A binder based on a cyclic ether and containing a secondary amine group.

Abstract

The present invention relates to a method for producing polyaspartic acid ester compositions by reacting cyclic ethers having primary amino and / or primary aminoalkyl groups with fumaric acid esters and / or maleic acid esters, the polyaspartic acid ester compositions thus obtained, and their use in two-component coating agents.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polyaspartate ester composition by reacting a cyclic ether having a primary amino and / or primary aminoalkyl group with a fumarate ester and / or maleate ester, the polyaspartate ester composition thus obtained, and its use in a two-component coating composition. [Background technology]

[0002] Two-component (2C) coating compositions containing a reactive component that is reactive to isocyanate groups, particularly a polyisocyanate component combined with a polyhydroxyl component, have long been known as binders. They are suitable for producing high-quality coatings that can be tuned to be hard, elastic, abrasion-resistant, and above all, weather-resistant.

[0003] Within the scope of this 2C polyurethane coating technology, certain ester-containing secondary polyamines have been established in recent years. So-called polyaspartate esters or polyaspartates, when combined with paint polyisocyanates, are particularly suitable as binders in low-solvent or solvent-free (high-solids content) coating compositions, enabling rapid curing of coatings at low temperatures.

[0004] The use of polyaspartate esters in 2C coating compositions is described, for example, alone or in mixtures with further components that are reactive to isocyanate groups, as described in EP0403921, EP0639628, EP0667362, EP0689881, US5214086, EP0699696, EP0596360, EP0893458, DE19701835, EP0470461, WO15130501, WO15130502 and US5243012.

[0005] The preparation of amino-functional aspartate esters is well known. The synthesis is described in detail in the literature (Houben-Weyl, Meth.d.Org.Chemie vol.11 / 1,272 (1957), Usp.Khim.1969,38,1933), and is carried out by the addition of a primary polyamine to the active carbon-carbon double bond of a vinylogous carbonyl compound, such as those found in maleic acid or fumarate esters. In commercially available polyaspartate esters, maleic acid esters are used as the vinylogous carbonyl compound. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] EP0403921 [Patent Document 2] EP0639628 [Patent Document 3] EP0667362 [Patent Document 4] EP0689881 [Patent Document 5] US5214086 [Patent Document 6] EP0699696 [Patent Document 7] EP0596360 [Patent Document 8] EP0893458 [Patent Document 9] DE19701835 [Patent Document 10] EP0470461 [Patent Document 11] WO15130501 [Patent Document 12] WO15130502 [Patent Document 13] US5243012 [Non-patent literature]

[0007] [Non-Patent Document 1] Houben-Weyl,Meth.d.Org.Chemie vol.11 / 1,272 (1957) [Non-Patent Document 2] Usp.Khim.1969,38,1933 [Overview of the project]

[0008] The object of the present invention was to provide a polyaspartate ester-based coating composition that provides a coating with substantially improved solvent resistance compared to coatings based on conventional polyaspartate ester-containing coating compositions.

[0009] Surprisingly, it was found that this objective could be achieved by using polyaspartate ester compositions obtained by reacting cyclic ethers having primary amino and / or primary aminoalkyl groups with fumarate and / or maleate esters.

[0010] EP 141 062 states that the reaction of oxetanes and tetrahydrofurans having primary amino groups with isocyanates yields prepolymers that are further processed into elastomers.

[0011] The use of polyaspartate ester compositions based on cyclic ethers having primary amino and / or primary aminoalkyl groups, as well as their use in coating compositions for producing solvent-stable coatings, is not known from the prior art.

[0012] The present invention relates to general formula (I) [ka]

[0013] [During the ceremony, X is an m-valent organic group that can be obtained by removing a primary amino group from a corresponding cyclic ether, wherein the ether is a monocyclic or condensed bicyclic based on a monocyclic ether, and at least two of the ring carbon atoms have groups selected from primary amino groups and aliphatic-bonded primary amino groups, where R1 and R2 are identical or different organic groups, each having 1 to 18 carbon atoms. and m is an integer greater than 1. one or more polyaspartic acid esters and Optionally, general formula (II) [ka]

[0014] [During the ceremony, n is m-1, and X and bases R1 and R2 are as defined above. Contains or consists of one or more polyaspartate esters. Composition A1 is provided.

[0015] In formulas I and II, R1 and R2 are preferably the same or different alkyl groups having 1 to 18 carbon atoms each, more preferably the same or different alkyl groups having 1 to 8 carbon atoms each, and most preferably, in each case, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, or isobutyl groups. Ethyl is most preferred.

[0016] A cyclic ether from which X is derived has at least two primary amino groups and groups selected from aliphatic-bonded primary amino groups on its ring carbon atoms, and is monocyclic or dicyclic according to the following general formulas III and IV: [ka] [ka]

[0017] 〔Here, Y 4 is

Chem.

[0018] and Y is 2

Chem.

Chem.

[0019] and Y is 3

Chem.

Chem.

[0020] and and R 1 、R 2 、R 7 、R 8 、R 13 、R 14 is, independently, an alkylene group having 1 to 6 carbon atoms or hydrogen or an organic group, the latter being a saturated or unsaturated, linear or branched, aliphatic or alicyclic or optionally substituted aromatic or aromatic aliphatic monovalent group having up to 18 carbon atoms, which may contain heteroatoms from a series of oxygen, sulfur and nitrogen, and the heteroatom-containing groups include, for example, functional groups reactive with isocyanate groups and / or functional groups inert to isocyanate groups at temperatures up to 100 °C (excluding primary amino groups), and R 3 、R 4 、R​​​​​​​​​The first is an alkylene group or bond or hydrogen or organic group having 1 to 6 carbon atoms, the latter being a saturated or unsaturated, linear or branched, aliphatic or alicyclic or substituted aromatic or aromatic aliphatic monovalent group having up to 18 carbon atoms, which may contain a series of heteroatoms from oxygen, sulfur and nitrogen, and which heteroatom-containing groups may contain, for example, functional groups that are reactive with isocyanate groups and / or functional groups that are inert with isocyanate groups at temperatures up to 100°C (excluding primary amino groups). Here, In the case of equation III, base R 1 ~R 8 At least two of them are bonded to an NH2 group (i.e., C1-C6 alkylene group-NH2 (e.g., CH2-NH2) or bonded-NH2), and In the case of formula IV, base R 1 ~R 8 At least one of them is bonded to an NH2 group and R 10 ~R 14 At least one group of is bonded to an NH2 group (i.e., a C1-C6 alkylene group-NH2 (e.g., CH2-NH2) or bonded-NH2), and R 9 and R 9 ' is independently an H or a methyl group, and R 1 '~R 8 'and R 10 '~R 14 ' is independently a hydrogen or organic group, the latter being a saturated or unsaturated, linear or branched, aliphatic or alicyclic or substituted aromatic or aromatic aliphatic monovalent group having up to 18 carbon atoms, which may contain a series of heteroatoms from oxygen, sulfur and nitrogen, the heteroatom-containing group including, for example, functional groups reactive with isocyanate groups and / or functional groups inert with isocyanate groups at temperatures up to 100°C (excluding primary amino groups). The alkylene group having 1 to 6 carbon atoms may be linear or branched, and the alkylene group is preferably CH2, CH2-CH2, CH2-CH2-CH2 or CH2-CH2-CH2-CH2, more preferably CH2.

[0021] base R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 , R 13 , R 14 If the group is hydrogen or an organic group, it is preferably hydrogen and / or an alkyl group, each having 1 to 8 carbon atoms, very preferably hydrogen and / or an alkyl group such as a methyl, ethyl, propyl, isopropyl, butyl or isobutyl group, and most preferably hydrogen.

