Phytic acid oligomer

Abstract

The present invention relates to a phytic acid oligomer, to a process for preparing the phytic acid oligomer, to the use of the phytic acid oligomer, to a process for preparing polymers comprising the phytic acid oligomer, and to polymers prepared according to said process.

Description

[0001] Phytic acid oligomer

[0002] Description

[0003] The present invention relates to a phytic acid oligomer, a process for producing the phytic acid oligomer, a use of the phytic acid oligomer, a process for producing polymer compositions comprising the phytic acid oligomer, and polymer compositions produced by the process.

[0004] Phytic acid is known in itself, but has so far found little industrial application. Phytic acid is extracted from corn steep liquor and rice hulls, for example, and occurs naturally as an anion.

[0005] A major challenge in the polymer industry is to make better use of raw materials derived from renewable sources. A common problem with the use of raw materials from renewable sources is that they often have a rather complex structure and are therefore difficult to process into polymers with controllable properties.

[0006] The object is therefore to provide novel starting products for the production of polymers with good properties that can be obtained from renewable raw materials. This object is achieved by the phytic acid oligomer according to claim 1, as well as the process for producing the phytic acid oligomer according to claim 6, the use according to claim 8, the process for producing a polymer composition according to claim 9, and the polymer composition according to claim 10. Preferred embodiments of the invention are specified in the subclaims and in the description, wherein further features described or shown in the subclaims or in the description can constitute an object of the invention, individually or in any combination, unless the context clearly indicates the opposite.

[0007] The invention proposes a phytic acid oligomer consisting of at least two independently selected groups of the following formula (I) and at least one independently selected group of the following formula (II) wherein n is independently selected from an integer in a range from greater than or equal to 1 to less than or equal to 6, wherein m is independently selected from an integer in a range from greater than or equal to 2 to less than or equal to 6, wherein all R are independently selected from H or an organic radical, and wherein L is selected from an organic linker or a siloxane linker; and wherein each group of formula (II) connects at least two independent groups of formula (I) to one another via covalent bonds, wherein the stars represent bonding positions.

[0008] It was surprisingly demonstrated that the phytic acid oligomer is particularly easy to prepare and, at the same time, can be readily processed with other reactants to form polymer compositions with good properties. In particular, it was surprisingly demonstrated that the phytic acid oligomer, despite its complex structure, can be readily converted into polymer compositions. Furthermore, it was surprisingly demonstrated that, despite the high number of functional groups of phytic acid, the phytic acid oligomer can be prepared predictably and easily in a one-pot reaction without the uncontrolled formation of long-chain and / or branched polymers. Furthermore, it was surprisingly demonstrated that the phytic acid oligomer can be prepared without the use of anhydrides, as is usually necessary in the production of phosphoric acid esters.

[0009] Without being bound to any theory, it is assumed that the reaction to form phytic acid oligomer is particularly controlled because the acid groups of phytic acid do not all have the same acid constants.

[0010] Furthermore, it was shown that the polarity of the phytic acid oligomer can be adjusted, particularly by the choice of linkers and organic residues, and especially by the number of R residues that are not H. Accordingly, the phytic acid oligomer can be advantageously adapted to various applications.

[0011] As a result, the phytic acid oligomer is advantageously a particularly environmentally friendly starting material for polymers because its components can largely be easily obtained from renewable raw materials. Furthermore, the phytic acid oligomer can be used to functionalize polymer compositions with phosphates, which is why the resulting polymer compositions can exhibit good corrosion protection properties. Preferably, the phytic acid oligomer can have a maximum of 20 independently selected groups of formula (I), more preferably a maximum of 15, more preferably a maximum of 10, more preferably a maximum of 6, for example 5, 4, or 3.

[0012] Preferably, the phytic acid oligomer may comprise a maximum of 19 independently selected groups of formula (II), more preferably a maximum of 14, more preferably a maximum of 9, particularly preferably a maximum of 5, for example 4, 3, or 2.

[0013] Preferably, it can be provided that the phytic acid oligomer has at least one independently selected group of formula (II) less than independently selected groups of formula (I).

[0014] Preferably, it can be provided that in the phytic acid oligomer at least two of all R together are selected from H, and the remaining R are not H.

[0015] Preferably, it can be provided that in the phytic acid oligomer greater than or equal to 5% to less than or equal to 100% of all R together are selected from H, based on the total number of R, preferably greater than or equal to 9% to less than or equal to 91%, more preferably greater than or equal to 10% to less than or equal to 90%, more preferably greater than or equal to 12% to less than or equal to 70%, more preferably greater than or equal to 14% to less than or equal to 50%, more preferably greater than or equal to 16% to less than or equal to 30%, particularly preferably greater than or equal to 18% to less than or equal to 20, wherein in each case the remaining R are not H.

