Patent Application
20250115703
The present invention relates to a process for preparing a carbodiimide, wherein the process comprises provision of a specific catalytic compound particularly comprising a metal M and oxygen, wherein at least a portion of the metal M is bound to oxygen via one or more single bonds, via one or more double bonds, or via one or more single and double bonds, and wherein M is one or more of Mo and W. Further, the present invention relates to a carbodiimide, obtained and/or obtainable by the inventive process, and use thereof.
Carbodiimides, preferably in their oligomeric or polymeric form as polycarbodiimides, are known compounds, which are used as stabilizers in plastics, in particular with respect to undesired degradation due to hydrolysis. In the context of the present invention the term polycarbodiimides includes oligomeric as well as polymeric forms thereof. For example, in particular thermoplastic polyurethanes or polyesters are typically stabilized with polycarbodiimides.
Generally, carbodiimides and also polycarbodiimides can be prepared by known methods, especially by elimination of carbon dioxide from monoisocyanates, oligoisocyanates or polyisocy-anates under catalytic conditions. In particular, two diisocyanates can react in an elimination reaction to a carbodiimide. Further elimination reaction(s) with additional isocyanates can lead to a carbodiimide of formula (I):
Q
1-[Q2−N═C═N]n-Q3-Q4 (I)
wherein n is in the range of from 1 to 500, preferably in the range of from 2 to 20, more preferably in the range of from 3 to 15, more preferably in the range of from 4 to 10, and wherein Q2 and Q3 stands for an organic backbone and Q1 and Q4 stands for an organic end group, wherein n is typically in the range of from 1 to 500, preferably in the range of from 2 to 20, more preferably in the range of from 3 to 15, more preferably in the range of from 4 to 10, and wherein Q represents an organic backbone.
Said carbodiimidization reaction is typically run in the presence of a catalyst. Suitable catalysts include heterocyclic compounds containing phosphorus, e.g. phospholines, phospholenes and phospholidines and also their oxides and sulfides and/or metal carbonyls. Typical catalysts include phospholene oxides, in particular 1-methyl-2-phospholene-1-oxide or 3-Methyl-1-phenyl-2-phospholene 1-oxide.
For example, a typical hydrolysis stabilizer for thermoplastic polyurethanes (Elastostab) can be synthesized from tetramethyixylene diisocyanate (TMXDI), wherein the synthesis is homoge-nously catalyzed by 1-methyl-2-phospholene-1-oxide (MPO). However, the used phospholene oxide-containing catalyst is comparatively expensive and it has to be removed from the end-product, typically via distillation, in order to avoid any side reaction when formulated in thermoplastic polyurethanes.
U.S. Pat. No. 3,406,197 A relates to the use of transition metal carbonyl compounds as catalysts for con-verting isocyanates to carbodiimides and particularly discloses use of molybdenum hexacarbonyl or tungsten hexacarbonyl as catalyst.
JP S54 66656 A discloses a method for producing dicyclohexylcarbodiimide (DCC) heating CHI together with a catalyst at 150 to 250° C.
DE 198 14 169 A1 discloses a process of reacting at least one polyol (a) with at least one di- or polyisocyanate (such as MDI) (b) followed by carbodiimidization of the reaction product thereof using a catalyst.
U.S. Pat. No. 3,632,620 A discloses decomposition of carbodiimide using MoO2/CuC12 catalyst into respective isocyanate.
Thus, a need remains for a process for preparing a carbodiimide, preferably for preparing a carbodiimide having formula (I), avoiding the disadvantages of known processes, in particular with respect to resource and process efficiency. Further, the need remains for a process making use of less toxic catalytic compounds, which thus avoids using potentially harmful materials. Thus, the need remains for an improved process for preparing a carbodiimide, preferably for preparing a carbodiimide having formula (I), in particular as an alternative to existing processes.
It was an object of the present invention to provide a novel process for preparing a carbodiimide, preferably for preparing a carbodiimide having formula (I), in particular avoiding the draw-backs of known processes. Thus, it was an object of the present invention to provide a novel process for preparing a carbodiimide, preferably for preparing a carbodiimide having formula (I), avoiding toxic catalytic compounds while particularly achieving a good selectivity towards the formation of a carbodiimide. Also, it was an object to provide such a process under reaction conditions allowing comparatively low temperatures while achieving excellent yields.
Surprisingly, it was found that a catalytic compound comprising a metal M and oxygen, wherein at least a portion of the metal M is bound to oxygen via one or more single bonds, via one or more double bonds, or via one or more single and double bonds, and wherein M is one or more of Mo and W, is an active catalyst for preparing a carbodiimide, preferably for preparing a carbodiimide having formula (I), via condensation of one or more isocyanates. Thus, a process for preparing a carbodiimide is provided, preferably for preparing a carbodiimide having formula (I), wherein the process comprises use of a catalytic compound which is less toxic than catalytic compounds of the prior art, especially in comparison with known carbonyl compounds, and which can be prepared in a cost efficient manner saving resources. Further, the present invention allows for homogeneous as well as heterogeneous processes.
The carbodiimides of the present invention display a high hydrolysis inhibition action and light stability. Further, the carbodiimides of the present invention have good compatibility with the polyaddition and polycondensation products containing ester groups, in particular with polyester urethane rubbers, and can also be homogeneously mixed with these materials in the melt without problems.
The carbodimides of the present invention are very suitable as acceptor for carboxyl compounds and are therefore preferably used as stabilizers against hydrolytic degradation of compounds containing ester groups, for example polymers containing ester groups, e.g. polycondensation products such as thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyether esters, polyamides, polyesteramides, polycaprolactones and also unsaturated polyester resins and polyester esters, e.g. block copolymers of polyethylene terephthalate or polybutylene terephthalate and polycaprolactone, and polyaddition products, e.g. polyurethanes, polyureas and polyurethane-polyurea elastomers containing ester groups.
Owing to their good solubility in the formative components for preparing polyurethanes and their good compatibility with the polyurethanes formed, the carbodiimides of the present invention are particularly suitable as stabilizers against hydrolytic degradation of polyurethanes, preferably compact or cellular polyurethane elastomers and in particular thermoplastic polyurethanes, and also cellulose or compact elastomers.
Therefore, the present invention relates to a process for preparing a carbodiimide, preferably for preparing a carbodiimide having formula (I):
Q
1-[Q2-N═C═N]n-Q3-Q4 (I)
wherein n is in the range of from 1 to 500, preferably in the range of from 2 to 20, more preferably in the range of from 3 to 15, more preferably in the range of from 4 to 10, and wherein Q2 and Q3 stands for an organic backbone and Q1 and Q4 stands for an organic end group, the process comprising
It is preferred that from 90 to 100 mol-%, more preferably from 95 to 100 mol-%, more preferably from 99 to 100 mol-%, of the metal M comprised in the catalytic compound, calculated as elemental M, is bound to oxygen via one or more single bonds, via one or more double bonds, or via one or more single and double bonds.
It is preferred that at least a portion of the metal M comprised in the catalytic compound is bound to oxygen via one or more double bonds, more preferably via one or two double bonds, more preferably via two double bonds.
It is preferred that the metal M is in oxidation state +IV or +VI, more preferably in oxidation state +VI.
It is preferred that the catalytic compound comprises, more preferably consists of, one or more salts, wherein the one or more salts more preferably comprise one or more of an anionic complex of one or more atoms of the metal M, a cationic complex of one or more atoms of the metal M, a cationic oxidic compound of one or more atoms of the metal M, and an anionic oxidic compound of one or more atoms of the metal M, more preferably one or more of an anionic complex of one or more atoms of the metal M and an anionic oxidic compound of one or more atoms of the metal M.
It is preferred that the catalytic compound comprises a salt comprising a cation selected from the group consisting of ammonium (NH4+), trimethylammonium (NH(CH3)3+), anilinium (C6H5NH3+), the diammonium ion of ethylenediamine (H3NCH2CH2NH32+), tetrabutylammonium (Bu4N+), Li+, Na+, K+, Mg2+, Ca2+, Sr2+, Ba2+, and a mixture of two or more thereof,
more preferably selected from the group consisting of Li+, Na+, K+, and a mixture of two or more thereof,
wherein the catalytic compound more preferably comprises a salt comprising Li+.
It is preferred that the catalytic compound comprises an anionic or cationic complex of one or more atoms of the metal M, and wherein the complex further comprises one or more, optionally substituted, ligands L, more preferably one or two, optionally substituted, ligands L.
Two specific alternatives apply with respect to the number of atoms of the metal M of the catalytic compound, in the case where the catalytic compound comprises an anionic or cationic complex of one or more atoms of the metal M, and wherein the complex further comprises one or more, optionally substituted, ligands L, preferably one or two, optionally substituted, ligands L.
According to a first alternative, it is preferred that the catalytic compound comprises a complex, more preferably an anionic complex or a cationic complex, comprising a single atom of the metal M, wherein one or more ligands L independently from each other are coordinated to the single atom of the metal M,
wherein the one or more ligands L independently from each other more preferably comprise one or more of O and S, more preferably two O, or two S, or one O and one S, and
wherein the one or more ligands L independently from each other more preferably are coordinated to the single atom of the metal M via one O, or one S, or two O, or two S, or one O and one S, more preferably via two O or two S.