[0022] base R 1 '~R 8 'and R 10 '~R 14 Preferably, the group is hydrogen and / or an alkyl group having 1 to 8 carbon atoms each, most preferably hydrogen and / or an alkyl group such as a methyl, ethyl, propyl, isopropyl, butyl, or isobutyl group, and most preferably hydrogen.

[0023] A cyclic ether has at least two carbon atoms in the ring that are selected from primary amino groups and aliphatic-bonded primary amino groups.

[0024] The cyclic ether of formula III preferably has groups selected from primary amino groups and aliphatic-bonded primary amino groups on exactly three or two of the ring carbon atoms, more preferably on exactly two of the ring carbon atoms.

[0025] The bicyclic ether of formula III preferably has groups selected from primary amino groups and aliphatic-bonded primary amino groups on exactly two ring carbon atoms of one ring and exactly one ring carbon atom of the second ring. More preferably, each of the two rings has a group selected from primary amino groups and aliphatic-bonded primary amino groups on exactly one ring carbon atom.

[0026] If exactly three ring carbon atoms have groups selected from primary amino groups and aliphatic-bonded primary amino groups, then m in formulas I and II has a value of 3. If exactly two ring carbon atoms have such groups, then m in formulas I and II has a value of 2.

[0027] Preferred embodiment of Formula III: In equation III, Y 1 Preferably, the following applies:

[0028] i) Y 1 a, R 1 and R 2 It is CH2, And, R 1 ', R 2 ', R 3 , and R 3 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. ii) Y 1 b, base R 1 ~R 4 Two of them are CH2, And the remaining two of these groups and R 1 '~R 4 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. Or, R 3 and R 4 It is a combination, And, R 1 , R1 ’, R 2 , R 2 ’, R 3 ’, and R 4 ’ are, independently, an organic group having up to 18 carbon atoms as defined above or H, preferably an alkyl group having 1 to 8 carbon atoms or H, iii) Y 1 c, Group R 1 , R 2 , R 3 , R 5 Two of them are CH2, and the remaining two of these groups and R 1 ’ to R 5 ’ and R 4 are, independently, an organic group having up to 18 carbon atoms as defined above or H, preferably an alkyl group having 1 to 8 carbon atoms or H, or, R 3 and R 4 is a bond, and, R 1 , R 2 , R 5 and R 1 ’ to R 5 ’ are, independently, an organic group having up to 18 carbon atoms as defined above or H, preferably an alkyl group having 1 to 8 carbon atoms or H, or, R 3 and R 5 is a bond, and, R 1 , R 2 , R 4 and R 1 ’ to R 5 ’ are, independently, an organic group having up to 18 carbon atoms as defined above or H, preferably an alkyl group having 1 to 8 carbon atoms or H, or, R 1 is CH2, and R 3 , R 4 or R 5 is a bond, and, R 3 , R 4 and R5 The remaining two groups from, as well as R 1 ’~R 5 ’ and R 2 are an alkyl group or H having up to 18 carbon atoms or H as defined above, preferably having 1 to 8 carbon atoms, iv) Y 1 d, the group R 1 , R 2 , R 3 , R 6 two of which are CH2, and the remaining two of these groups and R 4 , R 5 , and R 1 ’~R 6 ’ are, independently, an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms, or, R 3 and R 6 are a bond, and, R 1 , R 2 , R 4 , R 5 and R 1 ’~R 6 ’ are, independently, an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms, or, R 1 is CH2, and R 3 or R 6 is a bond, and, R 3 and R 6 the remaining groups from, as well as R 1 ’~R 5 ’ and R 2 are, independently, an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms, v) Y 1 e, the group R 1 , R 2 , R 7Two of them are CH2, And the remaining one of these three groups, and R 1 ', R 2 'and R 7 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. vi) Y 1 f, base R 1 , R 2 , R 7 , R 8 Two of them are CH2, And the remaining two of these groups, and R 1 ', R 2 ', R 7 ', and R 8 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. vii) Y 1 g, base R 1 , R 2 , R 3 , R 7 Two of them are CH2, And the remaining two of these groups, and R 1 ', R 2 ', R 3 ', and R 7 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. Or, R 1 is CH2, and R 3 This is a combination, And, R 2 , R 7 , R 1 ', R 2 ', R 3 ', and R 7 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. viii) Y1 h, base R 1 , R 2 , R 3 , R 7 , R 8 Two of them are CH2, And the remaining three of these groups, and R 1 ', R 2 ', R 3 ', R 7 ', and R 8 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. Or, R 1 is CH2, and R 3 This is a combination, And, R 2 , R 7 , and R 8 , and R 1 ', R 2 ', R 3 ', R 7 ', and R 8 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. ix) Y 1 i, base R 1 , R 2 , R 3 , R 4 , R 7 Two of them are CH2, And the remaining three of these groups, and R 1 ', R 2 ', R 3 ', R 4 ', and R 7 ' is independently an organic group or H having 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. Or, R 1 is CH2, and R 3 or R 4 It is a combination, And, R 3and R 4 The remaining groups from, as well as R 2 , R 7 , R 1 ', R 2 ', R 3 ', R 4 ', and R 7 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms.

[0029] Particularly preferred embodiments of Formula III are embodiments ii), iii), v), vi), and vii).

[0030] Embodiments ii) and iii) are particularly preferred, and here ii) Y1 is Y 1 b is, R 1 and R 2 It is CH2, And, R 3 , R 4 and R 1 '~R 4 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. Or, R 3 and R 4 is CH2 or bond, And, R 1 , R 2 and R 1 '~R 4 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. iii) Y1 is Y 1 c, R 1 and R 2 It is CH2, And, R 3 , R 4 , R 5 and R 1 '~R 5' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. Or, R 3 and R 5 is CH2 or a bond, And, R 1 , R 2 , R 4 and R 1 '~R 5 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms.

[0031] The most preferred embodiments are ii) and iii), where ii) Y1 is Y 1 b is, R 1 and R 2 It is CH2, And, R 3 , R 4 and R 1 '~R 4 ' is independently a methyl group or H, preferably H. Or, R 3 and R 4 is CH2 or a bond, And, R 1 , R 2 and R 1 '~R 4 ' is independently a methyl group or H, preferably H. iii) Y1 is Y 1 c, R 1 and R 2 It is CH2, And, R 3 , R 4 , R 5 and R 1 '~R 5 ' is independently a methyl group or H, preferably H. Or, R 3 and R 5 is CH2 or a bond, And, R 1 , R 2 , R 4 and R 1 '~R 5 ' is independently a methyl group or H, preferably H.

[0032] Examples of the most preferred compounds of formula III are oxacyclopentane-2,3-,-2,4-,-2,5- or-3,4-di-methyleneamine or oxacyclohexane-2,3-,-2,4-,-2,5-,-2,6-,-3,4- or-3,5-di-methyleneamine.

