WO2011128437A1 - Polymères d'amine et oligomères d'amine très ramifiés comme agent de protection anticorrosion - Google Patents

Polymères d'amine et oligomères d'amine très ramifiés comme agent de protection anticorrosion Download PDF

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WO2011128437A1
WO2011128437A1 PCT/EP2011/056007 EP2011056007W WO2011128437A1 WO 2011128437 A1 WO2011128437 A1 WO 2011128437A1 EP 2011056007 W EP2011056007 W EP 2011056007W WO 2011128437 A1 WO2011128437 A1 WO 2011128437A1
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amine
alkylene
alkyl
melamine
use according
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Maxim Peretolchin
Stephan Hüffer
Guido Vandermeulen
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints

Definitions

  • the present invention relates to the use of highly branched polymers or oligomeric compounds, which are prepared by condensation of melamine (derivatives) and / or urea (derivatives) with di- or polyamines, to reduce or prevent the corrosion of corrosion-prone materials. Furthermore, the invention relates to a method for reducing, delaying or preventing the corrosion of materials susceptible to corrosion, in which the materials and / or the corrosive medium to which the materials are exposed are brought into contact with at least one of these hyperbranched polymers and / or oligomers, and a corrosion inhibitor containing these highly branched polymers and / or oligomers and an anticorrosion pigment.
  • Corrosion is generally understood as the reaction of a material with its environment, which causes a measurable change in the material and can lead to an impairment of the function of a component or an entire system. In most cases the reaction is electrochemical, in some cases it may be due to chemical or metal-physical processes.
  • corrosion is usually used for metallic materials, but in its broader meaning it also includes the modification of other materials, such as glass, plastics or building materials.
  • the corrosion protection measures can be differentiated between active and passive corrosion protection. Active measures include, for example, providing a sacrificial anode or an extraneous anode, reducing or preventing the contact of the material to be protected with the corrosive medium, the use of corrosion inhibitors and the passivation of metal surfaces. Passive corrosion protection primarily refers to providing the material surface to be protected with a protective layer which, for example, prevents or at least considerably delays the diffusion of the corrosive medium, such as water, oxygen or corrosion-promoting ions.
  • the protective layers may be metallic, inorganic-non-metallic or organic in nature.
  • Metallic protective layers form a composite system with the materials to be protected and are produced, for example, by plating, lining or coating. Suitable metals depend on the material to be coated; For example, stainless steel, silver, nickel, copper can be used as protective material for steel. fer, aluminum or their alloys.
  • Inorganic non-metallic protective layers include, for example, enamel, silica, graphite, metal oxides, metal carbides, phosphates, chromates and oxalates.
  • Organic protective layers are based, for example, on unsaturated polyesters, polyurethanes, vinyl esters or epoxy resins.
  • the present invention therefore relates to the use of condensation products which are selected from
  • (ii-2) at least one amine having at least two primary and / or secondary amino groups, wherein at least one amine must contain at least three primary and / or secondary amino groups;
  • (iii-3) at least one amine having at least two primary amino groups other than melamine and the at least one melamine derivative
  • (v-2) at least one amine having at least two primary and / or secondary amino groups, wherein at least one amine must contain at least three primary and / or secondary amino groups;
  • (v-3) optionally at least one further amine other than component (v-2); and (vi) oligomeric compounds obtainable by the condensation of (vi-1) melamine and / or at least one melamine derivative;
  • (vi-4) optionally at least one further amine other than components (vi-1) and (vi-3); to reduce or prevent the corrosion of materials susceptible to corrosion.
  • the invention also relates to a method for reducing, delaying or preventing the corrosion of materials susceptible to corrosion, comprising subjecting the materials and / or the corrosive medium to which the materials are exposed to at least one of the hyperbranched polymers and / or oligomers according to the above Definition brings into contact, preferably coated.
  • polymer is understood broadly and encompasses polymers, polyadducts and polycondensates, ie. H. he does not specify the way in which the propagation of the chain runs. Most commonly, it refers to polycondensates in the present invention.
  • Highly branched polymers in the context of the present invention are understood as meaning polymers having a branched structure and a high functionality, ie a high density of functional groups.
  • hyperbranched polymers see PJ Flori, J. Am. Chem. Soc., 1952, 74, 2718, and H. Frey et al., Chem. Eur. J., 2000, 6, No. 14, 2499.
  • star polymers include star polymers, dendrimers, structurally and molecularly nonuniform highly branched polymers and various high molecular weight branched polymers, such as comb polymers.
  • Star polymers are those polymers in which three or more chains emanate from one center.
  • the center can be a single atom or a group of atoms.