[0016] Preferably, formula (I) can be selected from formula (Ia): where R, n and * are as defined for formula (I). Preferably, formula (I) can be selected from formula (Ib) where R, n and * are as defined for formula (I).

[0017] Preferably, it can be provided that n is independently selected from an integer in a range from greater than or equal to 1 to less than or equal to 5, more preferably from greater than or equal to 1 to less than or equal to 4, particularly preferably from greater than or equal to 1 to less than or equal to 3, for example 1 or 2.

[0018] Preferably, the phytic acid oligomer may comprise at least two groups of formula (I) in which n is selected from 1.

[0019] Preferably, the phytic acid oligomer may comprise at least two groups of formula (I) in which n is selected from 1, and at least one group of formula (I) in which n is selected from 2.

[0020] Preferably, the phytic acid oligomer may comprise at least three groups of formula (I) in which n is selected from 1, and at least one group of formula (I) in which n is selected from 3.

[0021] Preferably, the phytic acid oligomer may comprise at least three groups of formula (I) in which n is selected from 1, at least one group of formula (I) in which n is selected from 3, and at least one group of formula (I) in which n is selected from 2.

[0022] Preferably, groups of formula (I) may be independently selected from the following formula (1-1) in the case where n is selected from 1:

[0023] where R, and * are as defined for formula (I). Preferably, groups of formula (I), in the case where n is selected from 2, are independently selected from the following formulas (I-2a), (I-2b), and (I-2c):

[0024] (I-2a)

[0025]

[0026] (I-2c) where R, and * are as defined for formula (I).

[0027] Preferably, groups of formula (I) can be provided, in the case where n is selected from 2, independently selected from formulas (I-2a) and (I-2b). Preferably, groups of formula (I) can be provided, in the case where n is selected from 3, independently selected from the following formulas (I-3a), (I-3b), and (I-3c): (I-3c) where R, and * are as defined for formula (I).

[0028] Preferably, it can be provided that groups of formula (I), in the case that n is selected from 2, are independently selected from formulas (I-3a) and (I-3b), particularly preferably from formula (I-3b).

[0029] Preferably, all R are independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted haloalkenyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted heterocycloalkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted aminocarboxylic acid.

[0030] The term "substituted" means, in particular in the context of the present invention, that the corresponding fragment has at least one radical that is not hydrogen or deuterium, where the radical can be selected, in particular, from the group consisting of halogen, -OH, C1-6 alkyl, C1-6 haloalkyl, C2-6 alkenyl, C1-6 alkoxy, and C1-6 haloalkoxy. The term "unsubstituted" in the sense of the present invention means, in particular, that the corresponding fragment has no radicals other than hydrogen or deuterium, apart from substituents that have already been explicitly described for this fragment.

[0031] Preferably, it can be provided that all R are independently selected from H, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C2-30 alkynyl, substituted or unsubstituted C1-30 haloalkyl, substituted or unsubstituted C2-30 haloalkenyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C3-30 cyclalkenyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or

[0032] REPLACEMENT SHEET (RULE 26) unsubstituted C2-30 heterocycloalkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C3-30 heteroaryl, and substituted or unsubstituted C2-30 aminocarboxylic acid.

[0033] Preferably, it can be provided that all R are independently selected from H, CI-30 alkyl, CI-30 heteroalkyl, C2-30 alkenyl, C2-30 alkynyl, CI-30 haloalkyl, C2-30 haloalkenyl, C3-30 cycloalkyl, C3-30 cyclalkenyl, C2-30 heterocycloalkyl, C2-30 heterocycloalkenyl, C6-30 aryl, C3-30 heteroaryl, and C2-30 aminocarboxylic acid.

[0034] Preferably, it can be provided that all R are independently selected from H, C1-30 alkyl, C2-30 alkenyl, C2-30 alkynyl, C3-30 cycloalkyl, C3-30 cyclalkenyl, and C6-30 aryl.

[0035] Preferably, all R are independently selected from H, C1-30 alkyl, C2-30 alkenyl, and C6-30 aryl.

[0036] Preferably, all R are independently selected from H, C1-30 alkyl, and C6-30 aryl.

[0037] Preferably, all R are independently selected from H, C4-20 alkyl, and C6-24 aryl.

[0038] Preferably, all R are independently selected from H, C4-20 alkyl, and C6-24 aryl.

[0039] Preferably, all R are independently selected from H, C6-16 alkyl, and C6-12 aryl.

[0040] Preferably, all R are independently selected from H and C8-12 alkyl.

[0041] Preferably, all R are independently selected from H and a linear C8-12 alkyl.

[0042] Preferably, all R are independently selected from H and a linear CIO alkyl.

[0043] Preferably, it can be provided that m is independently selected from an integer in a range from greater than or equal to 2 to less than or equal to 5, more preferably from

[0044] REPLACEMENT LEAF (RULE 26) greater than or equal to 2 to less than or equal to 4, especially less than or equal to 3, most preferably 2.