[0033] Preferred embodiment of formula IV: In equation IV, Y 2 and Y 3 Preferably, the following applies:

[0034] a) Y 2 a and Y 3 a, R 2 is CH2, or R 10 is CH2 or bond, and R 1 is CH2, or R 3 is CH2 or bond, And, R 2 and R 10 The remaining group from R 1 and R 3 The remaining groups from, as well as R 1 ', R 2 ', R 3 ', and R 10 ' is independently a methyl, ethyl, propyl, isopropyl, butyl or isobutyl group or H, preferably H. b) Y 2 a and Y 3 b, R 2 is CH2, or R 10 is CH2 or bond, and R 1 is CH2, or R 3or R 4 is CH2 or bond, And, R 2 and R 10 The remaining group from R 1 , R 3 , and R 4 The remaining groups from, as well as R 1 ', R 2 ', R 3 ', R 4 ', and R 10 ' is independently a methyl, ethyl, propyl, isopropyl, butyl or isobutyl group or H, preferably H, and R 9 , R 9 ' is independently CH3 or H, preferably H, c) Y 2 a and Y 3 d, R 2 is CH2, or R 10 is CH2 or bond, and R 1 or R 7 CH2 is, And, R 2 and R 10 The remaining group from R 1 and R 7 The remaining groups from, as well as R 1 ', R 2 ', R 7 ', and R 10 ' is independently a methyl, ethyl, propyl, isopropyl, butyl or isobutyl group or H, preferably H, and R 9 , R 9 ' is independently CH3 or H, preferably H, d) Y 2 b and Y 3 b, R 2 is CH2, or R 10 or R 11 is CH2 or bond, and R 1 is CH2, or R 3 or R 4 is CH2 or bond, And, R 2 , R 10 , and R 11 The remaining group from R 1 , R 3 , and R 7 The remaining groups from, as well as R 1 ', R 2 ', R 3 ', R 4 ', R 10 ', and R 11 ' is independently a methyl, ethyl, propyl, isopropyl, butyl or isobutyl group or H, preferably H, and R 9 , R 9 ' is independently CH3 or H, preferably H, e) Y 2 d and Y 3 d, R 2 or R 13 CH2 is, and R 1 or R 7 CH2 is, And, R 2 and R 13 The remaining group from R 1 and R 7 The remaining groups from, as well as R 1 ', R 2 ', R 7 ', and R 13 ' is independently a methyl, ethyl, propyl, isopropyl, butyl or isobutyl group or H, preferably H, and R 9 , R 9 ' is independently CH3 or H, preferably H, f) Y 2 b and Y 3 d, R 2 is CH2, or R 10 or R 11 is CH2 or a bond, or R 1 or R 7 CH2 is, And, R 2 , R10 and R 11 The remaining group from R 1 and R 7 The remaining groups from, as well as R 1 ', R 2 ', R 7 ', R 10 ', and R 11 These are independently methyl, ethyl, propyl, isopropyl, butyl or isobutyl groups or H, preferably H, and R 9 , R 9 ' is independently CH3 or H, preferably H.

[0035] Particularly preferred embodiments of formula IV are embodiments a), b), and d). Very particularly preferred is R 9 , R 9 Embodiments a), b), and d) are subject to the constraint that the CH2 or non-bonded group is independently a methyl group or H, preferably H. Most preferred is R 9 , R 9 Embodiment a) is subject to the constraint that the CH2 or non-bonded group is independently a methyl group or H, preferably H.

[0036] Examples of particularly preferred compounds of formula IV include 3R,3aR,6R,6aR-hexahydrofloo[3,2-b]furan-3,6-diamine, 3R,3aR,6S,6aR-hexahydrofloo[3,2-b]furan-3,6-diamine, 3S,3aR,6S,6aR-hexahydrofloo[3,2-b]furan-3,6-diamine, and [3R,3aR,6R,6aR-6-(amino These are methyl)-hexahydrofl[3,2-b]furan-3-yl]methaneamine, [3R,3aR,6S,6aR-6-(aminomethyl)-hexahydrofl[3,2-b]furan-3-yl]methaneamine, [3S,3aR,6S,6aR-6-(aminomethyl)-hexahydrofl[3,2-b]furan-3-yl]methaneamine, and mixtures thereof.

[0037] Bio-based diamines: The diamine in formula III, where Y1 is Y 1 b is and base R 1 ~R 4 Two of them are CH2, And the remaining two of these groups and R 1 '~R 4 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. Or, R 3 and R 4 It is a combination, And, R 1 , R 1 ', R 2 , R 2 ', R 3 ', and R 4 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. and The diamine of formula IV, where Y 2 and Y 3 is Y 2 a and Y 3 a, R 10 is CH2 or a bond, and R 3 is a CH2 or bond, And, R 1 , R 2 , R 1 ', R 2 ', R 3 'and R 10 ' is independently a methyl, ethyl, propyl, isopropyl, butyl or isobutyl group or H, preferably H and R 9 , R 9 ' is independently CH3 or H, preferably H, In particular, the above-mentioned oxacyclopentane-2,5-di-methyleneamine (bis(aminomethyl)tetrahydrofuran / Formula III) and hexahydroflou[3,2-b]furan-3,6-diamine or [(aminomethyl)-hexahydroflou[3,2-b]furan-3-yl]-methaneamine stereoisomers (Formula IV) can be prepared, for example, from furfural or substituted furfural, such as 5-hydroxymethylfurfural, or from isosorbide, isomannide, or isoidide as a starting material. These starting materials can be obtained from bio-based or non-bio-based sources.

[0038] The term "starting material" refers to the chemical transformation that occurs during the production of diamines, meaning that the material is used up.

[0039] In the context of the present invention, the term "biobase" is defined as a compound, material, etc., such as a starting material of formula III or IV or a polyamine, obtained from or prepared from a renewable source such as plants, microorganisms, algae, or animals.

[0040] On the other hand, non-biobased compounds and materials are obtained from or prepared from non-renewable sources. Non-renewable sources include, for example, fossil raw materials formed from dead organisms of geological prehistoric times. These include, in particular, crude oil, lignite, coal, peat, and natural gas. Compounds and materials obtained from or prepared from non-renewable sources are defined in the context of this invention as non-biobased or “synthetically produced.”

[0041] Bio-based starting materials can be obtained directly from the renewable sources mentioned above, or they can be produced by subsequent reactions from compounds or materials obtained from such sources.

[0042] When bio-based diamines are used to produce the polyaspartate ester composition A1 of the present invention, this means that these diamines are entirely or partially bio-based. This depends on the extent to which bio-based starting materials are used in the production. In the case of partially bio-based diamines, at least one bio-based starting material is used.

[0043] The furfural or its substituted derivatives described above, such as 5-hydroxymethylfurfural, can be obtained in a biobased manner from pentoses and hexoses, which can then be obtained from fractions of cellulose, starch, or other polysaccharides. The described synthesis is merely one example of a possible synthesis. Of course, any other form of biobased production of furfural or its derivatives is also possible.

[0044] The synthesis of 2,5-bis(aminomethyl)tetrahydrofuran can be carried out, for example, by the chemical conversion of biobased 5-hydroxymethylfurfural via 2,5-franzicarboxylic acid, 2,5-bis(hydroxymethyl)furan, and 2,5-dihydroxymethyl-tetrahydrofuran, or by the chemical conversion of biobased furfural via furfuryl alcohol, tetrahydrofurfuryl alcohol, 2-hydroxymethyl-vinylfuran, 2,5-bis(hydroxymethyl)furan, and 2,5-dihydroxymethyl-tetrahydrofuran. These synthesis methods are also mentioned purely as examples and should not be understood as definitive.

[0045] Isosorbide, isomannide, or isoidide can also be obtained in a bio-based manner from, for example, pentoses and hexoses. These sugars are used to produce sorbitol or mannitol, which are then dehydrated to isosorbide and isomannide, respectively. Isosorbide can also be isomerized to isomannide. Isooidide is obtained from the isomerization of isosorbide or isomannide. The synthesis described herein is, likewise, merely an example. Of course, bio-based production of any other form of isosorbide, isomannide, or isoidide is also possible.

[0046] In this regard, it should also be made clear that the above-mentioned diamine can also be obtained in a non-biobased manner and can itself be used for the production of the polyaspartate ester composition A1 of the present invention.