  • Dendrimers (cascade polymers) are molecularly uniform polymers with a highly symmetric structure. They are structurally derived from star polymers, with their chains again branching like stars. Dendrimers are made from small molecules through repeated reaction sequences. The number of monomer end groups grows exponentially with each reaction step, resulting in a spherical, tree-like structure. On- Due to their uniform structure, dendrimers have a uniform molecular weight.
  • highly branched polymers are preferably provided which are different from dendrimers, ie. H. which are both structurally and molecularly non-uniform (and thus have no uniform molecular weight, but a molecular weight distribution).
  • dendrimers ie. H. which are both structurally and molecularly non-uniform (and thus have no uniform molecular weight, but a molecular weight distribution).
  • they may be based on the one hand, starting from a central molecule analogous to dendrimers, but with nonuniform chain length of the branches.
  • they can also start from linear molecules and be built up with branched functional side groups.
  • “Highly branched” in the context of the present invention also means that the degree of branching (DB) is 10 to 99.9%, preferably 20 to 99% and in particular from 20 to 95%.
  • the degree of branching is the mean number of dendritic linkages plus the average number of end groups per molecule divided by the sum of the average number of dendritic links, the average number of linear links, and the average number of endpoints multiplied by 100.
  • dendritic is understood in this context that the degree of branching at this point in the molecule is 99.9 to 100%. To define the degree of branching, see also H. Frey et al., Acta. Polym. 1997, 48, 30.
  • the highly branched polymers according to the invention are essentially not crosslinked.
  • “Substantially non-crosslinked” or “uncrosslinked” in the sense of the present invention means that a degree of crosslinking of less than 15 wt .-%, preferably less than 10 wt .-% is present, wherein the degree of crosslinking over the insoluble portion of the polymer is determined.
  • the insoluble portion of the polymer is, for example, by extraction for 4 hours with the same solvent as used for gel permeation chromatography (GPC), that is, preferably dimethylacetamide or hexafluoroisopropanol, depending on the solvent in which the polymer is more soluble Soxhlet apparatus and, after drying the residue to constant weight, weighing the remaining residue determined.
  • GPC gel permeation chromatography
  • the highly branched polymers according to the invention have a number average molecular weight M n of at least 500, z. From 500 to 200,000, or preferably from 500 to 100,000 or more preferably from 500 to 50,000 or more preferably from 500 to 30,000 or even more preferably from 500 to 20,000 or in particular from 500 to 15,000; more preferably of at least 1000, e.g. From 1000 to 200,000 or preferably from 1000 to 100,000 or more preferably from 1000 to 50,000 or more preferably from 1000 to 30,000 or even more preferably from 1000 to 20,000 or especially from 1000 to 15,000; more preferably at least 2000, e.g.
  • the highly branched polymers of the present invention have a weight average molecular weight M w of at least 1000, e.g. From 1000 to
  • the molecular weights (M n , M w ) and the polydispersity given in the context of the present invention refer to values which are determined by gel permeation chromatography (GPC) in a suitable solvent, such as hexafluoroisopro panol, tetrahydrofuran, ⁇ , ⁇ - Dimethylacetamide or water, with PMMA calibration.
  • GPC gel permeation chromatography
  • the oligomeric compounds (oligomers) (iv), (v) and (vi) are low molecular weight products formed by the condensation of a few molecules, preferably 2, 3, 4 or 5 molecules, especially preferably of 2, 3 or 4 molecules are formed and have a defined molecular weight.
  • the oligomeric compounds (iv) are formed by the condensation of a melamine molecule or a melamine derivative molecule with one or two amine molecules
  • the oligomeric compounds (v) are formed, for example, by the condensation of a urea molecule or a urea derivative molecule with one or two amine molecules.
  • the oligomeric compounds (vi) are formed, for example, by the condensation of a melamine molecule or a melamine derivative molecule with one, two or three amine molecules and a urea molecule or a urea derivative molecule.
  • C 1 -C 4 -alkyl is a linear or branched alkyl radical having 1 to 4 carbon atoms. These are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
  • Ci-C4-alkyl represents a linear alkyl radical having 1 to 4 carbon atoms. These are methyl, ethyl, n-propyl and n-butyl.
  • C 2 -C 6 -alkyl is a linear or branched alkyl radical having 2 to 6 carbon atoms. Examples are ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl and their constitution isomers.
  • Ci-Ci2-alkyl is a linear or branched alkyl radical having 1 to 12 carbon atoms.
  • Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, 4 Methyl 2-propylhexyl, undecyl, dodecyl and their constitutional isomers.
  • C 1 -C 20 -alkyl is a linear or branched alkyl radical having 1 to 20 carbon atoms. Examples thereof are, in addition to the radicals cited above for C 1 -C 12 -alkyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and their constitutional isomers.