According to a second alternative, it is preferred that the catalytic compound comprises a complex, more preferably an anionic complex or a cationic complex, comprising two atoms of the metal M, wherein one or more ligands L independently from each other coordinate to two atoms of the metal M,
wherein the one or more ligands L independently from each other more preferably comprise one or more of O and S, more preferably two O, or two S, or one O and one S, and wherein the one or more ligands L independently from each other more preferably coordinate to the two atoms of the metal M via one O, or one S, or two O, or two S, or one O and one S, more preferably via two O, wherein the one or more ligands L more preferably are a bridging ligand.
Further in the case where the catalytic compound comprises an anionic or cationic complex of one or more atoms of the metal M, and wherein the complex further comprises one or more, optionally substituted, ligands L, preferably one or two, optionally substituted, ligands L, it is preferred that one or more ligands L independently from each other comprise a hydroxyl anion, wherein more preferably one, two, or three of the one or more ligands L independently from each other are a hydroxyl anion.
Further, three specific alternatives apply with respect to the one or more ligands L of the catalytic compound, in the case where the catalytic compound comprises an anionic or cationic complex of one or more atoms of the metal M, and wherein the complex further comprises one or more, optionally substituted, ligands L, more preferably one or two, optionally substituted, ligands L.
According to a first alternative, it is preferred that the one or more ligands L independently from each other are selected from the group consisting of 1,1-methanediolate, 1,1-thiomethanediolate, 1,1-dithiomethanediolate, formate, thioformate, dithioformate, 1,2-ethanediolate, 1,2-thioethanediolate, 1,2-dithioethanediolate, 1,3-propanediolate, 1,3-thiopropanediolate, 1,3-dithiopropanediolate, and a mixture of two or more thereof, more preferably from the group consisting of 1,1-methanediolate, 1,1-thiomethanediolate, 1,1-dithiomethanediolate, formate, thioformate, dithioformate, 1,2-ethanediolate, 1,2-thioethanediolate, 1,2-dithioethanediolate, and a mixture of two or more thereof, more preferably from the group consisting of formate, thioformate, dithioformate, 1,2-ethanediolate, 1,2-thioethanediolate, 1,2-dithioethanediolate, and a mixture of two or more thereof,
more preferably from the group consisting of formate, thioformate, dithioformate, 1,2-ethanediolate, 1,2-thioethanediolate, 1,2-dithioethanediolate, and a mixture of two or more thereof,
wherein the one or more ligands L more preferably are one or more of dithioformate and 1,2-ethanediolate.
In the case where one or more ligands L independently from each other are selected from the group consisting of 1,1-methanediolate, 1,1-thiomethanediolate, 1,1-dithiomethanediolate, formate, thioformate, dithioformate, 1,2-ethanediolate, 1,2-thioethanediolate, 1,2-dithioethanediolate, 1,3-propanediolate, 1,3-thiopropanediolate, 1,3-dithiopropanediolate, and a mixture of two or more thereof, it is preferred that the one or more ligands L are substituted with one or more substituents, more preferably with one or two substituents.
In the case where one or more ligands L are substituted with one or more substituents, preferably with one or two substituents, it is preferred that the one or more substituents are independently from each other selected from the group consisting of Oxo (═O), Thio (═S), hydroxyl, NR1R2, wherein R1 and R2 independently from each other are (C1-C6)alkyl, more preferably methyl, ethyl, n-propyl, or n-butyl, more preferably methyl, optionally substituted (C1-C12)alkyl, optionally substituted cycloaliphatic (C5-C10)alkyl, optionally substituted (C6-C9)aryl, optionally substituted (C7-C15)aralkyl, and optionally substituted (C7-C15)alkaryl,
more preferably selected from the group consisting of optionally substituted (C1-C8)alkyl, optionally substituted cycloaliphatic (C5-C6)alkyl, optionally substituted (C6-C9)aryl, optionally substituted (C7-C12)aralkyl, and optionally substituted (C7-C12)alkaryl,
more preferably selected from the group consisting of optionally substituted (C1-C6)alkyl, optionally substituted cycloaliphatic (C5-C6)alkyl, optionally substituted (C6)aryl, and optionally substituted (C7-C10)alkaryl,
more preferably selected from the group consisting of optionally substituted (C7-C9)alkaryl,
wherein the optionally substituted (C1-C12)alkyl, the optionally substituted cycloaliphatic (C5-C10)alkyl, the optionally substituted (C6-C9)aryl, the optionally substituted (C7-C15)aralkyl, and the optionally substituted (C7-C15)alkaryl, are more preferably substituted with one or more of F, Cl, Br, I, OH, SH, and NR3R4, wherein R3 and R4 independently from each other are H, or (C1-C6)alkyl, more preferably methyl, ethyl, n-propyl, or n-butyl, more preferably methyl,
wherein one or more of the optionally substituted (C1-C12)alkyl, the optionally substituted cycloaliphatic (C5-C10)alkyl, the optionally substituted (C6-C9)aryl, the optionally substituted (C7-C15)aralkyl, and the optionally substituted (C7-C15)alkaryl, independently from each other are more preferably linear, branched, or cyclic, more preferably linear.
According to a second alternative, it is preferred that the catalytic compound comprises a complex, more preferably an anionic complex or a cationic complex, comprising a single atom of the metal M, wherein one or more ligands L independently from each other are coordinated to the single atom of the metal M,
wherein the one or more ligands L independently from each other more preferably comprise a carboxylate,
more preferably a carboxylate of an amino acid, wherein the amino acid is preferably selected from the group consisting of alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, proline, phenylalanine, serine, threonine, tryptophan, tyrosine, valine.
According to a third alternative, it is preferred that the catalytic compound comprises a complex,
more preferably an anionic complex or a cationic complex, comprising two atoms of the metal M, wherein one or more ligands L independently from each other coordinate to two atoms of the metal M,
wherein the one or more ligands L independently from each other more preferably comprise a carboxylate,
more preferably a carboxylate of an amino acid, wherein the amino acid is more preferably selected from the group consisting of alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, proline, phenylalanine, serine, threonine, tryptophan, tyrosine, valine.
Two specific alternatives apply with respect to the metal M of the catalytic compound.
According to a first alternative, it is preferred that the metal M is Mo.
In the case where the metal M is Mo, it is preferred that the catalytic compound comprises,
more preferably consists of, one or more of MoO2 and MoO3, wherein the catalytic compound more preferably comprises, more preferably consists of, MoO3.
Further in the case where the metal M is Mo, it is preferred that the catalytic compound comprises a salt comprising a molybdate anion, optionally a hydrated molybdate anion, more preferably a molybdate anion selected from the group consisting of MoO42−, Mo2O72−, Mo3O102−, Mo4O132−, Mo5O162-, Mo6O192-, Mo7O246-, Mo8O264−, and a mixture of two or more thereof, wherein the catalytic compound more preferably comprises MoO42−.
Further in the case where the metal M is Mo, it is preferred that the catalytic compound comprises, more preferably consists of, one or more of Li2MoO4, Na2MoO4, and K2MoO4, more preferably one or more of Li2MoO4 and K2MoO4, wherein the catalytic compound more preferably comprises, more preferably consists of, Li2MoO4.
Further in the case where the metal M is Mo, it is preferred that the catalytic compound comprises, more preferably consists of, one or more of Li2MoO4, K2MoO4, Na2MoO4, bis(diethyldithiocarbamato)-dioxomolybdenum(VI), potassium dioxobis[glycolato(2−)]-molybdate(VI), sodium dioxobis[methylglycolato(2−)]molybdate(VI), a dihydroxydi-μ-hydroxytetraoxodimolybdenum carboxylate, more preferably dihydroxydi-μ-hydroxytetraoxo-dimolybdenum 2-(Dimethylamino)-3-phenylpropanoate or dihydroxydi-μ-hydroxytetraoxo-dimolybdenum 2-amino-3-phenylpropanoate.
According to a second alternative, it is preferred that the metal M is W.
In the case where the metal M is W, it is preferred that the catalytic compound comprises, more preferably consists of, one or more of WO2 and WO3, wherein the catalytic compound more preferably comprises, more preferably consists of, WO3.
Further in the case where the metal M is W, it is preferred that the catalytic compound compris-es a tungstate anion, optionally a hydrated tungstate anion, more preferably a tungstate anion WO42-.
It is preferred that from 95 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.9 to 100 weight-%, of the catalytic compound consist of the metal M, O, optionally H, optionally C, optionally N, and optionally S, preferably of the metal M, O, H, C, and N.