[0045] Preferably, groups of formula (II) can be independently selected from groups of the following formula (IIa):

[0046] ^L^

[0047] (Ila) where L and * are as defined for formula (II).

[0048] Preferably, it can be provided that in the phytic acid oligomer all groups of formula (II) are selected the same, particularly preferably all groups of formula (IIa).

[0049] L is selected from an organic linker and a siloxane linker.

[0050] Organic linkers:

[0051] Preferably, L can be selected from substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted haloalkyl, substituted or unsubstituted haloalkenyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted heterocycloalkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted aminocarboxylic acid.

[0052] Preferably, L can be selected from substituted or unsubstituted C2-30 alkyl, substituted or unsubstituted C2-30 heteroalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C2-30 alkynyl, substituted or unsubstituted C2-30 haloalkyl, substituted or unsubstituted C2-30, haloalkenyl, substituted or unsubstituted C3-30

[0053] REPLACEMENT SHEET (RULE 26) Cycloalkyl, substituted or unsubstituted C3-30 cycloalkenyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 heterocycloalkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C3-30 heteroaryl, substituted or unsubstituted C1-30 aminoalkyl, and substituted or unsubstituted C2-30 aminocarboxylic acid.

[0054] Preferably, L can be selected from C2-30 alkyl, C2-30 heteroalkyl, C2-30 alkenyl, C2-30 alkynyl, C2-30 haloalkyl, C2-30 haloalkenyl, C3-30 cycloalkyl, C3-30 cyclalkenyl, C2-30 heterocycloalkyl, C2-30 heterocycloalkenyl, C6-30 aryl, C3-30 heteroaryl and C2-30 aminocarboxylic acid.

[0055] Preferably, L can be selected from C2-30 alkyl, C2-30 alkenyl, C2-30 alkynyl, C3-30 cycloalkyl, C3-30 cycloalkenyl, and C6-30 aryl.

[0056] Preferably, L can be selected from C1-30 alkyl, C1-30 alkenyl, and C6-30 aryl.

[0057] Preferably, L can be selected from C1-30 alkyl and C6-30 aryl.

[0058] Preferably, L can be selected from C2-20 alkyl and C6-24 aryl.

[0059] Preferably, L can be selected from C3-12 alkyl and C6-18 aryl.

[0060] Preferably, L can be selected from C4-6 alkyl and C6-12 aryl.

[0061] Preferably, L can be selected from C2-12 alkyl.

[0062] Preferably, L can be selected from linear C4-6 alkyl.

[0063] Preferably, L can be selected from ethyl, propyl, iso-butyl, n-butyl, iso-pentyl, n-pentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, and cyclohexyl.

[0064] Preferably, L can be selected from propyl, iso-butyl, n-butyl, iso-pentyl, and n-pentyl.

[0065] REPLACEMENT LEAF (RULE 26) It can preferably be provided that L is selected from propyl, n-butyl, and n-pentyl, particularly preferably from n-butyl.

[0066] Preferably, it can be provided that n is independently selected from an integer in a range from greater than or equal to 1 to less than or equal to 3, and m is selected from 2, and wherein the phytic acid oligomer has at least two groups of formula (I) in which n is selected from 1.

[0067] Preferably, all R are independently selected from H and a linear C8-12 alkyl, and L is selected from propyl, iso-butyl, n-butyl, iso-pentyl, and n-pentyl.

[0068] Preferably, it can be provided that all R are independently selected from H and a linear CIO alkyl, and L is selected from propyl, n-butyl, and n-pentyl, particularly preferably from n-butyl.

[0069] Preferably, all R of the phytic acid oligomer are H or the same organic residue.

[0070] Preferably, all L of the phytic acid oligomer may be the same organic linker.

[0071] Preferably, it can be provided that all R of the phytic acid oligomer are H or the same organic residue, and all L of the phytic acid oligomer are the same organic linker.

[0072] Siloxane linker

[0073] Preferably, it can be provided that L is selected from the group Where k is selected from an integer from 0 to 20, preferably 0, 1 or 2 and each R is independently of the other Ci to C4 alkyl and aryl, preferably methyl or ethyl.

[0074] Particularly preferred are compounds of the following structure: with X 1 = Dimethylsiloxane, X 2 = Aryl, Alkyl, H and n= 1 -3

[0075] Preferably, the phytic acid oligomer may have a molecular weight in a range of greater than or equal to 1344 g / mol to less than or equal to 17000 g / mol.

[0076] Preferably, it can be provided that the phytic acid oligomer has a molecular weight in a range of greater than or equal to 2000 g / mol to less than or equal to 10000 g / mol, more preferably 2000 g / mol to less than or equal to 9000 g / mol, more preferably 4000 g / mol to less than or equal to 8000 g / mol, particularly preferably 6000 g / mol to 7000 g / mol.