[0047] In one embodiment of the present invention, composition A1 comprising a polyaspartate ester corresponds to one in which X can be obtained by removing a primary amino group from the above-mentioned type of cyclic ether, based on starting materials obtained in a bio-based manner.

[0048] In a preferred modification of this embodiment, composition A1 comprising polyaspartate ester composition A1 is The diamine of formula III [where Y 1 is Y 1 b is and base R 1 ~R 4 Two of them are CH2, And the remaining two of these groups and R 1 '~R 4 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. Or, R 3 and R 4 It is a combination, And, R 1 , R 1 ', R2 , R 2 ', R 3 ', and R 4 ' is independently an organic group or H having up to 18 carbon atoms as defined above, preferably an alkyl group or H having 1 to 8 carbon atoms. or The diamine of formula IV [where Y 2 and Y 3 Y 2 a and Y 3 a, R 10 is CH2 or bond, and R 3 is CH2 or bond, and R 1 , R 2 , R 1 ', R 2 ', R 3 'and R 10 ' is independently a methyl, ethyl, propyl, isopropyl, butyl or isobutyl group or H, preferably H, and R 9 , R 9 ' is independently CH3 or H, preferably H. [These diamines are based on starting materials obtained in a bio-based manner.] This corresponds to a cyclic ether from which X can be obtained by removing a primary amino group.

[0049] In a particularly preferred modification of this embodiment, composition A1 containing polyaspartate ester is 3R,3aR,6R,6aR-hexahydrofl[3,2-b]furan-3,6-diamine, 3R,3aR,6S,6aR-hexahydrofl[3,2-b]furan-3,6-diamine, [3S,3aR,6S,6aR-hexahydrofl[3,2-b]furan-3,6-diamine, 3R,3aR,6R,6aR-6-(aminomethyl)-hexahydrofl[3,2-b]furan-3-yl]- This corresponds to those from which X can be obtained by removing a primary amino group from tanamines, [3R,3aR,6S,6aR-6-(aminomethyl)-hexahydrofluoro[3,2-b]furan-3-yl]methaneamine, [3S,3aR,6S,6aR-6-(aminomethyl)-hexahydrofluoro[3,2-b]furan-3-yl]methaneamine, or oxacyclopentan-2,5-di-methyleneamine (these diamines are based on starting materials obtained in a bio-based manner).

[0050] If composition A1 contains one or more polyaspartate esters of general formula (II), they are present in proportion to >0%, preferably 0.1% or more (≧0.1%), more preferably 1% or more (≧1%), most preferably 4% or more (≧4%), and preferably 20% or less (≦20%), more preferably 15% or less (≦15%) of the GC area (measured as area %) in a gas chromatogram (where the sum of the GC areas of the two compounds of general formulas (I) and (II) is 100%). Any combination of the specified upper and lower limits is possible. It is considered that all possible combinations are disclosed.

[0051] Composition A1 comprises or consists of one or more polyaspartate esters of general formula (I) and optionally formula (II), preferably having a platinum-cobalt color index ≤ 100, more preferably ≤ 50. The platinum-cobalt color index is measured in accordance with DIN EN ISO 6271:2016-05.

[0052] The present invention also provides a method for producing composition A1 comprising or consisting of one or more polyaspartate esters of general formula (I) and optionally formula (II).

[0053] Composition A1, which contains or consists of one or more polyaspartate esters of general formula (I) and formula (II), can be prepared by the following method: General formula (V) [ka]

[0054] [Here, X is an m-valent organic group obtained by removing a primary amino group from a corresponding cyclic ether which is monocyclic or polycyclic and has saturated and / or unsaturated carbon-carbon bonds in the ring and primary amino groups attached to at least two of the ring carbon atoms by aliphatic bonds, where, m is an integer > 1, preferably 3, and more preferably 2. Polyamine General formula (VI) [ka]

[0055] [Here, R1 and R2 are the same or different organic groups, preferably the same or different alkyl groups having 1 to 18 carbon atoms each, more preferably the same or different alkyl groups having 1 to 8 carbon atoms each, and very preferably, in each case, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl groups, and most preferably ethyl. Reaction with the compound.

[0056] To produce composition A1 containing or comprising one or more polyaspartate esters of general formulas (I) and (II), compounds of general formulas (V) and (VI) are reacted at a temperature of 0°C to 100°C, preferably 20 to 80°C, more preferably 20 to 60°C, until the ratio of the equivalent amount of primary amino groups in the compound of general formula (V) to the equivalent amount of C=C double bonds in the compound of general formula (VI) is 1:1.2 to 1.2:1, preferably 1:1.05 to 1.05:1, and the residual content of the compound of general formula (VI) is 2 to 15% by weight, preferably 3 to 10% by weight.

[0057] Composition A1, which contains only polyaspartate ester of general formula (I) but not polyaspartate ester of formula (II), can be prepared in a similar manner, but in excess of the compound of general formula (VI), i.e., the ratio of the equivalent amount of primary amino groups in the compound of general formula (V) to the equivalent amount of C=C double bonds in the compound of general formula (VI) is 1:10, preferably 1:5, more preferably 1:2.

[0058] Following the above method, a distillation step may be performed to remove the unreacted portion of the compound of general formula (VI). This procedure is preferred.

[0059] Therefore, composition A1 is preferred, which contains or consists of one or more polyaspartate esters of general formula (I) and optionally formula (II), and the proportion of the compound of formula (VI) is 0.01% to 1.2% by weight (≧0.01% to ≦1.2% by weight), preferably 0.01% to 1% by weight (≧0.01% to ≦1% by weight), and more preferably 0.01% to 0.1% by weight (≧0.01% to ≦0.1% by weight), based on the total weight of component A, and dialkyl fumarate is preferred.

[0060] The appropriate conditions during distillation are a pressure range of 0.01 to 2 mbar, and a bottom outflow temperature ≤ 170°C and above (≧) the temperature resulting from the following equation (VII): [Formula 1] T(bottom outflow)=27×ln(p)+150 (VII) [Here, T (bottom runoff) is the temperature (°C) of the bottom runoff and p is the pressure (mbar) inside the distillation apparatus. Maintaining this pressure range ensures that the moderate temperature of the bottom outflow is sufficient to deplete the dialkyl fumarate content to the desired level, while also guaranteeing that the method remains usable on an industrial scale. At lower pressures, the gas density becomes too low, resulting in the need for very large equipment, and consequently, the method becomes economically unfeasible.

[0061] The temperature of the bottom outflow is preferably ≤170°C, but at least 20K higher than the temperature obtained from equation (VII), and more preferably 20K to 40K higher than the temperature obtained from equation (VII), but 170°C or less.

[0062] The primary polyamine of general formula (V) used in the above method corresponds to the monocyclic and polycyclic ethers described in the discussion of formulas I and II, and includes the preferred range described therein.

[0063] The preferred compounds of general formula (VI) used in the above method are maleic acid esters or fumaric acid esters of general formula (VI) in which R1 and R2 are the same or different organic groups each having 1 to 18 carbon atoms. Preferably, R1 and R2 are independently linear or branched alkyl groups having 1 to 8 carbon atoms, more preferably they are alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, or isobutyl groups, and particularly preferably ethyl.

[0064] Examples of compounds of general formula (VI) include the following: dimethyl maleate, diethyl maleate, di-n-propyl maleate or diisopropyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate or the corresponding fumarate ester. Diethyl maleate is particularly preferred.

[0065] The present invention also provides a composition A1 containing or comprising a polyaspartate ester in a mixture with a further polyaspartate ester different from A1 or a composition containing or comprising a polyaspartate ester (component A2).