  • C 2 -C 4 -alkyl represents a linear or branched alkyl radical having 2 to 4 carbon atoms in which a hydrogen atom is replaced by a hydroxy group. Examples of these are 2-hydroxyethyl, 2- and 3-hydroxypropyl, 1-hydroxy-2-propyl, 2-, 3- and 4-hydroxybutyl and the like.
  • C2-Cio-alkenyl is a linear or branched aliphatic radical having 2 to 10 carbon atoms and a CC double bond.
  • Examples thereof are ethenyl (vinyl), 1-propenyl, allyl (2-propenyl), 1-, 2- or 3-butenyl, 1-, 2-, 3- or 4-pentenyl, 1-, 2-, 3-, 4- or 5-hexenyl, 1-, 2-, 3-, 4-, 5- or 6-heptenyl, 1-, 2-, 3-, 4-, 6- or 7- octenyl, 1- , 2-, 3-, 4-, 5-, 6-, 7- or 8-nonenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-decenyl and their constitutional isomers.
  • C3-C6-Cycloalkyl represents a cycloaliphatic saturated radical having 3 to 6 carbon atoms. Examples of these are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Aryl represents a carbocyclic aromatic radical having 6 to 14 carbon atoms, such as phenyl, naphthyl, anthracenyl or phenanthrenyl.
  • Aryl is preferably phenyl or naphthyl and in particular phenyl.
  • Aryl-Ci-C4-alkyl is Ci-C4-alkyl, which is as defined above, wherein a hydrogen atom is replaced by an aryl group. Examples are benzyl, phenethyl and the like.
  • C 1 -C 4 -alkoxy represents a linear or branched alkyl radical having 1 to 4 carbon atoms bound via an oxygen atom. Examples of these are methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy.
  • C 1 -C 4 -alkylene is a linear or branched divalent alkyl radical having 1, 2, 3 or 4 carbon atoms. Examples are -CH 2 -, -CH 2 CH 2 -, -CH (CH 3 ) -, -CH 2 CH 2 CH 2 -,
  • Linear C 1 -C 4 -alkylene is a linear divalent alkyl radical having 1, 2, 3 or 4 carbon atoms. Examples are -CH2CH2-, -CH2CH2CH2- and -CH2CH2CH2CH2-.
  • C 2 -C 3 -alkylene is a linear or branched divalent alkyl radical having 2 or 3 carbon atoms. Examples are -CH 2 CH 2 -, -CH (CH 3 ) -, -CH 2 CH 2 CH 2 -, -CH (CH 3 ) CH 2 -, CH 2 CH (CH 3 ) - and -C (CH 3 ) 2 - .
  • Linear or branched C 2 -C 4 -alkylene is a linear or branched divalent alkyl radical having 2, 3 or 4 carbon atoms. Examples are -CH 2 CH 2 -, -CH (CH 3 ) -, -CH 2 CH 2 CH 2 -, -CH (CH 3 ) CH 2 -, -CH 2 CH (CH 3 ) -, -C (CH 3 ) 2 -, -CH 2 CH 2 CH 2 CH 2 -,
  • Linear C 2 -C 4 -alkylene is a linear divalent alkyl radical having 2, 3 or 4 carbon atoms. Examples are -CH2CH2-, -CH2CH2CH2- and -CH2CH2CH2CH2-.
  • Linear or branched C 2 -C 8 -alkylene is a linear or branched divalent alkyl radical having 2, 3, 4 or 5 carbon atoms. Examples are -CH2CH2-, -CH (CH3) -, -CH2CH2CH2-, -CH (CH 3) CH 2 -, -CH 2 CH (CH 3) -, -C (CH 3) 2 -, -CH2CH2CH2CH2- .
  • Linear or branched C 2 -C 6 -alkylene is a linear or branched divalent alkyl radical having 2, 3, 4, 5 or 6 carbon atoms. Examples are -CH2CH2-, -CH (CH3) -, -CH2CH2CH2-, -CH (CH 3) CH 2 -, -CH 2 CH (CH 3) -, -C (CH 3) 2 -, -CH2CH2CH2CH2- .
  • Linear C2-C6-alkylene is a linear divalent alkyl radical having 2, 3, 4, 5 or 6 carbon atoms. Examples are -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -,
  • Linear or branched C 4 -C 8 -alkylene is a linear or branched divalent alkyl radical having 4 to 8 carbon atoms. Examples are -CH 2 CH 2 CH 2 CH 2 -,
  • Linear or branched C 4 -C 10 -alkylene is a linear or branched divalent alkyl radical having 4 to 10 carbon atoms.
  • Linear or branched C 2 -C 10 -alkylene is a linear or branched divalent alkyl radical having 2 to 10 carbon atoms. Examples are, in addition to the previously mentioned in C2-C6-alkylene radicals, the higher homologues having 7 to 10 carbon atoms, such as heptylene, octylene, nonylene and decylene.