It is preferred that the mixture obtained in (i) comprises an amount in the range of from 0 to 5 mol-%, more preferably in the range of from 0 to 2.5 mol-%, more preferably in the range of from 0 to 2.0 mol-%, more preferably in the range of from 0 to 1.5 mol-%, more preferably in the range of from 0 to 1.0 mol-%, more preferably in the range of from 0 to 0.7 mol-%, more prefer-ably in the range of from 0 to 0.5 mol-%, more preferably in the range of from 0 to 0.2 mol-%, more preferably in the range of from 0 to 0.1 mol-%, more preferably in the range of from 0 to 0.05 mol-%, more preferably in the range of from 0 to 0.02 mol-%, more preferably in the range of from 0 to 0.01 mol-%, of a phospholene oxide, calculated as molar amount of the phospho-lene oxide, more preferably of a compound comprising a phosphorous oxygen double bond, calculated as molar amount of the compound comprising a phosphorous oxygen double bond, more preferably of a compound comprising P, calculated as molar amount of the compound comprising P, more preferably of P, calculated as elemental P, based on the amount of the one or more isocyanates, calculated as sum of the molar amounts of the one or more isocyanates, wherein the mixture obtained in (i) more preferably is essentially free of a phospholene oxide, more preferably of a compound comprising a phosphorous oxygen double bond, more preferably of a compound comprising P, and more preferably of P.
It is preferred that the mixture obtained in (i) comprises an amount in the range of from 0 to 5 mol-%, more preferably in the range of from 0 to 1.0 mol-%, more preferably in the range of from 0 to 0.1 mol-%, more preferably in the range of from 0 to 0.01 mol-%, of an alkali metal, calculated as elemental alkali metal, based on the amount of the one or more isocyanates, cal-culated as sum of the molar amounts of the one or more isocyanates, wherein the mixture ob-tained in (i) is more preferably essentially free of an alkali metal.
It is preferred that the mixture obtained in (i) comprises an amount in the range of from 0 to 5 mol-%, more preferably in the range of from 0 to 1.0 mol-%, more preferably in the range of from 0 to 0.1 mol-%, more preferably in the range of from 0 to 0.01 mol-%, of Mg, calculated as elemental Mg, more preferably of one or more of Mg and Ca, calculated as elemental Mg and elemental Ca, respectively, more preferably of one or more of Mg, Ca, and Ba, calculated as elemental Mg, as elemental Ca and elemental Ba, respectively, more preferably of one or more of an alkali earth metal, calculated as elemental alkali earth metal, based on the amount of the one or more isocyanates, calculated as sum of the molar amounts of the one or more isocya-nates, wherein the mixture obtained in (i) more preferably is essentially free of Mg, more prefer-ably of one or more of Mg and Ca, more preferably of one or more of Mg, Ca, and Ba, more preferably of one or more of an alkali earth metal.
It is preferred that the one or more isocyanates comprised in the mixture according to (i) com-prise, more preferably consist of, one or more of a primary isocyanate, a secondary isocyanate and a tertiary isocyanate.
It is preferred that the one or more isocyanates comprised in the mixture according to (i) com-prise, more preferably consist of, one or more of a monoisocyanate and a diisocyanate.
It is preferred that the one or more isocyanates comprised in the mixture according to (i) com-prise, more preferably consist of, one or more of a primary monoisocyanate, a primary diisocya-nate, a secondary monoisocyanate, a secondary diisocyanate, a tertiary monoisocyanate, and a tertiary diisocyanate, wherein the one or more isocyanates more preferably comprise, more preferably consist of, one or more of a secondary diisocyanate and a tertiary diisocyanate.
It is preferred that the one or more isocyanates comprised in the mixture according to (i) com-prise, more preferably consist of, an isocyanate, more preferably a primary monoisocyanate, a secondary monoisocyanate or a tertiary monoisocyanate, having the formula (II):
OCN—C(R6,R7)—R8—C(R9,R10)—R11 (II),
wherein R6 and R7 independently from one another are H or alkyl, wherein the alkyl is more preferably linear or branched, more preferably linear,
wherein R6 and R7 independently from one another more preferably are (C1-C22)alkyl, more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R6 and R7 independently from one another more preferably are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl,
wherein R9 and R10 independently from one another is H or alkyl, wherein the alkyl is more preferably linear or branched, more preferably linear,
wherein R9 and R10 independently from one another more preferably are H or (C1-C22)alkyl, more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R9 and R10 independently from one another more preferably are H, methyl, ethyl, pro-pyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl,
wherein R8 is alkylene, alkarylene, aralkylene, or arylene, wherein the one or more of the al-kylene, the alkarylene, the aralkylene, and the arylene is more preferably linear, branched or cyclic,
wherein R8 is more preferably selected from the group consisting of (C1-C16)alkylene, cycloali-phatic (C5-C20)alkylene, (C6-C18)arylene, (C7-C20)aralkylene, and (C7-C20)alkarylene, preferably selected from the group consisting of (C1-C5)alkylene, cycloaliphatic (C5-C10)alkylene, (C6-C9)arylene, (C7-C15)aralkylene, and (C7-C15)alkarylene, more preferably selected from the group consisting of (C1-C6)alkylene, (C5-C6)alkylene, (C6)arylene, (C7-C12)aralkylene, and (C7-C12)alkarylene, more preferably selected from the group consisting of (C3-C6)alkylene, (C7-C10)aralkylene, and (C7-C10)alkarylene, more preferably selected from the group consisting of (C7-C9)aralkylene, and (C7-C9)alkarylene, wherein R8 is more preferably selected from the group consisting of (C8-C9)aralkylene, and (C8-C9)alkarylene,
wherein R8 is more preferably selected from the group consisting of methylene, ethylene, tri-methylene, tetramethylene, pentamethylene, hexamethylene, ortho-phenylene, meta-phenylene, and para-phenylene,
wherein R8 is more preferably selected from the group consisting of pentamethylene, hexa-methylene, ortho-phenylene, meta-phenylene, and para-phenylene,
wherein R8 more preferably is para-phenylene,
wherein R11 is selected from the group consisting of isopropenyl, NCNR12, NHCONHR13, NHCONR14R15, and NHCOOR16,
wherein R12 is one or more of (C1-C18)alkylene, (C5-C18)cycloalkylene, arylene, (C7-C18)alkarylene and (C7-C18)aralkylene, more preferably one or more of (C7-C18)alkylarylene and (C7-C18)aralkylene,
wherein R13, R14, R15, and R16 independently from one another are selected from the group con-sisting of alkyl, cycloalkyl, alkaryl, aralkyl, a polyester group, a polyamide group, and —(CH2)h—O—[(CH2)k—O]g—R17,
wherein h is in the range of from 1 to 3, k is in the range of from 1 to 3, g is in the range of from 0 to 12, and wherein R17 is H or (C1-C4)alkyl,
wherein R13, R14, R15, and R16 independently from one another are more preferably selected from the group consisting of (C1-C12)alkyl, cycloaliphatic (C5-C10)alkyl, (C6-C9)aryl, (C7-C15)aralkyl, and (C7-C15)alkaryl, wherein one or more of the (C1-C12)alkyl, cycloaliphatic (C5-C10)alkyl, (C6-C9)aryl, (C7-C15)aralkyl, and (C7-C15)alkaryl independently from each other prefer-ably are linear, branched, or cyclic, more preferably linear,
more preferably selected from the group consisting of (C1-C5)alkyl, cycloaliphatic (C5-C6)alkyl, (C6-C9)aryl, (C7-C12)aralkyl, and (C7-C12)alkaryl,
more preferably selected from the group consisting of (C1-C6)alkyl, cycloaliphatic (C5-C6)alkyl, and (C6)aryl,
more preferably selected from the group consisting of (C1-C5)alkyl,
more preferably selected from the group consisting of (C1-C4)alkyl,
wherein more preferably R13, R14, R15, and R16 independently from one another are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl.
It is preferred that the one or more isocyanates comprised in the mixture according to (i) comprises, more preferably consists of, an isocyanate, more preferably a tertiary diisocyanate, hav-ing the formula (III):
OCN—C(R18,R19)—R20—C(R21,R22)—NCO (III),
wherein R18, R19, R21 and R22 independently from one another are alkyl, wherein the alkyl more preferably is linear or branched,
wherein R18, R19, R21 and R22 independently from one another more preferably are (C1-C22)alkyl,
more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl, more preferably (C1-C8)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R18, R19, R21 and R22 independently from one another more preferably are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl,
wherein R20 is alkylene, alkarylene, aralkylene, or arylene, wherein one or more of the alkylene, the alkarylene, the aralkylene, and the arylene independently from each other are linear, branched or cyclic, more preferably linear,
wherein R20 is more preferably selected from the group consisting of (C1-C15)alkylene, cycloali-phatic (C5-C20)alkylene, (C6-C18)arylene, (C7-C20)aralkylene, and (C7-C20)alkarylene, more preferably selected from the group consisting of (C1-C8)alkylene, cycloaliphatic (C5-C10)alkylene, (C6-C9)arylene, (C7-C15)aralkylene, and (C7-C15)alkarylene, more preferably selected from the group consisting of (C1-C6)alkylene, (C5-C6)alkylene, (C6)arylene, (C7-C12)aralkylene, and (C7-C12)alkarylene, more preferably selected from the group consisting of (C3-C6)alkylene, (C7-C10)aralkylene, and (C7-C10)alkarylene, more preferably selected from the group consisting of (C7-C9)aralkylene, and (C7-C9)alkarylene, wherein R20 is more preferably selected from the group consisting of (C8-C9)aralkylene, and (C8-C9)alkarylene,
wherein R20 is more preferably selected from the group consisting of methylene, ethylene, tri-methylene, tetramethylene, pentamethylene, hexamethylene, ortho-phenylene, meta-phenylene, and para-phenylene,
wherein R20 more preferably is selected from the group consisting of pentamethylene, hexa-methylene, ortho-phenylene, meta-phenylene, and para-phenylene,
wherein R20 more preferably is para-phenylene.