[0066] These compositions A2 include, for example, composition A2.1 described below, and composition A1 may be blended within certain limitations: General formula (VIII) [ka]

[0067] [During the ceremony, Z is a p-valent organic group, which may contain one or more heteroatoms, has a (cyclo)aliphatic or aromaticaliphatic bonded amino group, has a molecular weight in the range of 60 to 6000 g / mol, and may contain further functional groups that are reactive to the isocyanate group and / or further functional groups that are inactive to the isocyanate group at temperatures up to 100°C. It can be obtained by removing a primary amino group from a corresponding polyamine. R 15 and R 16 These are identical or different organic groups, each having 1 to 18 carbon atoms. p is an integer > 1, preferably 2. one or more polyaspartic acid esters and Optionally, general formula (IX) [ka]

[0068] [Here q is p-1, Z, group R 15 and R 16 This is as defined above. One or more polyaspartic acid esters having a primary amino group. A2.1 composition containing or consisting of.

[0069] Here, R 15 and R 16 A polyaspartate ester-containing composition A2.1 is preferred, which contains or comprises one or more polyaspartate esters of general formula (VIII) and optionally formula (IX), where each is an identical or different alkyl group having 1 to 18 carbon atoms, preferably an identical or different alkyl group having 1 to 8 carbon atoms, most preferably an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, or isobutyl. Ethyl is most preferred.

[0070] Polyaspartate ester-containing composition A2.1 is a composition comprising or consisting of one or more polyaspartate esters of general formula (VIII) and optionally formula (IX), which are organic groups obtained by removing a primary amino group from a corresponding polyamine having a primary amino group to which Z is (cyclo)aliphatic or aromaticaliphatic.

[0071] Examples of polyamines include: etheramines such as ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 2,5-diamino-2,5-dimethylhexane, 1,5-diamino-2-methylpentane (Dytek® A from DuPont), 1,6-diaminohexane, 2,2,4 and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane or triaminononane, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine, or high molecular weight polyether polyamines having aliphatically linked primary amino groups, such as those marketed by Huntsman under the name Jeffamine®. Aliphatic polycyclic polyamines, such as tricyclodecan bismethylamine (TCD diamine) or bis(aminomethyl)norbornane, amino-functional siloxanes, such as diaminopropylsiloxane G10 DAS (Momentive), oleoalkyl-based amines, such as Solvay's Fentamine, and dimeric fatty acid diamines, such as Croda's Priamine, can also be used.

[0072] Further examples of diamines that can be used include 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (IPDA), 2,4- and / or 2,6-hexahydrotolylenediamine (H6-TDA), isopropyl-2,4-diaminocyclohexane and / or isopropyl-2,6-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 2,4'- and / or 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (Laromin® C 260, BASF AG), isomers of diaminodicyclohexylmethane substituted with methyl groups in the ring (=C-monomethyl-diaminodicyclohexylmethane), 3(4)-aminomethyl-1-methylcyclohexylamine (AMCA), and aromatic aliphatic diamines such as 1,3-bis(aminomethyl)benzene or m-xylenediamine.

[0073] Preferred amines are: polyether polyamines having aliphatically bonded primary amino groups, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,5-diamino-2-methylpentane, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4- and / or 2,6-hexahydrotolylenediamine, 1,5-diaminopentane, 2,4'- and / or 4,4'-diaminodicyclohexylmethane or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane. 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,5-diamino-2-methylpentane, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4- and / or 2,6-hexahydrotolylenediamine, 2,4'- and / or 4,4'-diaminodicyclohexylmethane or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane are particularly preferred.

[0074] Very particularly preferred are 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 2,4'- and / or 4,4'-diaminodicyclohexylmethane, and 1,5-diamino-2-methylpentane.

[0075] Composition A2.1 can be produced in a manner similar to the production method described above for Composition A1 using the amines specified above, which is also disclosed, for example, in EP19158880.5 or EP19158883.9.

[0076] For mixtures of compositions A1 and A2.1, the following applies: The proportion of the compound of formula VIII or the compound of formula VIII and IX (total amount, if the compound of formula IX is present) in the total weight of the compounds of formulas I, II (if present), VIII, and IX (if present) is ≤20% by weight, preferably ≤15% by weight, and more preferably ≤10% by weight.

[0077] The present invention also provides the use of composition A1 containing one or more polyaspartates of general formula (I) and any formula (II) in the production of a coating composition, preferably a two-component coating composition (2C coating composition), optionally in a mixture with composition A2 containing or comprising further polyaspartates; and provides a coating composition obtained thereby, its use in coating a substrate, a method for coating a substrate, and a substrate obtained thereby.

[0078] Therefore, the present invention is a1) Composition A1 containing at least one polyaspartate ester, a2) Optionally, composition A2 comprising or consisting of a further polyaspartate ester or polyaspartate ester different from A1, b) At least one polyisocyanate component B, c) Optionally, one or more components C that are reactive to isocyanate groups, unlike A1 and A2. d) Optionally, auxiliary agents and additives (component D) The present invention provides a coating composition containing, preferably a two-component coating composition (2C coating composition).

[0079] The two-component coating composition of the present invention preferably comprises at least one polyisocyanate component B.

[0080] A suitable polyisocyanate component B is an organic polyisocyanate having an average NCO functional value of at least 2 and a molecular weight of at least 140 g / mol. Particularly preferred are unmodified organic polyisocyanates in the molecular weight range of 140 to 300 g / mol, polyisocyanates for coatings in the molecular weight range of 300 to 1000 g / mol, and NCO prepolymers having urethane, urea and / or allophanate groups and a molecular weight exceeding 400 g / mol, or mixtures thereof.

[0081] In the context of the present invention, the term “polyisocyanate for coatings” is understood to mean a compound or mixture of compounds that can be obtained from simple polyisocyanates by oligomerization reactions known in themselves. Examples of suitable oligomerization reactions include carbodiimide, dimerization, trimerization, biuretization, urea formation, urethaneization, allophanate formation, and / or cyclization with the formation of an oxadiazine structure. The oligomerization may consist of more than one of the above reactions, carried out simultaneously or sequentially.

[0082] "Polyisocyanates for paints" are preferably biuret polyisocyanates, polyisocyanates containing isocyanurate groups, mixtures of polyisocyanates containing isocyanurate and uretdione groups, polyisocyanates containing urethane and / or allophanate groups, or mixtures of polyisocyanates containing isocyanurate and / or allophanate groups based on simple organic polyisocyanates.

[0083] Similarly, suitable polyisocyanate component B is a prepolymer containing isocyanate groups based on simple organic polyisocyanates and / or paint polyisocyanates, which are known in themselves, and on the one hand, an organic polyhydroxy compound having a molecular weight greater than 300 g / mol. Paint polyisocyanates containing urethane groups are derivatives of low molecular weight polyols with molecular weights in the range of 62 to 300 g / mol, and suitable polyols are, for example, ethylene glycol, propylene glycol, trimethylolpropane, glycerol, or mixtures thereof, while prepolymers containing isocyanate groups are prepared using polyhydroxy compounds having a molecular weight greater than 300 g / mol, preferably greater than 400 g / mol, and more preferably 400 to 8000 g / mol. Such polyhydroxy compounds particularly have 2 to 6, preferably 2 to 3, hydroxyl groups per molecule and are selected from the group consisting of ethers, esters, thioethers, carbonates, and polyacrylate polyols and mixtures of such polyols.

[0084] In the production of a prepolymer containing isocyanate groups, the above high molecular weight polyol may also be used in the form of a mixture with the above low molecular weight polyol, directly producing a mixture of a low molecular weight polyisocyanate for coatings containing urethane groups, which is equally suitable as the polyisocyanate component b) of the present invention, and a high molecular weight NCO prepolymer.