  • Linear or branched C 1 -C 10 -alkylene is a linear or branched divalent alkyl radical having 1 to 10 carbon atoms. Another example is in addition to the previously mentioned in C2-Cio-alkylene radicals -CH2-.
  • Linear or branched C 2 -C 20 -alkylene is a linear or branched divalent alkyl radical having 2 to 20 carbon atoms.
  • Examples are, in addition to the previously mentioned in C2-C5-alkylene radicals, the higher homologues having 6 to 20 carbon atoms, such as hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene and eicosyls.
  • Alkenylene is a linear or branched aliphatic one or more times, for. B. one or two times, olefinically unsaturated divalent radical having for example 2 to 20 or 2 to 10 or 4 to 8 carbon atoms. If the radical contains more than one carbon-carbon double bond, these are preferably not vicinal, i. H. not allish.
  • Alkynylene is a linear or branched aliphatic divalent radical having, for example, 2 to 20 or 2 to 10 or 4 to 8 carbon atoms, which has one or more, for. B. contains 1 or 2 carbon-carbon triple bonds.
  • C5-C8 cycloalkylene is a divalent monocyclic saturated hydrocarbon group of 5 to 8 carbon ring members.
  • Examples are cyclopentane-1, 2-diyl, cyclopentane-1, 3-diyl, cyclohexane-1, 2-diyl, cyclohexane-1, 3-diyl, cyclohexane-1, 4-diyl, cycloheptane-1, 2-diyl, Cycloheptane-1, 3-diyl, cycloheptane-1, 4-diyl, cyclooctane-1, 2-diyl, cyclooctane-1, 3-diyl, cyclooctane-1, 4-diyl and cyclooctane-1, 5-diyl.
  • a 5- or 6-membered saturated, partially unsaturated or aromatic heterocycle containing 1, 2 or 3 heteroatoms selected from O, S and N as ring members is, for example, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, oxazolidinyl, isoxazolidinyl , Thiazolidinyl, isothiazolidinyl, triazolidinyl oxadiazolidiny, thiadiazolidinyl, piperidinyl, tetrahydropyranyl, piperazinyl, morpholinyl, thiomorpholinyl;
  • pyrrole-1-yl, pyrazol-1-yl, imidazol-1-yl and triazole-1 bonded via N which may additionally contain a further nitrogen atom as ring member, are bonded via N or 5-membered unsaturated aromatic heterocycle. yl.
  • a primary amino group By a primary amino group is meant a radical -IMH2.
  • a secondary amino group is meant a radical -NHR, where R is other than H.
  • Melamine derivatives optionally used to prepare the polymers or oligomers (i), (iii), (iv) or (vi) as components (i-1), (iii-1), (iv-1) or (vi-1) are preferably selected from benzoguanamine, substituted melamines and melamine condensates and mixtures thereof.
  • Substituted melamines are, for example, mono- or di-N-alkylated melamines, such as 2,4-diamino-6-methylamino-1, 3,5-triazine, 2,4-diamino-6-dimethylamino-1, 3,5- triazine, 2,4-di- (methylamino) -6-amino-1, 3,5-triazine, aminoalkyl-substituted melamines, such as N, N ', N "-tris- (2-aminoethyl) melamine, N, N' , N "-Tris (3-aminopropyl) melamine, ⁇ , ⁇ ', ⁇ " - tris (4-aminobutyl) melamine, N, N', N "-Tris (5-aminopentyl) melamine and N, N ', N Tris (6-aminohexyl) melamine and the like.
  • the melamine condensates are preferably selected from melam, Meiern, melon and higher condensates.
  • Melam empirical formula CeHgNu
  • Meiern empirical formula ⁇ - ⁇
  • Melon empirical formula C6H3N9 is also a heptazine.
  • component (i-1), (iii-1), (iv-1) or (vi-1) melamine, optionally in admixture with at least one melamine derivative, d. H.
  • the components (i-1), (iii-1), (iv-1) and (vi-1) preferably comprise melamine in any case.
  • the weight ratio of melamine to the total amount of the at least one melamine derivative is preferably 1: 2 to 1000: 1, more preferably 1: 1 to 500: 1 and especially 2: 1 to 100: 1 , However, it is particularly preferable to use as component (i-1), (iii-1), (iv-1) or (vi-1) no melamine derivative but only melamine.
  • the at least one amine having at least two primary and / or secondary amino groups of components (ii-2) and (v-2) is preferably an amine having at least two primary amino groups.
  • it is at least one amine having at least two primary amino groups of components (i-2), (iii-3), (iv-2) and (vi-3) and at least one amine having at least two primary and / or secondary amino groups the components (ii-2) and (v-2) selected from amines of the formula I.