In the case where the one or more isocyanates comprised in the mixture according to (i) comprises, more preferably consists of, an isocyanate, more preferably a tertiary diisocyanate, hav-ing the formula (III):
OCN—C(R18,R19)—R20—C(R21,R22)—NCO (III),
wherein R18, R19, R21 and R22 independently from one another are alkyl, wherein the alkyl more preferably is linear or branched,
wherein R20 is alkylene, alkarylene, aralkylene, or arylene, wherein one or more of the alkylene, the alkarylene, the aralkylene, and the arylene independently from each other are linear, branched or cyclic, more preferably linear, it is preferred that the one or more isocyanates com-prised in the mixture according to (i) comprises, more preferably consists of, a tertiary diisocya-nate, more preferably 1,3-bis(1-methyl-1-isocyanatoethyl)-benzene.
It is preferred that the one or more isocyanates comprised in the mixture according to (i) comprises from 10 to 44 weight-%, more preferably from 15 to 40 weight-%, more preferably from 32 to 37 weight-%, of NCO, based on the amount of the one or more isocyanates, more prefer-ably of the amount of the one or more tertiary isocyanates, calculated as sum of the weights of the one or more isocyanates, more preferably of the sum of the weights of the one or more ter-tiary isocyanates.
It is preferred that the one or more isocyanates comprised in the mixture according to (i) com-prise, more preferably consist of, an isocyanate, more preferably a tertiary monoisocyanate, having the formula (IV):
OCN—C(R25,R26)—R27—C(R28,R29)—R30 (IV),
wherein R25 and R26 independently from one another is alkyl, wherein the alkyl is more preferably linear or branched, more preferably linear,
wherein R25 and R26 independently from one another more preferably is (C1-C22)alkyl, more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl, more preferably (C1-C8)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R25 and R26 independently from one another more preferably are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl,
wherein R28 and R29 independently from one another are H or alkyl, wherein the alkyl is more preferably linear or branched, more preferably linear,
wherein R28 and R29 independently from one another more preferably are H or, (C1-C22)alkyl,
more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl, more preferably (C1-C8)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R28 and R29 independently from one another more preferably are H, methyl, ethyl, pro-pyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl,
wherein R27 is alkylene, alkarylene, aralkylene, or arylene, wherein one or more of the alkylene, the alkarylene, the aralkylene, and the arylene independently from each other are branched or cyclic,
wherein R27 is more preferably selected from the group consisting of (C1-C16)alkylene, cycloali-phatic (C5-C20)alkylene, (C6-C18)arylene, (C7-C20)aralkylene, and (C7-C20)alkarylene, more preferably selected from the group consisting of (C1-C8)alkylene, cycloaliphatic (C5-C10)alkylene, (C6-C9)arylene, (C7-C15)aralkylene, and (C7-C15)alkarylene, more preferably selected from the group consisting of (C1-C6)alkylene, (C5-C6)alkylene, (C6)arylene, (C7-C2)aralkylene, and (C7-C12)alkarylene, more preferably selected from the group consisting of (C3-C6)alkylene, (C7-C10)aralkylene, and (C7-C10)alkarylene, more preferably selected from the group consisting of (C7-C9)aralkylene, and (C7-C9)alkarylene, wherein R27 is more preferably selected from the group consisting of (C8-C9)aralkylene, and (C8-C9)alkarylene,
wherein R27 is more preferably selected from the group consisting of methylene, ethylene, tri-methylene, tetramethylene, pentamethylene, hexamethylene, ortho-phenylene, meta-phenylene, and para-phenylene,
wherein R27 more preferably is selected from the group consisting of pentamethylene, hexa-methylene, ortho-phenylene, meta-phenylene, and para-phenylene,
wherein R27 more preferably is para-phenylene,
wherein R30 is selected from the group consisting of isopropenyl, NCNR31, NHCONHR32, NHCONR33R34, and NHCOOR35,
wherein R31 is (C1-C18)alkylene, (C5-C18)cycloalkylene, arylene, (C7-C18)alkarylene or (C7-C18)aralkylene, more preferably (C7-C18)alkylarylene or (C7-C18)aralkylene, wherein R32, R33, R34, and R35 independently from one another are selected from the group con-sisting of alkyl, cycloalkyl, alkaryl, aralkyl, a polyester group, a polyether group, a polyamide group, and —(CH2)h—O—[(CH2)k-0]g-R36,
wherein h is in the range of from 1 to 3, k is in the range of from 1 to 3, g is in the range of from 0 to 12, and wherein R36 is H or (C1-C4)alkyl, wherein R32, R33, R34, and R35 independently from one another is more preferably selected from the group consisting of (C1-C12)alkyl, cycloaliphatic (C5-C10)alkyl, (C6-C5)aryl, (C7-C15)aralkyl, and (C7-C15)alkaryl, wherein one or more of the (C1-C12)alkyl, cycloaliphatic (C5-C10)alkyl, (C6-C9)aryl, (C7-C15)aralkyl, and (C7-C15)alkaryl independently from each other are linear, branched, or cyclic, more preferably linear,
more preferably selected from the group consisting of (C1-C8)alkyl, cycloaliphatic (C5-C6)alkyl, (C6-C9)aryl, (C7-C12)aralkyl, and (C7-C12)alkaryl,
more preferably selected from the group consisting of (C1-C6)alkyl, cycloaliphatic (C5-C6)alkyl, and (C6)aryl,
more preferably selected from the group consisting of (C1-C5)alkyl,
more preferably selected from the group consisting of (C1-C4)alkyl,
wherein more preferably R32, R33, R34, and R35 independently from one another are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl.
In the case where the one or more isocyanates comprised in the mixture according to (i) com-prise, preferably consist of, an isocyanate, preferably a tertiary monoisocyanate, having the formula (IV):
OCN—C(R25,R26)—R27—C(R28,R29)—R30 (IV),
wherein R25 and R26 independently from one another is alkyl, wherein the alkyl is preferably lin-ear or branched, more preferably linear,
wherein R28 and R29 independently from one another are H or alkyl, wherein the alkyl is preferably linear or branched, more preferably linear,
wherein R27 is alkylene, alkarylene, aralkylene, or arylene, wherein one or more of the alkylene, the alkarylene, the aralkylene, and the arylene independently from each other are branched or cyclic,
wherein R30 is selected from the group consisting of isopropenyl, NCNR31, NHCONHR32, NHCONR33R34, and NHCOOR35,
wherein R31 is (C1-C18)alkylene, (C5-C18)cycloalkylene, arylene, (C7-C18)alkarylene or (C7-C18)aralkylene, preferably (C7-C18)alkylarylene or (C7-C18)aralkylene,
wherein R32, R33, R34, and R35 independently from one another are selected from the group con-sisting of alkyl, cycloalkyl, alkaryl, aralkyl, a polyester group, a polyether group, a polyamide group, and —(CH2)h—O—[(CH2)k-0]g-R36,
wherein h is in the range of from 1 to 3, k is in the range of from 1 to 3, g is in the range of from 0 to 12, and wherein R36 is H or (C1-C4)alkyl, it is preferred that R30 is NHCOOR35 wherein R35 is a polyether group, wherein R35 is more preferably O—(R40—O)m—R41,
wherein R40 is an alkylene group,
wherein R40 is more preferably selected from the group consisting of methylene, ethylene, tri-methylene, tetramethylene, pentamethylene, hexamethylene, ortho-phenylene, meta-phenylene, para-phenylene,
wherein R40 more preferably is ethylene,
wherein R41 is alkyl, wherein the alkyl is more preferably linear or branched, more preferably linear,
wherein R41 more preferably is (C1-C22)alkyl, more preferably (C1-C18)alkyl, more preferably par-tially unsaturated (C1-C18)alkyl, more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl,
more preferably (C1-C8)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R41 more preferably is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl, and
wherein m is an integer of 0 to 150, more preferably an integer of 2 to 150, preferably an integer of 5 to 100, more preferably an integer of 7 to 50, more preferably an integer of 8 to 25, more preferably an integer of 9 to 20, more preferably an integer of 10 to 15.
In the case where R30 is NHCOOR35, and wherein R35 is O—(R40—O)m—R41, it is preferred that R41 is substituted alkyl, wherein the substituted alkyl more preferably comprises one or more sub-stituents, wherein the one or more substituents of the substituted alkyl independently from each other are more preferably selected from the group consisting of (C1-C3)alkoxy, hydroxyl, amino, halides, and combinations of two or more thereof, more preferably from the group consisting of (C1-C2)alkoxy, hydroxyl, amino, chloro, bromo, fluoro, and combinations of two or more thereof,
more preferably from the group consisting of hydroxyl, amino, chloro, and combinations thereof,
wherein more preferably the one or more substituents independently from each other are hy-droxyl,
wherein the substituted alkyl preferably comprises one or more substituents, more preferably one to four substituents, more preferably 1one to three substituents, more preferably one or two substituents, wherein the substituted alkyl more preferably comprises one substituent.