[0085] For the preparation of a prepolymer containing isocyanate groups or a mixture thereof with a polyisocyanate for coatings, a simple organic polyisocyanate or polyisocyanate for coatings of the type described as an example below is reacted with a high molecular weight hydroxyl compound or a mixture thereof with a low molecular weight polyhydroxyl compound of the type described as an example below, while maintaining an NCO / OH equivalent ratio of 1.1:1 to 40:1, preferably 2:1 to 25:1, to form a urethane and / or allophanate. If an excess of distillable simple organic polyisocyanate is used, it may be optionally removed by distillation after the reaction, resulting in a monomer-free NCO prepolymer containing isocyanate groups, which can also be used as polyisocyanate component b).

[0086] Examples of suitable simple organic polyisocyanates include 1,4-diisocyanate butane, 1,5-diisocyanate pentane, 1,6-diisocyanate hexane (HDI), 1,5-diisocyanate-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanate hexane, tetramethylxylene diisocyanate (TMXDI), 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane (isophorone diisocyanate, IPDI), 1-isocyanate-1-methyl-4(3)-isocyanate methylcyclohexane, dicyclohexylmethane 2,4'-diisocyanate and / or 4,4 '-diisocyanates, 1,10-diisocyanate todecane, 1,12-diisocyanate dodecane, cyclohexane 1,3- and 1,4-diisocyanates, xylene diisocyanate isomers, triisocyanate nonane (TIN), naphthylene 1,5-diisocyanate, 2,4-diisocyanate toluene, or mixtures thereof with 2,6-diisocyanatotoluene, preferably based on the mixture, up to 35% by weight of 2,6-diisocyanatotoluene, diphenylmethane-based 2,2'-, 2,4'-, 4,4'-diisocyanate diphenylmethane or industrial polyisocyanate mixtures, or any desired mixture of the above polyisocyanates.

[0087] Here, 1,4-diisocyanate butane, 1,5-diisocyanate pentane, 1,6-diisocyanate hexane (HDI), 1,5-diisocyanate-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanate hexane, tetramethylxylene diisocyanate (TMXDI), 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane (isophorone diisocyanate, IPDI), 1-isocyanate-1-methyl It is preferable to use aliphatic, alicyclic or aromatic aliphatic polyisocyanates selected from -4(3)-isocyanate methylcyclohexane, dicyclohexylmethane 2,4'- and / or 4,4'-diisocyanate, 1,10-diisocyanate todecane, 1,12-diisocyanate todecane, cyclohexane 1,3- and 1,4-diisocyanate, xylylene diisocyanate isomers, triisocyanate nonane (TIN), or any desired mixture of such polyisocyanates.

[0088] In principle, and naturally, it is also possible to use a mixture of the different types of polyisocyanate components mentioned above.

[0089] In addition to the polyaspartate ester-containing composition A1 and optionally A2, the preferred two-component coating composition of the present invention may contain a further component (component C) that is reactive to isocyanate groups.

[0090] These can be, for example, low molecular weight polyols in the molecular weight range of 62 to 300 g / mol, such as ethylene glycol, propylene glycol, trimethylolpropane, glycerol or mixtures of these alcohols, or polyhydroxy compounds having a molecular weight of more than 300 g / mol, preferably more than 400 g / mol, more preferably 400 to 8000 g / mol. Such polyhydroxyl compounds particularly have 2 to 6, preferably 2 to 3 hydroxyl groups per molecule and are selected from the group consisting of ethers, esters, thioethers, carbonates and polyacrylate polyols and mixtures of such polyols.

[0091] The preferably two-component coating composition of the present invention may further contain auxiliaries and additives (component D). These are auxiliaries and additives customary in coating technology, such as, for example, inorganic or organic pigments, other organic light stabilizers, radical scavengers, paint additives such as dispersants, leveling agents, thickeners, defoamers and other auxiliaries, binders, bactericides, fungicides, stabilizers or inhibitors, catalysts and solvents.

[0092] The ratio of the isocyanate groups in the polyisocyanate component B to the isocyanate-reactive groups in components A1, A2 and C is preferably 0.5:1.0 to 3.0:1.0. A ratio of 0.9:1.0 to 1.5:1.0 is particularly preferred, and a ratio of 1.0:1.0 to 1.25:1.0 is very particularly preferred.

[0093] The coating composition of the present invention is preferably neither foaming nor foam-forming. The composition is preferably not free-radical polymerizable, particularly not photopolymerizable, i.e., the composition does not cure by a free-radical process, particularly not by a free-radical polymerization process initiated by actinic radiation.

[0094] The coating composition of the present invention is produced by methods known per se in paint and coating technology.

[0095] A preferred method for producing a two-component coating composition is described below: The isocyanate-reactive (R) and isocyanate-containing components (H) are first prepared separately by mixing the respective isocyanate-reactive components A1 and optionally A2 and C, and then mixing them with the respective polyisocyanate component B. Auxiliaries and additives D1 and D2 are preferably mixed with the isocyanate-reactive component R. The components R and H thus produced are not mixed until immediately before or during application. If mixing is performed before application, it should be noted that the reaction of the components begins immediately after mixing. The reaction rate varies depending on the selection of components and additives. The processing time during which the composition must be applied is also known as the pot life and is defined as the time from mixing the components until the initial viscosity and / or flow time doubles (determined according to DIN EN ISO 2431:2012-03, but using a DIN 4 flow cup); this ranges from 1 minute to 24 hours, depending on the selection of components. The pot life is determined by methods known to those skilled in the art.

[0096] The present invention also relates to a method for coating a substrate, comprising at least the following steps: i) A step of applying the two-component coating composition of the present invention to at least a portion of the substrate to be coated, and ii) Curing of the coating composition from step i).

[0097] The substrate may already be fully or partially coated with one or more coating layers. These coating layers may be uncured or wet, and may be partially cured or fully cured; further coating layers on the substrate are preferably partially cured or fully cured. Examples of coating layers include primer coats, undercoats, fillers, sprinkling coats, base coats, or substrates that are already fully painted and recoated after possible pretreatment such as sanding or plasma activation.

[0098] The coating compositions of the present invention are preferably used in the fields of corrosion protection, initial coating of automobiles, refinishing of automobiles, coatings for heavy vehicles, coatings for plastics, general industrial coatings, floor coatings, and / or wood / furniture. [Examples]

[0099] Experiment Section Raw materials and base materials: Desmophene NH 1220: an amino-functional coreactant having an amine value of 240-248 mgKOH / g, a viscosity of ≤100 mPa·s (25°C), and a color index of ≤250 (Hazen). Manufacturer: Covestro.

[0100] Desmofen NH 1420: an amino-functional coreactant with an amine value of 199-203 mgKOH / g, viscosity of 900-2000 mPa·s (25°C), and a color index (Hazen) of ≤250. Manufacturer: Covestro.

[0101] Desmodur N 3900: A low-viscosity HDI trimer with approximately 23.5% NCO, a viscosity of approximately 730 mPa·s (25°C), and ≤0.25% free HDI. Manufacturer: Covestro.

[0102] Solvents: Solvesso 100, 1-methoxy-2-propyl acetate (MPA), ethyl acetate (EA), butyl acetate (BA), acetone (Ac), and xylene (Xy), Azelis, Germany.

[0103] Tetrahydrofrangimethaneamine, Merck, Germany.

[0104] 3S,3aR,6S,6aR-Hexahydrofl[3,2-b]furan-3,6-diamine, Merck, Germany.