  • A is a divalent aliphatic, alicyclic, aliphatic-alicyclic, aromatic or araliphatic radical, where the abovementioned radicals can also be interrupted by a carbonyl group or by a sulfone group and / or can be substituted by 1, 2, 3 or 4 radicals which are selected from Ci-C4-alkyl; or for a bivalent radical of the formula stands; wherein
  • each X is independently O or NR C in which R c is H, C 1 -C 4 -alkyl, C 2 -C 4 -hydroxyalkyl or C 1 -C 4 -alkoxy, preferably H or C 1 -C 4 -alkyl, particularly preferably H or methyl and especially H;
  • each B is independently C2-C6 alkylene and preferably C2-C3 alkylene;
  • n is a number from 1 to 100. Also suitable are mixtures of these amines.
  • Divalent aliphatic radicals are those which contain no cycloaliphatic, aromatic or heterocyclic constituents. Examples are alkylene, alkenylene and alkynylene radicals.
  • Divalent alicyclic radicals may be one or more, e.g. B. contain one or two alicyclic radicals; however, they contain no aromatic or heterocyclic constituents.
  • the alicyclic radicals may be substituted by aliphatic radicals, but there are binding sites for the two Nh groups on the alicyclic radical.
  • Divalent aliphatic-alicyclic radicals contain both at least one divalent aliphatic and at least one bivalent alicyclic radical, the two bonding sites for the two Nh groups either being attached to the alicyclic radical (s) or both to the aliphatic radical (s) ( en) or one may be on an aliphatic and the other on an alicyclic radical.
  • Divalent aromatic radicals may be one or more, e.g. B. contain one or two aromatic radicals; however, they contain no alicyclic or heterocyclic constituents.
  • the aromatic radicals may be substituted by aliphatic radicals, but both binding sites for the two Nh groups are located on the aromatic radical (s).
  • Divalent araliphatic radicals contain at least one divalent aliphatic as well as at least one divalent aromatic radical, whereby the two binding sites for the two Nh groups are either both on the aromatic radical (s) or both on the aliphatic radical (s). or one may be on an aliphatic and the other on an aromatic radical.
  • the bivalent aliphatic radical A is linear or branched C 2 -C 20 -alkylene, particularly preferably linear or branched C 2 -C 10 -alkylene and in particular linear or branched C 4 -C 8 -alkylene.
  • Examples of suitable amines in which the radical A has this meaning are 1, 2-ethylenediamine, 1, 2- and 1, 3-propylenediamine, 2,2-dimethyl-1,3-propanediamine , 1, 4-butylenediamine, 1, 5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, tetradecamethylenediamine, pentadecamethylenediamine, hexadecamethylenediamine, heptadecamethylenediamine, octadecamethylenediamine, nonadecamethylenediamine, eicosamethylenediamine, 2 Butyl 2-ethyl-1, 5-pentamethylenediamine, 2,2,4- or 2,4,4-trimethyl-1,6-he
  • A is linear or branched C 2 -C 10 -alkylene, such as in 1, 2-ethylenediamine, 1, 2- and 1, 3-propylenediamine, 2,2-dimethyl-1, 3-propanediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylenediamine, 1, 5-diamino-2 -methylpentan,
  • amines are used in which A is linear or branched C 4 -C 8 -alkylene, where in branched alkylene at most one branch originates from one carbon atom.
  • amines examples include 1, 4-butylenediamine, 1, 5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine and 1, 5-diamino-2-methylpentane, ie the amines listed above as particularly preferred except for 2,2-dimethyl-1 , 3-propanediamine and 1, 4-diamino-4-methylpentane. More particularly, amines are used in which A is linear C 4 -C 8 -alkylene, such as 1,4-butylenediamine, 1, 5-pentylenediamine, hexamethylenediamine, heptenamethylenediamine and octamethylenediamine.
  • the divalent alicyclic radicals A are selected from Cs-Cs-cycloalkylene which may carry 1, 2, 3 or 4 C 1 -C 4 -alkyl radicals.
  • suitable amines in which the radical A has this meaning are cyclopentylenediamine, such as 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, cyclohexyllenediamine, such as 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or
  • amino groups may be cis or trans to each other.
  • the divalent aliphatic-alicyclic radicals A are selected from C 5 -C 8 -cycloalkylene-C 1 -C 4 -alkylene, C 5 -C 8 -cycloalkylene-C 1 -C 4 -alkylene-C 6 -C 8 -cycloalkylene and C 1 -C 4 -alkylene C 5 -C 8 -cycloalkylene-C 1 -C 4 -alkylene, where the cycloalkylene radicals may carry 1, 2, 3 or 4 C 1 -C 4 -alkyl radicals.