Further in the case where R30 is NHCOOR35, and wherein R35 is O—(R40—O)m—R41, it is preferred that R41 is a partially unsaturated alkyl, wherein R41 more preferably comprises one or more,
more preferably from one to five, more preferably from one to three, more preferably one, C═C double bonds.
Further in the case where R30 is NHCOOR35, and wherein R35 is O—(R40—O)m—R41, it is preferred that m=0,
wherein R41 is alkyl, wherein the alkyl is more preferably partially unsaturated, wherein the alkyl is more preferably substituted,
wherein R41 more preferably is (C1-C22)alkyl, more preferably (C12-C22)alkyl, more preferably partially unsaturated (C12-C22)alkyl, more preferably partially unsaturated (C16-C20)alkyl, more preferably partially unsaturated (C18-C19)alkyl, wherein R41 preferably comprises one or more,
more preferably from one to five, more preferably from one to three, more preferably one, C—C double bonds, and wherein R41 more preferably is (2)-Octadec-9-en-yl (oleyl).
It is preferred that the one or more isocyanates comprises, preferably consists of, an aliphatic monoisocyanate or an aliphatic diisocyanate,
wherein the aliphatic monoisocyanate is more preferably selected from the group consisting of (C1-C20)alkylene monoisocyanates, and a mixture of two or more thereof, more preferably from the group consisting of (C3-C18)alkylene monoisocyanates, and a mixture of two or more thereof, more preferably from the group consisting of (C6-C13)alkylene monoisocyanates, and a mixture of two or more thereof,
wherein the aliphatic diisocyanate is more preferably selected from the group consisting of a (C1-C20)alkylene diisocyanates, and a mixture of two or more thereof, more preferably from the group consisting of (C3-C18)alkylene diisocyanates, and a mixture of two or more thereof, more preferably from the group consisting of (C6-C13)alkylene diisocyanates, and a mixture of two or more thereof,
wherein the aliphatic diisocyanate is more preferably selected from the group consisting of 1,6-diisocyanatohexane (HDI), 1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (4,4′-diisocyanato dicyclohexylmethane; H12MDI), 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane (isophorone diisocyanate; IPDI), and a mixture of two or more thereof,
wherein the aliphatic diisocyanate more preferably is 1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane (4,4′-diisocyanato dicyclohexylmethane; H12MDI).
It is preferred that the one or more isocyanates comprised in the mixture according to (i) com-prise, more preferably consist of, a tertiary monoisocyanate, more preferably 3-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate (TMI).
It is preferred that the one or more isocyanates comprised in the mixture according to (i) com-prise, more preferably consist of, an aromatic isocyanate, more preferably one or more of 1,3-diisopropyl-2-isocyanato benzene, 1,3,5-triisopropyl-2,4-diisocyanato benzene, and 1,3-Bis(2-isocyanatopropan-2-yl)benzene, more preferably 1,3-Bis(2-isocyanatopropan-2-yl)benzene.
It is preferred that Q1 and Q4 independently from each other are —NCO or R11 or R30, and
wherein Q2 and Q3 independently from each other are —C(R6,R7)—R8—C(R9,R10)— or —C(R18,R19)—R20—C(R21,R22)— or —C(R25,R26)—R27—C(R28,R29)—,
wherein R6 and R7 are defined as in any one of the embodiments hereinabove,
wherein R8 is defined as in any one of the embodiments hereinabove,
wherein R9 and R10 are defined as in any one of the embodiments hereinabove,
wherein R11 is defined as in any one of the embodiments hereinabove,
wherein R18 and R19 are defined as in any one of the embodiments hereinabove,
wherein R20 is defined as in any one of the embodiments hereinabove,
wherein R21 and R22 are defined as in any one of the embodiments hereinabove,
wherein R25 and R26 are defined as in any one of the embodiments hereinabove,
wherein R27 is defined as in any one of the embodiments hereinabove,
wherein R28 and R29 are defined as in any one of the embodiments hereinabove,
wherein R30 is defined as in any one of the embodiments hereinabove.
It is preferred that the reaction conditions in (ii) comprise a temperature in the range of from 50 to 220° C., more preferably in the range of from 60 to 200° C., more preferably in the range of from 80 to 180° C., more preferably in the range of from 130 to 180° C., more preferably in the range of from 150 to 180° C.
It is preferred that the gas atmosphere in (ii) comprises, more preferably consists of, an inert gas, wherein the gas atmosphere in (ii) more preferably comprises, more preferably consists of, one or more of nitrogen and argon.
It is preferred that the reaction conditions in (ii) comprise a pressure in the range of from 1 to 1000 hPa(abs), more preferably in the range of from 2 to 1000 hPa(abs), more preferably in the range of from 2.5 to 1000 hPa(abs).
It is preferred that the reaction conditions in (ii) comprise agitating the mixture obtained in (i),
more preferably stirring the mixture obtained in (i).
It is preferred that the mixture obtained in (i) is subjected to the reaction conditions in (ii) for a duration in the range of from 1 to 50 h, more preferably in the range of from 1.5 to 40 h, more preferably in the range of from to 2 to 25 h.
It is preferred that the mixture according to (i) is provided in a reactor, wherein the reactor more preferably comprises a reactor vessel or a tubular reactor.
It is preferred that the mixture provided in (i) further comprises a first end-capping agent, wherein the first end-capping agent has the formula (V):
HX—(R44—Y)n—R45 (V),
wherein X is O, S, or NR42, wherein R42 is alkyl, wherein the alkyl is preferably linear or branched, more preferably linear, wherein X is preferably O,
wherein R42 is more preferably (C1-C22)alkyl, more preferably (C1-C18)alkyl, more preferably par-tially unsaturated (C1-C18)alkyl, more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl,
more preferably (C1-C8)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R42 more preferably is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl,
wherein Y is O, S, or NR43, wherein R43 is alkyl, wherein the alkyl is more preferably linear or branched, more preferably linear, wherein X is more preferably O,
wherein R43 is more preferably (C1-C22)alkyl, more preferably (C1-C18)alkyl, more preferably par-tially unsaturated (C1-C18)alkyl, more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl,
more preferably (C1-C8)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R43 more preferably is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl,
wherein R44 is an alkylene group,
wherein R44 is more preferably selected from the group consisting of methylene, ethylene, tri-methylene, tetramethylene, pentamethylene, hexamethylene, ortho-phenylene, meta-phenylene, and para-phenylene,
wherein R44 more preferably is ethylene,
wherein R45 is alkyl, wherein the alkyl is preferably linear or branched, more preferably linear,
wherein R45 is more preferably (C1-C22)alkyl, more preferably (C1-C18)alkyl, more preferably par-tially unsaturated (C1-C18)alkyl, more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl,
more preferably (C1-C8)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R45 more preferably is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl, and
wherein n is an integer of 0 to 150, more preferably an integer of 2 to 150, preferably an integer of 5 to 100, more preferably an integer of 7 to 50, more preferably an integer of 8 to 25, more preferably an integer of 9 to 20, more preferably an integer of 10 to 15,
wherein the first end-capping agent more preferably is a methylpolyethylene glycol.
In the case where the mixture provided in (i) further comprises a first end-capping agent, wherein the first end-capping agent has the formula (V):
HX—(R44—Y)n—R45 (V),
wherein X is O, S, or NR42, wherein R42 is alkyl, wherein Y is O, S, or NR43, wherein R43 is alkyl,
wherein R44 is an alkylene group, wherein R45 is alkyl, and wherein n is an integer of 0 to 150, it is preferred that R45 is substituted alkyl, wherein the substituted alkyl preferably comprises one or more substituents, wherein the one or more substituents of the substituted alkyl independent-ly from each other are more preferably selected from the group consisting of (C1-C3)alkoxy, hy-droxyl, amino, halides, and combinations of two or more thereof, more preferably from the group consisting of (C1-C2)alkoxy, hydroxyl, amino, chloro, bromo, fluoro, and combinations of two or more thereof, more preferably from the group consisting of hydroxyl, amino, chloro, and combi-nations thereof, wherein more preferably the one or more substituents independently from each other are hydroxyl,
wherein the substituted alkyl group more preferably comprises one or more substituents, preferably 1 to 4 substituents, more preferably 1 to 3 substituents, more preferably 1 or 2 substitu-ents, wherein the substituted alkyl group more preferably comprises 1 substituent.
Further in the case where the mixture provided in (i) further comprises a first end-capping agent,
wherein the first end-capping agent has the formula (V):
HX—(R44—Y)n—R45 (V),
wherein X is O, S, or NR42, wherein R42 is alkyl, wherein Y is O, S, or NR43, wherein R43 is alkyl,
wherein R44 is an alkylene group, wherein R45 is alkyl, and wherein n is an integer of 0 to 150, it is preferred that R45 is partially unsaturated alkyl, wherein R44 more preferably comprises one or more, more preferably from one to five, more preferably from one to three, more preferably one, C═C double bonds.