[0077] The invention further proposes a process for producing a phytic acid oligomer according to the present invention, wherein a compound of the following formula (III) with at least one compound of the following formula (IV)

[0078] LX)

[0079] ' ' m

[0080] (IV) and optionally at least one compound of the following formula (V)

[0081] R' — X

[0082] (V) are reacted with one another under the influence of temperature to form the phytic acid oligomer, wherein m is independently selected from an integer in a range from greater than or equal to 2 to less than or equal to 6, wherein R' is selected from an organic radical, and wherein L is selected from an organic linker or a siloxane linker; and wherein all X are independently selected from a functional group reactive with formula (III) to form a phosphoric acid ester.

[0083] The preferred embodiments for m in formula (I) are also preferably provided for m in formula (IV).

[0084] The preferred embodiments for L in formula (I) are also preferably provided for L in formula (IV).

[0085] Preferably, it can be provided that in formula (IV) X is selected from OH. Preferably, it can be provided that formula (IV) is selected from C1-30 alkanediol, C1-30 alkenediol, and C6-30 aryldiol.

[0086] Phytic acid oligomer according to any one of claims 1 to 3, wherein L is selected from C1-30 alkanediol and C6-30 aryldiol.

[0087] Preferably, L can be selected from C2-20 alkanediol and C6-24 aryldiol.

[0088] Preferably, L can be selected from C3-12 alkanediol and C6-18 aryldiol.

[0089] Preferably, L can be selected from C4-6 alkanediol and C6-12 aryldiol.

[0090] Preferably, L can be selected from C2-12 alkanediol.

[0091] Preferably, L can be selected from linear C4-6 alkanediol.

[0092] Preferably, L can be selected from ethanediol, propanediol, iso-butanediol, n-butanediol, iso-pentanediol, n-pentanediol, n-hexanediol, 2-methylpentanediol, 3-methylpentanediol, 2,2-dimethylbutanediol, 2,3-dimethylbutanediol, and cyclohexanediol.

[0093] Preferably, L can be selected from propanediol, iso-butanediol, n-butanediol, iso-pentanediol, and n-pentanediol.

[0094] Preferably, it can be provided that L is selected from propanediol, n-butanediol, and n-pentanediol, particularly preferably from n-butanediol, in particular 1,4-n-butanediol.

[0095] Preferably, L can be selected from the following group:

[0096] Where k is selected from an integer from 0 to 20, preferably 0, 1, or 2, and each R, independently of the other C1 to C4 alkyl and aryl, preferably methyl or ethyl. Preferably, R' is selected like R, except for H. In other words, the organic radical R' is preferably selected from the same group as the organic radical R.

[0097] Preferably, it can be provided that in formula (V) X is selected from OH.

[0098] Preferably, the compound of formula (V) can be selected from C1-30 alkyl alcohol, C2-30 alkene alcohol, and C6-30 aryl alcohol.

[0099] Preferably, the compound of formula (V) is selected from C1-30 alkyl alcohol and C6-30 aryl alcohol.

[0100] Preferably, the compound of formula (V) may be selected from C4-20 alkyl alcohol and C6-24 aryl alcohol.

[0101] Preferably, the compound of formula (V) may be selected from C4-20 alkyl alcohol and C6-24 aryl alcohol.

[0102] Preferably, the compound of formula (V) may be selected from C6-16 alkyl alcohol and C6-12 aryl alcohol.

[0103] Preferably, the compound of formula (V) may be selected from C8-12 alkyl alcohols.

[0104] Preferably, the compound of formula (V) is selected from a linear C8-12 alkyl alcohol.

[0105] Preferably, the compound of formula (V) is selected from a linear CIO alkyl alcohol.

[0106] Preferably, the compound of formula (V) may be selected from saturated or unsaturated fatty alcohols.

[0107] Preferably, the compound of formula (V) is selected from caprylic alcohol, lauryl alcohol, margaryl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, montanyl alcohol, melissyl alcohol, palmitoleyl alcohol, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, and γ-linolenyl alcohol. Preferably, the compound of formula (V) is selected from saturated fatty alcohols.

[0108] Preferably, the compound of formula (V) can be selected from caprylic alcohol, lauryl alcohol, margaryl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, montanyl alcohol, and melissyl alcohol.

[0109] Preferably, the compound of formula (V) is selected from caprylic alcohol, lauryl alcohol, margaryl alcohol, stearyl alcohol.

[0110] Preferably, the compound of formula (V) is selected from and lauryl alcohol.

[0111] Preferably, all R' are independently selected from a linear C8-12 alkyl, and L is selected from propyl, iso-butyl, n-butyl, iso-pentyl, and n-pentyl.

