 N, 103 N, 109 N, and finally 117 N. The thermal conductivity of the resulting foam was 21.0 mW / (m×K).

[0103] Foam Example 13: Polyol 1 was completely replaced with the recycled polyol from Example 19. Additionally, the amount of blowing agent 1 was increased to 1.9 parts, and 1.05 parts of PMDTA were added, while the amount of isocyanate 1 was adjusted to 232 parts to maintain a mixing ratio of 100:199. The resulting index was 315. The recycled content of polyol component A was 13.7% by weight, and the recycled content of the resulting foam was 3.9% by weight. The system reactivity was measured by the onset time of 6 s, the milky time of 53 s, the rise time of 92 s, the surface drying time of 108 s, the needle height of 3.2 cm, and 44 kg / m³. 3 The free foaming bulk density and the maximum core temperature of 156°C were defined. After reaction times of 2.5 min, 3 min, 4 min, 5 min, 6 min, and 7 min, the surface hardening value developed from 50 N to 60 N, 83 N, 101 N, 110 N, and finally 115 N. The thermal conductivity of the resulting foam was 21.5 mW / (m×K).

Claims

1. A method for obtaining an isocyanate reactive substance from a polyisocyanurate material (a), wherein the polyisocyanurate material (a) comprises an isocyanurate structure, a carboxylic acid ester structure, and an organophosphorus ester. The method includes The polyisocyanurate material (a), polyol (b), catalyst (c), deaminating agent (d), and 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 the reaction mixture is reacted at a temperature of 130°C to 280°C. The catalyst (c) comprises a tertiary amine catalyst. The additive (e) mentioned above is selected from the group consisting of the following: (ei) 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 lactam, Or a mixture of two or more additives (e), In cases where at least one dialkylolamine (e-ii) is used as additive (e), the dialkylolamine (e-ii) is also used as polyol (b), and no additional polyol (b) is required. The total content of active groups in compounds (ei), (e-ii), (e-iii), and (e-iv) is at least 0.7 molar equivalents of the amount of the phospholipid present in the polyisocyanurate material, and The active group of the alkali metal hydroxide (ei) is an OH group. The active group of the compound (e-ii) having at least one tertiary amine group is a tertiary amine group. The active group of the carbonate (e-iii) is a carbonate group, and The active group of the lactam (e-iv) is a cyclic structure containing -N(H)-C(O)-.

2. The method according to claim 1, wherein the content of the at least one alkali metal hydroxide (EI) is less than 4 molar equivalents of the amount of the phospholipid present in the polyisocyanurate material.

3. The method according to claim 1 or 2, wherein the phosphate ester comprises a phosphate ester selected from the group consisting of triethyl phosphate (TEP) and trichlorophenyl phosphate (TCPP).

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

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

6. The method according to any one of claims 1 to 5, wherein the IR spectrum of the polyisocyanurate material (a) is displayed at approximately 1410 cm⁻¹. -1 The isocyanurate oscillation band at approximately 1600 cm⁻¹ -1 The height ratio of the aromatic oscillation zone at that location is at least 10.

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

8. The method according to claim 7, wherein the alkanolamine is N-methyl-diethanolamine.

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

10. The method according to any one of claims 1 to 9, wherein the deaminating agent (d) is glycidyl ether.

11. An isocyanate reactive substance, said isocyanate reactive substance being obtainable by the method according to any one of claims 1 to 10.

12. A polyurethane, which can be obtained by reacting the isocyanate reactive substance according to claim 11 with at least one polyisocyanate.

13. The polyurethane of claim 12, wherein the polyurethane is a rigid polyurethane.

14. Use of polyurethane as an insulating material according to claim 12 or 13.

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