Further in the case where the mixture provided in (i) further comprises a first end-capping agent,
wherein the first end-capping agent has the formula (V):
HX—(R44—Y)n—R45 (V),
wherein X is O, S, or NR42, wherein R42 is alkyl, wherein Y is O, S, or NR43, wherein R43 is alkyl,
wherein R44 is an alkylene group, wherein R45 is alkyl, and wherein n is an integer of 0 to 150, it is preferred that n=0,
wherein R45 is alkyl, wherein the alkyl is more preferably partially unsaturated, wherein the alkyl is more preferably substituted,
wherein R45 more preferably is (C1-C22)alkyl, more preferably (C12-C22)alkyl, more preferably partially unsaturated (C12-C22)alkyl, more preferably partially unsaturated (C16-C20)alkyl, more preferably partially unsaturated (C18-C19)alkyl, wherein R45 more preferably comprises one or more, more preferably from one to five, more preferably from one to three, more preferably one, C═C double bonds, and wherein R45 more preferably is (2)-Octadec-9-en-yl (oleyl).
It is preferred that the mixture provided in (i) further comprises a first end-capping agent, wherein the first end-capping agent has the formula (VI):
HX—R47 (VI)
wherein X is O, S, or NR46,
wherein R46 and R47 independently from each other is alkyl, wherein the alkyl is more preferably linear or branched, more preferably linear, wherein X is more preferably NR46,
wherein R46 and R47 independently from each other more preferably is (C1-C22)alkyl, more preferably (C1-C18)alkyl, more preferably partially unsaturated (C1-C18)alkyl, more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R46 and R47 independently from each other more preferably is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl.
In the case where the mixture provided in (i) further comprises a first end-capping agent, wherein the first end-capping agent has the formula (V) or (VI) as defined hereinabove, it is preferred that the first end-capping agent has an average molecular mass in the range of from 100 to 5500 daltons, more preferably in the range of from 200 to 3300 daltons, more preferably in the range of from 300 to 2200 daltons, more preferably in the range of from 400 to 1100 daltons,
more preferably in the range of from 400 to 800 daltons, more preferably in the range of from 450 to 550 daltons.
Further in the case where the mixture provided in (i) further comprises a first end-capping agent,
wherein the first end-capping agent has the formula (V) or (VI) as defined hereinabove, it is preferred that X is O, and wherein the first end-capping agent exhibits a hydroxyl number in the range of from 5 to 200 mg(KOH)/g, more preferably in the range of from 15 to 175 mg(KOH)/g,
more preferably in the range of from 45 to 145 mg(KOH)/g, more preferably in the range of from 75 to 130 mg(KOH)/g, more preferably in the range of from 100 to 120 mg(KOH)/g, wherein the hydroxyl number is more preferably determined according to DIN 53240.
Further in the case where the mixture provided in (i) further comprises a first end-capping agent,
wherein the first end-capping agent has the formula (V) or (VI) as defined hereinabove, it is preferred that the first end-capping agent exhibits viscosity in the range of from 5 to 200 mm2/s,
more preferably in the range of from 15 to 175 mm2/s, more preferably in the range of from 45 to 145 mm2/s, more preferably in the range of from 75 to 130 mm2/s, more preferably in the range of from 100 to 120 mm2/s, wherein the viscosity is more preferably determined at a temperature in the range of from 15 to 25° C., more preferably at a temperature of 19 to 21° C., more preferably at a temperature of 20° C., wherein the viscosity is more preferably determined according to DIN 51562.
Further in the case where the mixture provided in (i) further comprises a first end-capping agent,
wherein the first end-capping agent has the formula (V) or (VI) as defined hereinabove, it is preferred that the first end-capping agent comprises an amount of water in the range of from 0 to 1 weight-%, more preferably in the range of from 0 to 0.6 weight-%, more preferably in the range of from 0 to 0.55 weight-%, based on the weight of the first end-capping agent, wherein the wa-ter content is more preferably determined according to EN 13267.
It is preferred that a molar ratio of the one or more isocyanates comprised in the mixture ob-tained in (i), calculated as sum of the molar amounts of the one or more isocyanates, to the cat-alytic compound comprised in the mixture obtained in (i), calculated as molar amount of the cat-alytic compound, in the mixture obtained in (i) is in the range of from 1:5 to 100:1, more preferably in the range of from 1:3 to 75:1, more preferably in the range of from 1:2 to 50:1, more preferably in the range of from 1:1 to 10:1, more preferably in the range of from 2:1 to 8:1, more preferably in the range of from 4:1 to 7:1.
It is preferred that the mixture obtained in (i) comprises the catalytic compound in an amount in the range of from 0.1 to 100 mol-%, more preferably in the range of from 0.25 to 75 mol-%,
more preferably in the range of from 0.5 to 50 mol-%, more preferably in the range of from 0.75 to 40 mol-%, more preferably in the range of from 1 to 36 mol-%, based on the amount of the one or more isocyanates comprised in the mixture obtained in (i), calculated as sum of the mo-lar amounts of the one or more isocyanates comprised in the mixture obtained in (i).
It is preferred that the mixture obtained in (i) comprises the catalytic compound in an amount in the range of from 1 to 35 weight-%, more preferably in the range of from 2 to 31 weight-%, more preferably in the range of from 3 to 30 weight-%, based on the amount of the one or more iso-cyanates comprised in the mixture obtained in (i), calculated as sum of the weights of the one or more isocyanates comprised in the mixture obtained in (i).
It is preferred that the mixture obtained in (i) comprises an amount in the range of from 0 to 25 weight-%, more preferably in the range of from 0.1 to 10 weight-%, more preferably in the range of from 1 to 5 weight-%, of xylene, preferably of an alkyl substituted benzene or an alkyl substituted dibenzene, wherein the alkyl comprises one or more of methyl, ethyl, and propyl, more preferably of a solvent, based on the weight of the mixture obtained in (i),
wherein the mixture obtained in (i) is more preferably essentially free of xylene, more preferably of an alkyl substituted benzene or an alkyl substituted dibenzene, wherein the alkyl comprises one or more of methyl, ethyl, and propyl, more preferably of a solvent.
It is preferred that the mixture obtained in (i) comprises an amount in the range of from 0 to 5 weight-%, more preferably in the range of from 0.1 to 1 weight-%, of a primary diisocyanate, preferably of a primary isocyanate, based on the weight of the mixture obtained in (i), wherein the mixture provided in (i) is more preferably essentially free of a primary diisocyanate, preferably of a primary isocyanate.
It is preferred that the mixture obtained in (ii) comprises a residual amount of the one or more isocyanates in the range of from 0 to 35 mol-%, more preferably in the range of from 1 to 20 mol-%, more preferably in the range of from 5 to 15 mol-%, based on the amount of the one or more isocyanates comprised in the mixture obtained in (i), calculated as sum of the one or more isocyanates comprised in the mixture obtained in (i).
It is preferred that the process further comprises
Cooling the mixture obtained in (ii) according to (iii) can be carried out especially for inhibiting further carbodiimidization, preferably for inhibiting any further reaction.
It is preferred that the process further comprises
Subjecting the mixture obtained in (ii) or (iii) to distillation conditions in a gas atmosphere according to (iv) can be carried out especially for separating at least a portion of the one or more isocyanates from the mixture, and preferably for degradation of at least a portion of the catalytic compound.
In the case where the process further comprises (iv) as defined hereinabove, it is preferred that the distillation conditions comprise a temperature in the range of from 170 to 210° C., more preferably in the range of from 180 to 200° C.
Further in the case where the process further comprises (iv) as defined hereinabove, it is preferred that the distillation conditions comprise a pressure in the range of from 1 to 250 hPa(abs),
more preferably in the range of from 5 to 150 hPa(abs), more preferably in the range of from 5 to 10 hPa(abs).
Further in the case where the process further comprises (iv) as defined hereinabove, it is preferred that the mixture obtained in (iv) comprises an amount of isocyanate groups, calculated as NCO, in the range of from 0 to 10.5 weight-%, more preferably in the range of from 0 to 8.0 weight-%, based on the weight of the mixture obtained in (iv).
Further in the case where the process further comprises (iv) as defined hereinabove, it is preferred that the process further comprises
It is preferred that the process further comprises
In the case where the process further comprises (vi) and (vii) as defined hereinabove, it is preferred that the second end-capping agent according to (vi) has the formula (VII):
HX—(R50—Y)n—R51 (VII),
wherein X is O, S, or NR48, wherein R48 is alkyl, wherein the alkyl is more preferably linear or branched, more preferably linear, wherein X is more preferably O,
wherein R48 is more preferably (C1-C22)alkyl, more preferably (C1-C18)alkyl, more preferably par-tially unsaturated (C1-C18)alkyl, more preferably (C1-C18)alkyl, more preferably (C1-C12)alkyl,
more preferably (C1-C8)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R48 more preferably is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl,
wherein Y is O, S, or NR49, wherein R49 is alkyl, wherein the alkyl is preferably linear or branched, more preferably linear, wherein X is more preferably O,
wherein R49 is more preferably (C1-C22)alkyl, more preferably (C1-C18)alkyl, more preferably par-tially unsaturated (C1-C18)alkyl, more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl,
more preferably (C1-C8)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R49 more preferably is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl,
wherein R50 is an alkylene group,
wherein R50 is more preferably selected from the group consisting of methylene, ethylene, tri-methylene, tetramethylene, pentamethylene, hexamethylene, ortho-phenylene, meta-phenylene, and para-phenylene,
wherein R50 more preferably is ethylene,
wherein R51 is alkyl, wherein the alkyl is more preferably partially unsaturated, wherein the alkyl is more preferably substituted,
wherein R51 more preferably is alkyl, wherein the alkyl is more preferably linear or branched,
more preferably linear,
wherein R51 more preferably is (C1-C22)alkyl, more preferably (C1-C18)alkyl, more preferably par-tially unsaturated (C1-C18)alkyl, more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl,
more preferably (C1-C8)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R51 more preferably is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl, and
wherein n is an integer of 0 to 150, more preferably an integer of 2 to 150, preferably an integer of 5 to 100, more preferably an integer of 7 to 50, more preferably an integer of 8 to 25, more preferably an integer of 9 to 20, more preferably an integer of 10 to 15,
wherein the second end-capping agent according to (vi) more preferably is a methylpolyeth-ylene glycol.