[0112] Preferably, it can be provided that all R' are independently selected from a linear CIO alkyl, and L is selected from propyl, n-butyl, and n-pentyl, particularly preferably from n-butyl.

[0113] Preferably, it can be provided that all R' are the same organic radical.

[0114] Preferably, it can be provided that all L are the same organic linker.

[0115] Preferably, all X's may be the same functional group.

[0116] Preferably, it can be provided that all R are the same organic radical and all L are the same organic linker.

[0117] Preferably, it can be provided that all R are the same organic radical, all L are the same organic linker, and all X are the same functional group.

[0118] Preferably, it can be provided that in formula (IV) and optionally in formula (V) X is selected from OH.

[0119] Preferably, it can be provided that the compounds of formulas (III), (IV), and optionally (V) are reacted with each other stoichiometrically with respect to the desired phytic acid oligomer.

[0120] Preferably, it can be provided that the molar ratio of compound of formula (III) used to compound of formula (IV) used is less than or equal to 3:2 to greater than or equal to 1, more preferably greater than or equal to 20:19, more preferably greater than or equal to 10:9, more preferably greater than or equal to 6:5, more preferably greater than or equal to 5:4, particularly preferably greater than or equal to 4:3.

[0121] Preferably, it can be provided that the molar ratio of the compound of formula (III) used to the compound of formula (V) used is less than or equal to 1:12 to greater than or equal to 1:1, more preferably less than or equal to 1:11 to greater than or equal to 1:4, more preferably less than or equal to 1:10 to greater than or equal to 1:6, particularly preferably less than or equal to 1:9 to greater than or equal to 1:8.

[0122] Preferably, it can be provided that the molar ratio of the compound of formula (III) used to the compound of formula (IV) used is less than or equal to 3:2 to greater than or equal to 4:3, and the molar ratio of the compound of formula (III) used to the compound of formula (V) used is less than or equal to 1:9 to greater than or equal to 1:8.

[0123] Preferably, the reaction can be carried out with separation of a condensation product, preferably with separation of water.

[0124] Preferably, it can be provided that the compounds of formula (IV) and optionally (V) for the reaction of the process are dissolved in an organic solvent, preferably in an aprotic organic solvent, for example toluene.

[0125] Preferably, the compound of formula (III) for the reaction of the process is dissolved in a polar solvent, preferably a protic solvent, for example water.

[0126] Preferably, the reaction of the process can be carried out in a water separator.

[0127] Preferably, it can be provided that the process is carried out at a temperature in a range from greater than or equal to 100 °C to less than or equal to 200 °C, more preferably from greater than or equal to 120 °C to less than or equal to 190 °C, more preferably from greater than or equal to 140 °C to less than or equal to 180 °C, particularly preferably from greater than or equal to 150 °C to less than or equal to 170 °C. Preferably, it can be provided that the reaction is carried out until the theoretical amount of depositable condensation product is deposited or until no further condensation product is deposited.

[0128] The invention further proposes a use of the phytic acid oligomer for producing a polymer composition.

[0129] In a preferred embodiment, it can be provided that the phytic acid oligomer is used as a hardener for the crosslinking of a resin, in particular an epoxy resin or an OH-functionalized acrylate.

[0130] In an alternative preferred embodiment, it can be provided that the phytic acid oligomer is used with a hardener.

[0131] The invention further proposes a process for producing a polymer composition comprising the phytic acid oligomer according to the present invention, wherein the phytic acid oligomer according to the invention is mixed with reactants under the influence of temperature.

[0132] Preferably, the phytic acid oligomer can be mixed with an epoxy resin or an OH-functionalized acrylate under the influence of temperature.

[0133] The invention further proposes a polymer composition produced by the process according to the invention, wherein the polymer composition comprises the phytic acid oligomer according to the invention.

[0134] The invention is further explained below with reference to the figures and examples.

[0135] Fig. 1 shows schematically the course of temperature, storage modulus G' and loss modulus G" for a crosslinking reaction of an inventive

[0136] Phytic acid oligomer with a water-based epoxy. Figure 2 schematically shows the curves of temperature, storage modulus G', and loss modulus G" for a crosslinking reaction of a phytic acid oligomer according to the invention with a solvent-based epoxy.

[0137] Fig. 3 shows schematically the course of temperature, storage modulus G' and loss modulus G" for a crosslinking reaction of a phytic acid oligomer according to the invention with a solvent-based OH-acrylate.

[0138] Fig. 4 shows schematically the course of temperature, storage modulus G' and loss modulus G" for a crosslinking reaction of a phytic acid oligomer according to the invention with a water-based OH-acrylate.

[0139] Fig. 5 shows schematically the course of temperature, storage modulus G' and loss modulus G" for a crosslinking reaction of a phytic acid oligomer according to the invention with a water-based epoxy.