  • Suitable amines in which the radical A has this meaning are diamodicyclohexylmethane, isophoronediamine, bis (aminomethyl) cyclohexane, such as
  • the divalent aromatic radicals A are selected from phenylene, biphenylene, naphthylene, phenylene-sulfone-phenylene and phenylene-carbonyl-phenylene, where the phenylene and naphthylene radicals can carry 1, 2, 3 or 4 C 1 -C 4 -alkyl radicals ,
  • Suitable amines in which the radical A has this meaning are phenylenediamine, such as o-, m- and p-phenylenediamine, toluylenediamine, such as o-, m- and
  • diaminodiphenylsulfone such as 2,2'-, 3,3'- and
  • the divalent araliphatic radicals A are selected from phenylene-C 1 -C 4 -alkylene and phenylene-C 1 -C 4 -alkylene-phenylene, where the phenylene radicals may carry 1, 2, 3 or 4 C 1 -C 4 -alkyl radicals.
  • suitable amines in which the radical A has the meaning are diamodiphenylmethane, such as 2,2'-, 3,3'- and 4,4'-diaminodiphenylmethane, and the like.
  • X is O.
  • m is preferably a number from 2 to 100, preferably 2 to 80 and in particular 2 to 20, z. B. 2 to 10 or 2 to 6.
  • amine-terminated polyoxyalkylene polyols for example Jeff amines, such as 4,9-dioxadodecane-1, 12-diamine and 4,7,10-trioxatridecan-1, 13- diamine, or more regular amine-terminated polyoxyalkylene polyols, such as amine-terminated polyethylene glycols, amine-terminated polypropylene glycols or amine-terminated polybutylene glycols.
  • the last three amines (amine-terminated polyalkylene glycols) preferably have a molecular weight of 200 to 3000 g / mol.
  • X is NR C.
  • R c is preferably H or C 1 -C 4 -alkyl, particularly preferably H or methyl and in particular H.
  • Each B is independently in particular C 2 -C 3 -alkylene, such as 1, 2-ethylene, 1, 2-propylene and 1, 3-propylene, and especially for 1, 2-ethylene or 1, 3-propylene.
  • m here preferably stands for a number from 1 to 20, more preferably from 1 to 10, more preferably from 1 to 6 and in particular from 1 to 4.
  • Suitable amines in which the radical A has the meaning are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethylene lenheptamine, heptaethyleneoctamine, octaethyleneenenamine, higher polyimines, bis (3-aminopropyl) amine, bis (3-aminopropyl) methylamine, N3-amine (3- (2-aminoethylamino) propylamine), N4-amine (N, N'-bis (3-aminopropyl) ethylenediamine) and the like.
  • a in compounds I is particularly preferably a divalent aliphatic radical or a radical of the formula -f.sub.B-X ⁇ m -B-, in which B, X and m have one of the abovementioned general or, in particular, one of the abovementioned preferred meanings.
  • linear or branched C 2 -C 10 -alkylene particularly preferably linear or branched C 4 -C 8 -alkylene and in particular linear C 4 -C 8 -alkylene;
  • each X is independently NR C , wherein R c is as defined above, and is preferably H or C 1 -C 4 alkyl, more preferably H or methyl and especially H stands;
  • each B is independently C2-C3-alkylene and preferably 1, 2-ethylene or 1, 3-propylene;
  • m is a number from 1 to 20, preferably from 1 to 10, particularly preferably from 1 to 6 and in particular from 1 to 4.
  • a in compounds I is selected under
  • X is NH
  • each B is independently 1, 2-ethylene or 1, 3-propylene
  • m is a number from 1 to 10, preferably from 1 to 6 and especially from 1 to 4.
  • At least one amine having at least two primary amino groups of components (i-2), (iii-3), (iv-2) and (vi-3) and the at least one amine having at least two primary and / or secondary Amino groups of components (ii-2) and (v-2) selected from amines of formula I, wherein A is a radical of the formula -fB-X ⁇ m -B-, wherein B, X and m is one of the general above or in particular have one of the preferred meanings given above, and mixtures thereof with amines of the formula I in which A is a divalent aliphatic radical in which the divalent aliphatic radical has one of the abovementioned general or especially one of the abovementioned preferred meanings.
  • it is at least one amine having at least two primary amino groups of components (i-2), (iii-3), (iv-2) and (vi-3) and at least one amine having at least two primary and / or secondary Amino groups of components (ii-2) and (v-2) selected from amines of formula I, wherein A is a radical of the formula -fB-X ⁇ m -B-, wherein each B is independently 1, 2-ethylene or
  • X is NH; and m is a number from 1 to 10, preferably from 1 to 6 and especially from 1 to 4, and mixtures thereof with amines of formula I, wherein A is linear C 4 -C 8 alkylene.