In the case where the second end-capping agent according to (vi) has the formula (VII):
HX—(R50—Y)n—R51 (VII),
wherein X is O, S, or NR48, wherein R48 is alkyl, wherein Y is O, S, or NR49, wherein R49 is alkyl,
wherein R50 is an alkylene group, wherein R51 is alkyl, and wherein n is an integer of 0 to 150, it is preferred that R51 is substituted alkyl, wherein the substituted alkyl more preferably comprises one or more substituents, wherein the one or more substituents of the substituted alkyl independently from each other are more preferably selected from the group consisting of (C1-C3)alkoxy, hydroxyl, amino, halides, and combinations of two or more thereof, more preferably from the group consisting of (C1-C2)alkoxy, hydroxyl, amino, chloro, bromo, fluoro, and combina-tions of two or more thereof, more preferably from the group consisting of hydroxyl, amino, chlo-ro, and combinations thereof, wherein more preferably the one or more substituents independently from each other are hydroxyl,
wherein the substituted alkyl more preferably comprises one or more substituents, preferably one to four substituents, more preferably one to three substituents, more preferably one or two substituents, wherein the substituted alkyl group more preferably comprises one substituent.
Further in the case where the second end-capping agent according to (vi) has the formula (VII):
HX—(R50—Y)n—R51 (VII),
wherein X is O, S, or NR48, wherein R48 is alkyl, wherein Y is O, S, or NR49, wherein R49 is alkyl,
wherein R50 is an alkylene group, wherein R51 is alkyl, and wherein n is an integer of 0 to 150, it is preferred that R51 is partially unsaturated alkyl, wherein R51 more preferably comprises one or more, more preferably from one to five, more preferably from one to three, more preferably one, C═C double bonds.
Further in the case where the second end-capping agent according to (vi) has the formula (VII):
HX—(R50—Y)n—R51 (VII),
wherein X is O, S, or NR48, wherein R48 is alkyl, wherein Y is O, S, or NR49, wherein R49 is alkyl,
wherein R50 is an alkylene group, wherein R51 is alkyl, and wherein n is an integer of 0 to 150, it is preferred that n=0,
wherein R51 is alkyl, wherein the alkyl is more preferably partially unsaturated, wherein the alkyl is more preferably substituted,
wherein R51 is more preferably (C1-C22)alkyl, more preferably (C12-C22)alkyl, more preferably partially unsaturated (C12-C22)alkyl, more preferably partially unsaturated (C16-C20)alkyl, more preferably partially unsaturated (C18-C19)alkyl, wherein R51 preferably comprises one or more,
more preferably from one to five, more preferably from one to three, more preferably one, C═C double bonds, and wherein R51 more preferably is (2)-Octadec-9-en-yl (oleyl).
Further in the case where the second end-capping agent according to (vi) has the formula (VII):
HX—(R50—Y)n—R51 (VII),
wherein X is O, S, or NR48, wherein R48 is alkyl, wherein Y is O, S, or NR49, wherein R49 is alkyl,
wherein R50 is an alkylene group, wherein R51 is alkyl, and wherein n is an integer of 0 to 150, it is preferred that the mixture provided in (i) further comprises a first end-capping agent, wherein the first end-capping agent has the formula (VIII):
HX—R53 (VIII)
wherein X is O, S, or NR52,
wherein R52 and R53 independently from each other is alkyl, wherein X is preferably NR52,
wherein R52 and R53 independently from each other more preferably is (C1-C22)alkyl, more preferably (C1-C18)alkyl, more preferably partially unsaturated (C1-C18)alkyl, more preferably (C1-C16)alkyl, more preferably (C1-C12)alkyl, more preferably (C1-C8)alkyl, more preferably (C1-C6)alkyl, more preferably (C1-C5)alkyl, more preferably (C1-C4)alkyl,
wherein R52 and R53 independently from each other more preferably is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, more preferably methyl.
In the case where the process further comprises (vi) and (vii) as defined hereinabove, it is preferred that the second end-capping agent according to (vi) has an average molecular mass in the range of from 100 to 5500 daltons, more preferably in the range of from 200 to 3300 daltons, more preferably in the range of from 300 to 2200 daltons, more preferably in the range of from 400 to 1100 daltons, more preferably in the range of from 400 to 800 daltons, more prefer-ably in the range of from 450 to 550 daltons.
Further in the case where the process further comprises (vi) and (vii) as defined hereinabove, it is preferred that X is O, and wherein the second end-capping agent according to (vi) exhibits a hydroxyl number in the range of from 5 to 200 mg(KOH)/g, more preferably in the range of from 15 to 175 mg(KOH)/g, more preferably in the range of from 45 to 145 mg(KOH)/g, more prefer-ably in the range of from 75 to 130 mg(KOH)/g, more preferably in the range of from 100 to 120 mg(KOH)/g, wherein the hydroxyl number is more preferably determined according to DIN 53240.
Further in the case where the process further comprises (vi) and (vii) as defined hereinabove, it is preferred that the second end-capping agent according to (vi) exhibits a viscosity in the range of from 5 to 200 mm2/s, more preferably in the range of from 15 to 175 mm2/s, more preferably in the range of from 45 to 145 mm2/s, more preferably in the range of from 75 to 130 mm2/s,
more preferably in the range of from 100 to 120 mm2/s, wherein the viscosity is preferably de-termined at a temperature in the range of from 15 to 25° C., more preferably at a temperature of 19 to 21° C., more preferably at a temperature of 20° C., wherein the viscosity is more preferably determined according to DIN 51562.
Further in the case where the process further comprises (vi) and (vii) as defined hereinabove, it is preferred that the second end-capping agent according to (vi) comprises in the range of from 0 to 1 weight-%, more preferably in the range of from 0 to 0.6 weight-%, more preferably in the range of from 0 to 0.55 weight-%, of water, based on the weight of the second end-capping agent, wherein the water content is more preferably determined according to EN 13267.
Further in the case where the process further comprises (vi) and (vii) as defined hereinabove, it is preferred that the mixture obtained in (vii) comprises an amount in the range of from 55 to 85 weight-%, more preferably in the range of from 60 to 80 weight-%, more preferably in the range of from 65 to 75 weight-%, of the second end-capping agent, based on the weight of the carbodiimide obtained in (ii) or (iv).
Further in the case where the process further comprises (vi) and (vii) as defined hereinabove, it is preferred that the gas atmosphere in (vii) comprises, more preferably consists of, an inert gas, wherein the gas atmosphere in (vii) more preferably comprises, more preferably consists of, one or more of nitrogen and argon.
Further in the case where the process further comprises (vi) and (vii) as defined hereinabove, it is preferred that the end-capping conditions according to (vii) comprise a temperature in the range of from 80 to 160° C., more preferably in the range of from 100 to 140° C., more preferably in the range of from 110 to 130° C.
Further in the case where the process further comprises (vi) and (vii) as defined hereinabove, it is preferred that the mixture obtained in (vi) is subjected to end-capping conditions according to (vii) for a duration in the range of from 1 to 10 h, more preferably in the range of from 3 to 7 h,
more preferably in the range of from 4 to 6 h.
Further in the case where the process further comprises (vi) and (vii) as defined hereinabove, it is preferred that the carbodiimide being end-capped obtained in (vii) comprises an amount of isocyanate groups, calculated as NCO, in the range of from 0 to 0.1 weight-%, more preferably in the range of from 0 to 0.01 weight-%, more preferably in the range of from 0 to 0.001 weight-%, based on the weight of the mixture obtained in (vii).
It is preferred that the process further comprises
Further, the present invention relates to a carbodiimide, preferably a carbodiimide having formu-la (I):
Q
1-[Q2-N═C═N]n-Q3-Q4 (I)
wherein n is in the range of from 1 to 500, more preferably in the range of from 2 to 20, more preferably in the range of from 3 to 15, more preferably in the range of from 4 to 10, and wherein Q2 and Q3 stands for an organic backbone and Q1 and Q4 stands for an organic end group, as obtained and/or obtainable by the process according to any one of the embodiments disclosed herein.