[0140] Fig. 6 shows schematically the course of temperature, storage modulus G' and loss modulus G" for a crosslinking reaction of a phytic acid oligomer according to the invention with a solvent-based epoxy.

[0141] Fig. 7 shows schematically the course of temperature, storage modulus G' and loss modulus G" for a crosslinking reaction of a phytic acid oligomer according to the invention with a solvent-based OH-acrylate.

[0142] Fig. 8 shows schematically the course of temperature, storage modulus G' and loss modulus G" for a crosslinking reaction of a phytic acid oligomer according to the invention with a water-based OH-acrylate.

[0143] Fig. 9 shows schematically the course of temperature, storage modulus G' and loss modulus G" for a crosslinking reaction of a phytic acid oligomer according to the invention with a water-based epoxy.

[0144] Fig. 10 schematically shows the curves of temperature, storage modulus G', and loss modulus G" for a crosslinking reaction of a phytic acid oligomer according to the invention with a solvent-based epoxy. Fig. 11 schematically shows the curves of temperature, storage modulus G', and loss modulus G" for a crosslinking reaction of a phytic acid oligomer according to the invention with bisphenol A diglycidyl ether.

[0145] Preparation of a phytic acid oligomer according to the invention

[0146] Two mol of butanediol, 26 mol of lauryl alcohol, and an amount of toluene appropriate for the flask were weighed into a four-necked flask equipped with a water separator, dropping funnel, condenser, and stirrer motor. The mixture was heated to 160°C in a preheated oil bath and stirred until all components were dissolved. 3 mol of phytic acid were then rapidly added as an aqueous solution (>75 wt.% phytic acid). After foaming had subsided somewhat, the removal of the reaction water was begun. Once the theoretical amount of separated water had been reached, the reaction mixture was cooled with stirring, and the phytic acid oligomer was isolated from the toluene phase. Unreacted phytic acid could be washed out with water.

[0147] Preparation of polymer compositions according to the invention

[0148] The phytic acid oligomer according to the invention was mixed with a reactant selected from a water-based epoxy (Beckopox 387w / 52wa), a solvent-based epoxy (Beckopox EP 301 / 75x), a solvent-based OH-acrylate (Macrynal sm 500 / 60x), and a water-based OH-acrylate (Bayhydrol A 2470) using a DAC 150.1 FV Speedmixer and applied to glass plates or steel plates with a rubber spatula at a thickness of 120 μm. The resulting films were dried at 80 °C for 15 minutes and then at 160 °C for 30 minutes.

[0149] Well-adhering polymer coatings were obtained.

[0150] Technical effect

[0151] Furthermore, corresponding polymer compositions were prepared directly in a rotational rheometer (Anton Paar MCR 102). The previously described starting materials were used. A plate geometry of 25 mm was used, and the measurements were carried out in the linear viscoelastic range with a strain of y = 0.1%, a frequency of f = 10 rad / s, and a measuring gap of 1 mm. The temperature was increased by 2 °C / min up to a maximum of 160 °C and held there for up to one hour. The glass transition temperature of the resulting polymer composition was subsequently measured using the same rotational rheometer, with the samples being measured at 0.5 °C / min from 20 °C to 160 °C with a strain of y = 0.1% and a frequency of f = 10 rad / s.

[0152] Further measurements were taken as follows:

[0153] Impact test according to EN ISO 6272-1,

[0154] Cross-cut test according to DIN EN ISO 2409,

[0155] Pendulum damping test according to EN ISO 1522,

[0156] Chemical resistance according to DIN EN ISO 2812-4, contact angle measurement according to DIN EN ISO 19403-2:2020.

[0157] Successful crosslinking of the phytic acid oligomer was demonstrated using a rotational rheometer. The results of the measurements during the preparation of the polymer composition are shown in Figs. 1 to 4. These show that the compositions crosslink from a liquid to a gel at a gel point. The gel point is defined as the point at which the liquid or dissolved reaction mixture forms larger networks and becomes a gel. The various graphs in Figs. 1 to 4 show that the gel point was reached shortly after the reaction temperature reached 160 °C. Only the reaction with Bayhydrol® A 2470 required a longer reaction time.

[0158] The polymer compositions obtained had glass transition temperatures Tg as listed in Table 1:

[0159] Table 1: Glass transition temperatures

[0160] The resulting polymer compositions exhibited coating properties comparable to those of conventional coatings. The measurement results are shown in Table 2. In particular, the pendulum hardness is comparable to the pendulum hardness of known systems.

[0161] The contact angle with water shows that the phytic acid oligomer used is sufficiently hydrophobic.

[0162] The more elastic epoxies also showed good properties in the impact test.

[0163] All systems showed good resistance to water. Only the water-based systems showed clouding or softening when exposed to acetone. All systems showed poor resistance to methyl ethyl ketone, similar to known systems.