  • it is at least one amine having at least two primary amino groups of components (i-2), (iii-3), (iv-2) and (vi-3) and at least one amine having at least two primary and / or secondary amino groups the components (ii-2) and (v-2) selected from 1, 2-ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenemoneamine,
  • the at least one amine having at least three primary and / or secondary amino groups of components (ii-2) and (v-2) is selected under
  • a 1 is a bivalent radical of the formula
  • each X 1 is O or NR c1 is independently, at least one X 1 in the compound la NR c1, c1 wherein R is H, Ci-C 4 alkyl, C 2 -C 4 - Hydroxyalkyl or Ci-C4-alkoxy, wherein at least one radical R c1 is H;
  • each B 1 is independently C2-C6 alkylene
  • n 1 is a number from 1 to 20;
  • R a1 and R b1 independently of one another are H, C 1 -C 4 -alkyl, C 2 -C 4 -hydroxyalkyl or
  • Y is CR9, N, C 2 -C 6 alkyl, C 3 -C 6 cycloalkyl, phenyl or a 5- or
  • NR h -C 2-Cio-alkylene or 0-Ci-Cio-alkylene are provided, with the proviso that Ei, E2 and E3 are not a single bond and not for NR h -C2-Cio-alkylene, when Y is N. ;
  • R d , R e and R f independently of one another are H, C 1 -C 4 -alkyl, C 2 -C 4 -hydroxyalkyl or C 1 -C 4 -alkoxy;
  • R 9 and R h independently of one another are H, C 1 -C 4 -alkyl, C 2 -C 4 -hydroxyalkyl or C 1 -C 4 -alkoxy;
  • a a has one of the meanings given for A in one of claims 5 to 11;
  • a b , A c , A d and A e independently of one another are C 1 -C 10 -alkylene;
  • Z is N or CR m ;
  • R 1 , R j , R k , R 1 and R m independently of one another are H, C 1 -C 4 -alkyl, C 2 -C 4 -hydroxyalkyl or C 1 -C 4 -alkoxy; and - mixtures thereof.
  • R c1 taking into account the above proviso, is preferably H or C 1 -C 4 -alkyl, particularly preferably H, methyl or ethyl and in particular H.
  • B 1 is preferably C 2 -C 3 -alkylene, such as 1, 2-ethylene, 1, 2-propylene and
  • m 1 preferably represents a number from 1 to 10, particularly preferably from 1 to 6 and in particular from 1 to 4.
  • Suitable amines of the formula Ia are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethylenepheptamine, heptaethylenoc-tamine, octaethyleneamnonamine, higher polyimines, bis (3-aminopropyl) amine,
  • Y stands for N
  • Ei, E2 and E3 are not a single bond and not -NR h -C 2 -ioalkylene.
  • Y is N
  • Ei, E 2 and E3 are not methylene (Ci-alkylene).
  • Y is CR
  • at least two of the groups Ei, E2 and E3 are not a single bond.
  • the three arms can be -Ei-NHR d , -E2-NHR e and -E3-NHR f on carbon ring atoms as well be bound to nitrogen ring atoms of the heterocycle Y.
  • the arms -Ei-NHR d , -E2-NHR e, and -E3-NHR f are bonded to ring nitrogen atoms, then Ei, E2, and E3 are not a single bond and not -NR h -C2-Cio alkylene.
  • the arms are bonded to different ring atoms of the heterocycle Y.
  • the heterocyclic ring Y is preferably selected from 5- or 6-membered heteroaromatic rings having 1, 2 or 3 nitrogen atoms as ring members.
  • Hetraylringe examples include pyrrolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazonyl and triazinyl. More preferred among these are 6-membered hetaryl rings, such as pyridyl, pyrimidyl, pyrazinyl, pyridazinyl and triazinyl, with triazinyl being particularly preferred.
  • the compounds III are amines having at least four primary and / or secondary amino functions.
  • a a preferably has one of the meanings for A given as being preferred.
  • a a is C 2 -C 6 -alkylene, particularly preferably linear C 2 -C 6 -alkylene, such as 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, pentamethylene and hexamethylene.
  • Z is preferably N.
  • a b , A c , A d and A e are preferably C 2 -C 6 -alkylene, particularly preferably linear C 2 -C 6 -alkylene, such as 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, pentamethylene and hexamethylene, and in particular for linear C 2 -C 4 -alkylene, such as 1,2-ethylene,
  • R ', R, R k, R' and R m are each preferably H.
  • Examples of amines having at least three primary and / or secondary amino groups of the formulas Ia, II and III are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylene-nonamine, higher polyimines, eg.