[0105] [3S,3aR,6S,6aR-6-(aminomethyl)-hexahydrofluoro[3,2-b]furan-3-yl]methaneamine Merck, Germany.

[0106] Diethyl maleate: Aldrich, Germany.

[0107] 3R,3aR,6S,6aR-Hexahydroflo[3,2-b]furan-3,6-diamine was prepared by the method described in ChemSusChem 2011, 4, 1823-1829.

[0108] method: Dimethyl fumarate content was quantified using GC with an internal standard. An Agilent 6890 gas chromatograph with a standard GC capillary (100% polysiloxane phase) and an FID detector was used. The injector temperature (split outlet) was 180°C, and helium was used as the carrier gas. The limit of quantification for this method was 300 ppm.

[0109] GC-MS analysis was performed using an Agilent 6890 gas chromatograph and an Agilent 5973 mass spectral detector, employing standard ionization (electron bombardment) at 70 eV, a standard GC capillary (100% polysiloxane phase), and split injection at an injector temperature of 250°C. Gas chromatograms were evaluated based on area percentage.

[0110] All viscosity measurements were performed at 23°C using a Physica MCR 51 rheometer from Anton Paar Germany GmbH (DE), in accordance with DIN EN ISO 3219:1994-10.

[0111] The Hazen color index values ​​were measured using a Lico 400 colorimeter from Hach Lange GmbH (Germany), in accordance with DIN EN ISO 6271:2016-05.

[0112] The amine value was determined titrately in accordance with EN ISO 9702:1998 (perchloric acid method), except that the result was expressed as an amine value. The amine value at mgKOH / g was calculated according to the following formula:

[0113]

number

[0114] Drying was measured on glass in accordance with DIN EN ISO 9117-5:2012-11.

[0115] Solvent stability was measured in accordance with DIN EN ISO 4628-1:2016-07. Solvent stability tests were performed using xylene (hereinafter abbreviated as Xy), methoxypropyl acetate (hereinafter abbreviated as MPA), ethyl acetate (hereinafter abbreviated as EA), and acetone (hereinafter abbreviated as Ac) as solvents. The contact time for each was 5 minutes. Test specimens were prepared in accordance with the cited standards. Test surfaces were evaluated by visual inspection and scratching using the following classification: 0 = no apparent change; 1 = swelling ring, hard surface, only visible change; 2 = swelling ring, slight softening; 3 = clear softening (possibly slight blistering); 4 = significant softening (possibly severe blistering), potential for scratching of the substrate; 5 = coating completely destroyed without external influence.

[0116] The damping of the König pendulum on a glass plate was determined in accordance with DIN EN ISO 1522; 2007-04. The thickness of the dry film was 45–52 μm for all films.

[0117] The cross-cut test was performed in accordance with DIN EN ISO 2409:2006-13.

[0118] The gloss of the obtained coating at 20° was measured reflectivity-wise in accordance with DIN EN ISO 2813:2015-02.

[0119] Scratching - Clock meter: The coating material is scratched using a clock meter in accordance with DIN EN ISO 105-X12:2016-11. The coated substrate is positioned parallel to the direction of the friction fingers. Twenty linear friction motions are performed on the dry sample over a distance of 10⁴±3 mm at a frequency of one cycle per second, which includes 10 sets of back-and-forth motions with a downward force of 9±0.2 N. The gloss of the test specimen is then measured reflectivity.

[0120] Reflow: Reflow represents the recovery of a scratched coating surface after thermal stress, based on its gloss value. The coating is scratched by dry scratching (clock meter). Residual gloss is measured after the scratching cycle. The coating is placed in a 60°C oven for 2 hours, and then the gloss is measured according to the procedure described above. Reflow is reported as a percentage, i.e., the ratio of residual gloss after heat treatment to gloss before scratching.

[0121] Weathering: - CAM 180: Accelerated weathering tests in the presence of UV radiation were conducted in accordance with SAE J2527. Test plates were checked every 250 hours.

[0122] - UV-A test: UV-A testing of the coating materials was performed in accordance with DIN EN ISO 16474-3:2014-03 (Cycle 1). Test plates were checked every 250 hours.

[0123] - Calculation of b value and delta E: The Delta E value can be calculated using Dr.Lange Micro Color II from the L, a, and b values ​​determined in the Lab color space, in accordance with DIN ISO / CIE 11664-4:2019-04.

[0124] Synthesis of polyaspartate esters (PAEs) according to the present invention PAE 1: [ka]

[0125] It was prepared using tetrahydrofrangimethaneamine.

[0126] PAE 2: [ka]

[0127] It was prepared using [3S,3aR,6S,6aR-6-(aminomethyl)-hexahydrofluoro[3,2-b]furan-3-yl]methaneamine.

[0128] PAE3 and 4: [ka]

[0129] Prepared using two isomers: PAE 3:3S,3aR,6S,6aR-hexahydrofloo[3,2-b]furan-3,6-diamine and PAE 4:3R,3aR,6S,6aR-hexahydrofloo[3,2-b]furan-3,6-diamine.

[0130] Polyaspartate ester PAE 1 (the present invention) 340.2 g of tetrahydrofranimethaneamine (rel-((2R,5S)-tetrahydrofuran-2,5-diyl)methaneamine, cis) was initially charged at 30°C under dry nitrogen with stirring. 900.0 g of diethyl maleate was added dropwise, ensuring the temperature did not exceed 60°C. Upon completion of the addition, the temperature was adjusted to 45°C, and the mixture was stirred at 45°C for 1 hour. The mixture was then stored at 23°C for 1 week. A light-colored product with the following material data was obtained: Diethyl fumarate (GC) 1.74% by weight Viscosity 170mPas Color Index 22APHA Amine value: 234 mgKOH / g Polyaspartate ester PAE 3 (the present invention) 72.08 g of (3S,3aR,6S,6aR)-hexahydroflu[3,2-b]furan-3,6-diamine was first packed under dry nitrogen and heated to 90°C with stirring. 172.0 g of diethyl maleate was added dropwise to ensure the temperature was not maintained at 90°C. At the end of the addition, the temperature was adjusted to 60°C and the mixture was stirred at 60°C for 2 hours. The mixture was then stored at 23°C for 20 weeks. A product with the following material data was obtained: Diethyl fumarate (GC) 4.82% by weight Amine value: 240 mg KOH / g Viscosity 1010mPas Polyaspartate ester PAE 2 (the present invention) 86.11 g of [(3S,3aR,6S,6aR)-6-(aminomethyl)-hexahydrofluoro[3,2-b]furan-3-yl]methaneamine was initially charged at 30°C under dry nitrogen with stirring. 172.0 g of diethyl maleate was added dropwise, ensuring the temperature did not rise above 60°C. At the end of the addition, the temperature was adjusted to 45°C, and the mixture was stirred at 45°C for 1 hour. The mixture was then stored at 23°C for 4 weeks. A product with the following material data was obtained: Diethyl fumarate (GC) 5.35% by weight Amine value: 253 mgKOH / g Viscosity 850mPas Polyaspartate ester PAE 4 (the present invention) 72.08 g of (3R,3aR,6S,6aR)-hexahydroflu[3,2-b]furan-3,6-diamine was first packed under dry nitrogen and heated to 90°C with stirring. 172.0 g of diethyl maleate was added dropwise, ensuring that the temperature did not rise above 90°C. At the end of the addition, the temperature was adjusted to 60°C and the mixture was stirred at 60°C for 2 hours. The mixture was then stored at 23°C for 8 weeks. A product with the following material data was obtained: Diethyl fumarate (GC) 8.75% by weight Amine value: 226 mgKOH / g Viscosity 420mPas Coating preparation: Table 1: Weight (grams) [Table 1]

[0131] Mixing and applying the coating base and hardener: In both cases, components A (coating base) and B (curing agent) were combined and thoroughly mixed. The mixture was then applied to a glass plate using an applicator frame (wet layer thickness 90 μm) and dried at room temperature (23°C). A glossy, high-gloss coating with a dry film thickness of 45–52 μm was obtained. Tables 2–4 summarize the measured coating properties. [Table 2]

[0132] Solvent resistance: Measurements were taken on a clear coat on a glass plate. Rating: 0-5 (0 = film coating unchanged, 5 = completely dissolved) As can be seen from the table, the polyaspartate ester-based coating of the present invention has considerably better solvent resistance and considerably better reflow behavior than conventional polyaspartate ester-based coatings.