[0164] Overall, all measured properties of the resulting polymer compositions were comparable to those of systems prepared with known crosslinkers instead of the phytic acid oligomer according to the invention. Advantages arise in particular from the aspect of renewable raw materials and the phosphate content of the polymer compositions, which can be advantageous for corrosion protection properties.

[0165] Table 2: Results of measurements.

[0166] Preparation of further polymer compositions according to the invention

[0167] In an analogous manner as described above, the following two oligomers PH-A and PH-B were prepared:

[0168] PH-A

[0169] Yield: 95.6%

[0170] M eq : 245.7 g / eq

[0171] 'H-NMR (400 MHz, D6-DMSO, d, ppm): 1.28 (m, J=6, -(CH2)4-CH2-CH2-O); 1.54 (m; -CH2-CH2-O); 1.86 (qint, J= 6.5 (O-CH2-CH2-CH2-aromat);2.62 (m, CH2-aromat) 3.86

[0172] (multi, P-O-CH2-CH2-); 7.23 (multi, (aromat-H)

[0012] 13 C-NMR (300 MHz, Ü6-DMSO, ppm): 30.98-31.76 (various CH2); 64.57 & 64.63 (various CH2-O-P); 125.33 & 125.83 & 125.87 &128.34 & 128.92 & 141.19 & 141.39 (various aromatic CH)

[0012]

[0173] 31 P-NMR (300 MHz, Dö-DMSO, ppm): -1.04, -1.34 [phosphate ester] [12,13] IR (Resonanz in [cm 4 ]: 3085, 3064, 3032 (stretch, C-H);2937 (asym. stretch CH2),

[0174] 2861 (sym. stretch CH2); 2669 & 2325 (board, stretch P-OH vibration); 1658 (board, stretch [P=O]-OH); 1600, 1581 (stretch C=C); 1498 (def. CH2);1469 (mono substituted aromatic C=C); 1454 (def. CH2); 1390 (wagging CH2); 1209-1111 (various stretch P=O); 995 (asym. stretch P-O-C); 478 ((RO)2(HO)P=O) [6,8]

[0175] PH-B Ausbeute: >99%

[0176] M eq : 140.1 g / eq

[0177] 'H-NMR (300 MHz, D6-DMSO, d, ppm): 1.86 (qint, J= 6.5 (O-CH2-CH2-CH2- aromat); 2.62 (m, CHz-aromat) 3.86 (multi, P-O-CH2-CH2-); 7.23 (multi, (aromatic-H)

[0012] UC-NMR (300 MHz, D6-DMSO, ppm): 30.97-31.71 (various CH2); 64.56 & 64.62

[0178] (CH2-O);69,76 (aromat-CH2-O) 125.32 & 125.83 & 125.88 & 128.32 & 128.91 & 141.19 & 141.39 (various aromatic C-H);

[0012]

[0179] 31 P-NMR (300 MHz, DÖ-DMSO, ppm): -1.04 & -1.12 [phosphate ester]; -13.26 [polyphosphate] [12,13] IR (Resonanz in [cm 4 ]: 3081, 3060, 3023 (stretch, C-H);2919 (asym. stretch CH2),

[0180] 2863 (sym. stretch CH2);2663, 2318 (board, stretch P-OH vibration); 1660 (board, stretch [P=O]-OH); 1604, 1581 (stretch C=C); 1488 (def. CH2);1473 (mono substituted aromatic C=C); 1457 (def. CH2); 1388 (wagging CH2); 1209-1114 (various stretch P=O); 997 (asym. stretch POC); 472 ((RO)2(HO)P=O) [6.8]

[0181] The two oligomers were then cross-linked. The results are shown in the following table:

[0182] PH-A PH-B

[0183] Water Solvent Water Solvent based based based based

[0184] (BuAc) (BuAc)

[0185] Binder Beckopox™ Beckopox™ Beckopox™ Beckopox™ 301 / 75X 387W / 52WA 301 / 75X 387W / 52WA

[0186] Curing at 160°C

[0187] Pendulum hardness 53 117 21 107

[0188] Gloss [20°;60°85°] 0.5; 6; 59 24; 71; 82 5; 39; 71 52; 78; 86

[0189] L*[65K;10°] 36.8 36.9 35.5 37.3 a* [65K;10°] 20.3 22.6 23.3 22.9 b* [65K;10°] c 13.1 13.5 14.3

[0190] Curing at room temperature

[0191] Pendulum hardness 33 60 39 46

[0192] Gloss [20°;60°85° 49; 82; 91 63; 91; 94 31; 71; 81 52; 78; 86

[0193] L*[65K;10°] 36.1 37.0 36.9 37.5 a* [65K;10°] 22.8 22.3 23.0 23.1 b* [65K;10°] 13.3 12.7 14.3 14.3

[0194] Fig. 5 shows schematically the course of temperature, storage modulus G' and loss modulus G" for a crosslinking reaction of PH-A with Beckopox™ 301 / 75X in butyl acetate, Fig. 6 the analogous graph for PH-B.