Yet further, the present invention relates to a use of a carbodiimide according to any one of the embodiments disclosed herein as a stabilizer, more preferably as a hydrolysis stabilizer, for a polymer, more preferably for a thermoplastic polymer, more preferably for a thermoplastic poly-ester, more preferably for one or more of a polyurethane (PU), preferably a thermoplastic polyu-rethane (TPU), a polyurea, a polyethylene terephthalate (PET), a polybutylene terephthalate (PBT), a polyactide (PLA), a polyamide, a polyesteramide, a polycaprolactone, and a polyether-sulfone (PES).
By way of example, potassium dioxobis[glycolato(2−)]molybdate(VI) is considered according to the present invention as a catalytic compound comprising two double bonds, and sodium mo-lybdate (Na2MoO4) is considered as comprising two double bonds.
The carbodiimide preparation according to the inventive process can be carried out in the ab-sence or presence of solvents which are inert under the reaction conditions. It is preferred, however, that no solvent is used.
The carbodiimide groups of the carbodiimides and polycarbodiimides of the present invention are bound to non-aromatic carbon atoms. This offers the significant advantage that no aromatic amines are liberated on possible cleavage of the carbodiimides. The carbodiimides and poly-carbodiimides of the present invention are therefore of less toxicological concern.
In the context of the present invention, a tertiary monoisocyanate is a compound comprising one isocyanate group NCO, wherein said isocyanate group is connected to a tertiary carbon atom. Similarly, a primary monoisocyanate is a compound comprising one isocyanate group NCO, wherein said isocyanate group is connected to a primary carbon atom. Similarly, a sec-ondary monoisocyanate is a compound comprising one isocyanate group NCO, wherein said isocyanate group is connected to a secondary carbon atom.
Further, a tertiary diisocyanate is a compound comprising two isocyanate groups NCO, wherein each of said isocyanate groups is connected to a tertiary carbon atom. Similarly, a primary diisocyanate is a compound comprising two isocyanate groups NCO, wherein each of said iso-cyanate groups is connected to a primary carbon atom. Similarly, a secondary diisocyanate is a compound comprising two isocyanate groups NCO, wherein each of said isocyanate groups is connected to a secondary carbon atom.
Thus, in the context of the present invention, an isocyanate compound comprising two or more isocyanate groups NCO, wherein at least one of said isocyanate groups is connected to a pri-mary carbon atom or to a secondary carbon atom, is not considered as a tertiary diisocyanate.
In the context of the present invention, an alkyl group consists of carbon atoms and hydrogen atoms. Thus, an alkyl group according to the present invention does not comprise a further sub-stituent, e.g. a hydroxyl or chloride group, unless otherwise defined.
The present invention is further illustrated by the following set of embodiments and combina-tions of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for ex-ample in the context of a term such as “The process of any one of embodiments 1 to 4”, every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the word-ing of this term is to be understood by the skilled person as being synonymous to “The process of any one of embodiments 1, 2, 3, and 4”.
Further, it is explicitly noted that the following set of embodiments is not the set of claims deter-mining the extent of protection, but represents a suitably structured part of the description di-rected to general and preferred aspects of the present invention.
Q1-[Q2-N═C═N]n-Q3-Q4 (I)
OCN—C(R6,R7)—R8—C(R9,R10)—R11 (II),
OCN—C(R18,R19)—R20—C(R21,R22)—NCO (III),
OCN—C(R25,R26)—R27—C(R28,R29)—R30 (IV),
HX—(R44—Y)n—R45 (V),
HX—R47 (VI)
HX—(R50—Y)n—R51 (VII),
HX—R53 (VIII)
Q
1-[Q2-N═C═N]n-Q3-Q4 (I)
The present invention is further illustrated by the following reference examples, examples, and comparative examples.
FTIR spectra, in particular for determination of characteristic bands for isocyanate groups, were recorded via single reflection ATR module on an Eco-ATR from Brücker. A sample was added directly onto the ATR crystal without any modification. Typically, it is expected that an isocyanate group NCO shows a band at about 2200 cm−1 in the FTIR spectrum and that a carbodiimide group shows a band at about 2100 cm-1.
100.0 g tetramethylxylene diisocyanate (TMXDI), 100.0 g 4,4′-diisocyanato dicyclohexylmethane (H12MDI; Evonik) and 60.0 g methylpolyethylene glycol (Pluriol A500E; BASF SE; having an average weight of 500 g/mol) were charged into a 500 mL, 4-neck round bottom flask equipped with a thermometer (coupled with a temperature regulated oil-bath), mechanical stirring, a cold-water condenser and nitrogen inlet. The mixture was stirred and heated at a temperature of 120° C. After approximately 9 hours the NCO content, determined via infrared-spectroscopy, reached a value of 7.6% corresponding to full conversion of the alcohol into urethane.
Sodium molybdate (2.5 g, 12 mmol) were dissolved in water (40 ml, degassed). Then, N,N-Dimethyl-L-phenylalanine (1.17 g, 6 mmol) was added thereto. Via a dropping funnel, 25.5 ml of 1 M aqueous nitric acid (HNO3) was slowly added. During the addition of aqueous nitric acid the pH-value decreased from 6.8 to 1.8 and a white suspension is formed. The suspension was stirred for 1.5 h at room temperature. Then, the white solid was filtered off and washed with ace-tone and diethyl ether (each 2×10 ml). The white solid was dried under vacuum.
Molecular structure of dihydroxydi-μ-hydroxytetraoxodimolybdenum 2-(dimethylamino)-3-phenylpropanoate.
Reference Example 3 was repeated whereby L-phenylalanine was used as starting material instead of N,N-Dimethyl-L-phenylalanine.
Molecular structure of dihydroxydi-μ-hydroxytetraoxodimolybdenum 2-amino-3-phenylpropanoate.
Bis(N,N-diethyldithiocarbamato)dioxomolybdenum(VI) (CAS 19680-83-2) was purchased from Sigma Aldrich.
Molecular structure of bis(N,N-diethyldithiocarbamato)dioxomolybdenum(VI).
Potassium dioxobis[glycolato(2−)]molybdate(VI) was synthezised according to a known proce-dure disclosed in “Physicochemical studies on the reactions of Na tungstate and Na molybdate with glycolic acid” by Banerjee, S. P.; Bhattacharya, Arun K in Proceedings of the Institution of Chemists (India) 1963, vol. 35, issue 5, pages 247-250.
Molecular structure of potassium dioxobis[glycolato(2−)]molybdate(VI).
Sodium dioxobis[methylglycolato(2−)]molybdate(VI) was synthezised according to a known pro-cedure disclosed in “Physicochemical studies on the reactions of Na tungstate and Na molybdate with glycolic acid” by Banerjee, S. P.; Bhattacharya, Arun K.
Molecular structure of Sodium dioxobis[methylglycolato(2−)]molybdate(VI)
100.0 g tetramethylxylene diisocyanate (0.41 mol; TMXDI) and 3.0 g of the Mo-containing catalytic compound according to Reference example 3 were charged to a 250 ml, 4-neck round bottom flask equipped with a thermometer (coupled with a temperature regulated oil-bath), mechanical stirring, a cold-water condenser and nitrogen inlet. The mixture was stirred and heated at 175° C. After approximately 4 hours the NCO content reached a value of 13.8%. FTIR showed a strong band at 2100 cm−1 characteristic of the formation of a carbodiimide. The inte-gration of the band showed that more than 90 mol-% of the isocyanate groups were converted into carbodiimide. The mixture was then distillated for 2 hours (using a distillation bridge) at 190° C. and 100 mbar. The corresponding product had an NCO content of 5.0%. Subsequently, 54.0 g methylpolyethylene glycol (Pluriol A500E; BASF SE; having an average weight of 500 g/mol) were added. After 5 hours at 120° C., the NCO content, determined via infrared-spectroscopy, reached 0.0%. Then, the mixture was cooled down to room temperature. The resulting polycarbodiimide showed an NCN content of 5 weight-%.
Preparation of a polycarbodiimide was performed using the catalytic compounds noted in Table 1 below. For each example, 10 g of tetramethylxylene diisocyanate (TMXDI) were mixed with 3 g of the respective catalytic compound in a 50 ml vial sealed with a teflon-equipped cap. The vial was placed in the block reactor, stirred using a magnetic stirrer and heated up to 180° C. After the respective reaction time, the mixture was analyzed by Infrared spectroscopy (ATR-FTIR) which revealed the presence of carbodiimide groups via the appearance of the typical NCN band around 2100 cm-1. Further, NCO content and selectivity towards the formation of carbodiimide groups were measured.
As can be gathered from the results shown in Table 1, the process according to the present invention successfully resulted in the formation of a polycarbodiimide, wherein in particular a specific catalytic compound was used. In particular, it can be seen from the results shown in Table 1 that the selectivity towards the formation of carbodiimide groups was at least 28% for all of Examples 2-10. Thus, according to the process of Examples 2-10 a comparatively high selectivity towards the formation of carbodiimide groups can be achieved. In contrast thereto, the process of Comparative Examples 11-13 achieved a selectivity towards the formation of carbodiimide groups of below 5% showing that a catalytic compound which does not comprise in particular a Mo—O bond or a Mo═O bond achieves a lower selectivity.
| Number | Date | Country | Kind |
|---|---|---|---|
| 22150919.3 | Jan 2022 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2023/050471 | 1/10/2023 | WO |