[0133] Weather resistance test: i) Gloss development: [Table 3]

[0134] As can be seen from Table 3, the gloss phenomenon of the coating of the present invention is comparable to that of conventional polyaspartate ester-based coatings.

[0135] ii) Yellowing resistance: [Table 4]

[0136] As can be seen from Table 4, the coating of the present invention exhibits significantly better resistance to yellowing than the corresponding polyaspartate-based coatings of the prior art.

Claims

1. General formula (I) 【Chemistry 1】 [During the ceremony, X is an m-valent organic group that can be obtained by removing a primary amino group from a cyclic ether, wherein the cyclic ether is monocyclic or condensed bicyclic, and at least two of the ring carbon atoms have groups selected from primary amino groups and aliphatic-bonded primary amino groups, where R1 and R2 are identical or different organic groups each having 1 to 18 carbon atoms, and m is an integer greater than 1] One or more polyaspartate esters of general formula (II) 【Chemistry 2】 [During the ceremony, n is m-1, Composition A1 comprising or consisting of one or more polyaspartic acid esters having a primary amino group of X and groups R1 and R2 as defined above, The composition wherein the cyclic ether is a monocyclic or bicyclic ether according to the following general formulas III and IV. General formula III 【Transformation 7】 General formula IV 【Transformation 8】 [Here, Y １ teeth, 【Chemistry 9】 And, And, Y ２ teeth, 【Chemistry 10】 And, And, Y ３ teeth, 【Chemistry 11】 and R １ 、R ２ 、R ７ 、R ８ 、R １３ 、R １４ is independently an alkylene group having 1 to 6 carbon atoms bonded to an NH₂ group, or hydrogen, or an organic group, and the organic group is an alkyl group having up to 8 carbon atoms, and R ３ , R ４ , R ５ , R ６ , R １０ , R １１ , R １２ This is independently a linear or branched alkylene group or bond or hydrogen or organic group having 1 to 6 carbon atoms bonded to an NH2 group, and the organic group is an alkyl group having 1 to 8 carbon atoms, where, In the case of formula III, base R １ ~R ８ At least two of them are NH ２ It is bonded to the base, and In the case of formula IV, base R １ ~R ８ At least one of them is NH ２ The base is linked and the base R １０ ~R １４ At least one of them is NH ２ It is bonded to the base, and R ９ and R ９ ' is independently an H or a methyl group, and R １ '~R ８ 'and R １０ '~R １４ ' is independently hydrogen or an organic group, the organic group being an alkyl group having 1 to 8 carbon atoms.

2. General formula (I) 【Transformation 3】 [During the ceremony, X is an m-valent organic group that can be obtained by removing a primary amino group from a cyclic ether, wherein the cyclic ether is monocyclic or condensed bicyclic, and at least two of the ring carbon atoms have groups selected from primary amino groups and aliphatic-bonded primary amino groups, where R1 and R2 are identical or different organic groups each having 1 to 18 carbon atoms, and m is an integer greater than 1] One or more polyaspartate esters of general formula (II) 【Chemistry 4】 [During the ceremony, n is m-1, A method for producing composition A1 comprising or consisting of one or more polyaspartic acid esters having a primary amino group of X and groups R1 and R2 as defined above, and general formula (V) 【Transformation 5】 A polyamine of the form [wherein X and m are as defined above] is given by general formula (VI) 【Transformation 6】 The production method, comprising reacting with a compound of [wherein R1 and R2 are as defined above], The method for producing the cyclic ether, wherein the cyclic ether is monocyclic or bicyclic according to the following general formulas III and IV. General formula III 【Transformation 7】 General formula IV 【Transformation 8】 [Here, Y １ teeth, 【Chemistry 9】 And, And, Y ２ teeth, 【Chemistry 10】 And, And, Y ３ teeth, 【Chemistry 11】 and R １ , R ２ , R ７ , R ８ , R １３ , R １４ This is independently an alkylene group or hydrogen or organic group having 1 to 6 carbon atoms bonded to an NH2 group, and the organic group is an alkyl group having 1 to 8 carbon atoms, and R ３ , R ４ , R ５ , R ６ , R １０ , R １１ , R １２ This is independently a linear or branched alkylene group or bond or hydrogen or organic group having 1 to 6 carbon atoms bonded to an NH2 group, and the organic group is an alkyl group having 1 to 8 carbon atoms, where, In the case of formula III, base R １ ~R ８ At least two of them are NH ２ It is bonded to the base, and In the case of formula IV, base R １ ~R ８ At least one of them is NH ２ The base is linked and the base R １０ ~R １４ At least one of them is NH ２ It is bonded to the base, and R ９ and R ９ ' is independently an H or a methyl group, and R １ '~R ８ 'and R １０ '~R １４ ' is independently hydrogen or an organic group, the organic group being an alkyl group having 1 to 8 carbon atoms.

3. Composition A1 according to claim 1, wherein the alkylene group having 1 to 6 carbon atoms is CH ２ ,CH ２ -CH ２ ,CH ２ -CH ２ -CH ２ or CH ２ -CH ２ -CH ２ -CH ２ The composition A1 is as described above.

4. A composition A1 according to any one of claims 1 or 3, wherein X is obtained by removing a primary amino group from a cyclic ether of the above type based on a starting material obtained in a bio-based manner.

5. Composition A1 according to any one of claims 1 or 3 to 4, in a mixture with a further polyaspartate ester different from A1, or in a mixture with a composition comprising the further polyaspartate ester.

6. In the production of coating compositions, Use of composition A1 according to any one of claims 1 or 3 to 4, or The use of a mixture of composition A1 according to any one of claims 1 or 3 to 4 and a further polyaspartate ester different from composition A1, or a mixture of composition A1 and a composition containing the further polyaspartate ester.

7. A coating composition, a1) Composition A1 containing at least one polyaspartate ester according to any one of claims 1 or 3 to 4, a2) Optionally, a further polyaspartate ester different from A1, or composition A2 comprising the further polyaspartate ester, b) At least one polyisocyanate component B, c) Optionally, one or more components C that are reactive to isocyanate groups, unlike A1 and A2. (d) Optionally, auxiliary agents and additives (component D) The composition comprising the above.

8. At least the following steps: i) Applying the coating composition according to claim 7 to at least a portion of the substrate to be coated, ii) Curing the coating composition from step i). A method for coating a substrate, including [a specific component].

9. A substrate coated with a coating obtained according to the method of claim 8.

10. A method for producing composition A1 according to claim 2, wherein the alkylene group having 1 to 6 carbon atoms is CH ２ ,CH ２ -CH ２ ,CH ２ -CH ２ -CH ２ or CH ２ -CH ２ -CH ２ -CH ２ A method for producing the composition A1.

11. A method for producing composition A1 according to any one of claims 2 and 10, wherein X is obtained by removing a primary amino group from a cyclic ether of the above type based on a starting material obtained in a bio-based manner.

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