[0195] Fig. 7 shows schematically the course of temperature, storage modulus G' and loss modulus G'' for a crosslinking reaction of PH-A with Beckopox™ 301 / 75X in water, Fig. 8 the analogous graph for PH-B.

[0196] Fig. 9 shows schematically the course of temperature, storage modulus G' and loss modulus G" for a crosslinking reaction of PH-A with Macyrnal® SM 500 / 60X in butyl acetate, Fig. 10 the analogous graph for PH-B.

[0197] Fig. 11 shows schematically the course of temperature, storage modulus G' and loss modulus G" for a crosslinking reaction of PH-A with bisphenol A diglycidyl ether.

[0198] Subsequently, several pigment pastes were prepared in an analogous manner as above, consisting of: 69% Bayferrox® 130M

[0199] 17% PA oligomer (PH-A or PH-B)

[0200] 16% water or butyl acetate

[0201] In each case, the PA oligomer (PH-A or PH-B) was dissolved in the solvent or dispersed in water. Bayferrox 130M was then added while stirring and homogenized in a speed mixer. The resulting pigment paste is stable for at least 3 weeks.

[0202] Preparation of an oligomer according to the invention with a siloxane linker:

[0203] 26 mol of 3-phenylpropanol and an appropriate amount of toluene are weighed into a four-necked flask equipped with a water separator, two dropping funnels, a condenser, a foam breaker, and a stirrer motor. This mixture is heated to boiling point in a preheated oil bath. 3 mol of phytic acid and 2 mol of polydimethylsiloxane are then slowly added simultaneously, each through a dropping funnel. Once the theoretical amount of separated water has been reached, the reaction mixture is cooled while stirring. Unreacted phytic acid can be washed out with water.

[0204] The individual combinations of components and features of the aforementioned embodiments are exemplary; the replacement and substitution of these teachings with other teachings contained in this document and the cited documents is also expressly contemplated. Those skilled in the art will recognize that variations, modifications, and other embodiments described herein may also occur without departing from the spirit and scope of the invention.

[0205] Accordingly, the above description is to be considered exemplary and not limiting. The word "comprising" as used in the claims does not exclude other components or steps. The indefinite article "a" does not exclude the meaning of a plural. The mere fact that certain measures are recited in mutually different claims does not indicate that a combination of those measures cannot be used to advantage. The scope of the invention is defined in the following claims and their equivalents.

Claims

Patent claims 1. Phytic acid oligomer, consisting of at least two independently selected groups of the following formula (I) and at least one independently selected group of the following formula (II) where n is independently selected from an integer in a range from greater than or equal to 1 to less than or equal to 6, where m is independently selected from an integer in a range from greater than or equal to 2 to less than or equal to 6, where all R are independently selected from H or an organic residue, and where L is selected from an organic linker or a siloxane linker; and where each group of formula (II) links at least two independent groups of formula (I) together via covalent bonds, the asterisks representing bond positions.

2. Phytic acid oligomer according to claim 1, wherein in the phytic acid oligomer at least two of all R are selected together from H, and the remaining R are not H. Phytic acid oligomer according to claim 1 or 2, wherein all R are independently selected from H, Cl-30 alkyl, and C6-30 aryl. Phytic acid oligomer according to any one of claims 1 to 3, wherein L is selected from Cl-30 alkyl and C6-30 aryl. Phytic acid oligomer according to any one of claims 1 to 4, wherein the phytic acid oligomer has a molecular weight in the range of greater than or equal to 1344 g / mol to less than or equal to 17000 g / mol. Process for the preparation of a phytic acid oligomer according to any one of claims 1 to 5, wherein a compound of the following formula (III) with at least one combination of the following formula (IV) and optionally at least one combination of the following formula (V) R' — X (V) react with each other under the influence of temperature to form the phytic acid oligomer, wherein m is independently selected from an integer in the range of greater than or equal to 2 to less than or equal to 6, wherein R' is selected from an organic residue, and wherein L is selected from an organic linker or a siloxane linker; and wherein all X are independently selected from a functional group that can be reacted with formula (III) to form a phosphoric acid ester. A process according to claim 6, wherein the reaction is carried out with the deposition of a condensation product, preferably with the deposition of water. Use of the phytic acid oligomer according to any one of claims 1 to 5 for the preparation of a polymer composition. A process for the preparation of a polymer composition comprising the phytic acid oligomer according to any one of claims 1 to 5, wherein the phytic acid oligomer according to any one of claims 1 to 5 is mixed with a reactant under the influence of heat.Polymer composition produced according to the method of claim 9, wherein the polymer composition comprises the phytic acid oligomer according to any one of claims 1 to 5.

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