  • Polyethyleneimines and polypropyleneimines bis (3-aminopropyl) amine, bis (4-aminobutyl) amine, bis (5-aminopentyl) amine, bis (6-aminohexyl) amine, N4-amine, 3- (2-aminoethyl ) -aminopropylamine, N, N-bis (3-aminopropyl) ethylenediamine, N ', N-bis (3-aminopropyl) ethylenediamine, N, N-bis (3-aminopropyl) propane-1, 3 -diamine, N, N-bis (3-aminopropyl) -butane-1,4-diamine, N, N'-bis (3-amino-propyl) -propane-1,3-diamine, N, N ' Bis (3-aminopropyl) butane-1,4-diamine, ⁇ , ⁇ , ⁇ ' ⁇ '-tetra
  • Tris (5-aminopentyl) amine, tris (6-aminohexyl) amine, trisaminohexane, trisaminononane, 4-aminomethyl-1,8-octamethylenediamine, tri- or higher amine-terminated polyoxyalkylene polyols eg, Jeffamine, for example, polyetheramine T403 or poly etheramine T5000
  • Particularly preferred amines having at least three primary and / or secondary amino groups are selected from amines of the formula I.a, amines of the formula II and mixtures thereof.
  • Preferred amines of the formula Ia are diethylene triamine, triethylene tetramine, tetraethylene lenpentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethyleneenenamine, higher polyimines, eg. Polyethyleneimines and polypropyleneimines, bis (3-aminopropyl) amine, bis (4-aminobutyl) amine, bis (5-aminopentyl) amine,
  • Preferred amines of the formula II are those in which Y is N or a 1,3,5-triazine-2,4,6-triyl ring.
  • Preferred amines II, wherein Y is N are selected from N, N-bis (3-amino-propyl) -ethylenediamine, N, N-bis (3-aminopropyl) -propane-1,3-diamine, N , N-bis (3-aminopropyl) -butane-1, 4-diamine, tris (2-aminoethyl) amine, tris (2-aminopropyl) amine, tris (3-aminopropyl) amine, tris (2-aminobutyl) amine , Tris (3-aminobutyl) amine,
  • Preferred amines II in which Y is a 1,3,5-triazine-2,4,6-triyl ring are melamine and aminoalkyl-substituted melamines, such as N, N ', N "-tris (2-aminoethyl) melamine, N, N ', N "-tris (3-aminopropyl) melamine, N, N', N" -tris (4-aminobutyl) melamine,
  • the at least one amine having at least three primary and / or secondary amino groups of components (ii-2) and (v-2) is preferably selected from amines having at least three primary amino groups. Accordingly, in compounds la R a1, R b1 and R c1 is preferably H, and also in compounds II, the radicals R d, R e and R f preferably represent H. Similarly in compounds III, the radicals R ', R, R k and R 'are preferably H. In regard to suitable and preferred amines having at least three primary amino groups, reference is made to the above referenced statements (all the above examples are amines having at least three primary amino groups).
  • R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, C 1 -C 12 -alkyl, aryl and aryl-C 1 -C 4 -alkyl, where at least one of the radicals R 1 , R 2 , R 3 and R 4 does not stand for hydrogen;
  • R 1 and R 2 and / or R 3 and R 4 each together are C 2 -C 8 -alkylene, where a methylene group (ie a group CH 2 in the alkylene chain) may optionally be replaced by a carbonyl group;
  • R 1 and R 3 together represent C 2 -C 8 -alkylene, where a methylene group (ie a group CH 2 in the alkylene chain) may optionally be replaced by a carbonyl group;
  • R 1 and R 2 and / or R 3 and R 4 each together with the nitrogen atom to which they are attached form a 5- or 6-membered unsaturated aromatic or non-aromatic ring containing one or two further nitrogen atoms or a sulfur atom or Oxygen atom as a ring member may contain (ie
  • R 1 and R 2 or R 3 and R 4 together with the nitrogen atom to which they are bonded represent a 5- or 6-membered unsaturated aromatic or non-aromatic ring bonded via N and having one or two further nitrogen atoms or one sulfur atom or oxygen atom as ring member may contain);
  • R 5 , R 6 , R 7 and R 8 are independently selected from hydrogen, Ci-Ci2-alkyl, aryl and aryl-Ci-C4-alkyl, wherein at least one of R 5 , R 6 , R 7 and R 8 does not stand for hydrogen;
  • R 5 and R 6 and / or R 7 and R 8 each together are C 2 -C 8 -alkylene, where a methylene group (ie a group CH 2 in the alkylene chain) may optionally be replaced by a carbonyl group;
  • R 5 and R 7 together are C 2 -C 8 -alkylene, where a methylene group (ie a CH 2 group in the alkylene chain) may optionally be replaced by a carbonyl group;
  • R 5 and R 6 and / or R 7 and R 8 each together with the nitrogen atom to which they are attached, a 5- or 6-membered unsaturated aromatic or form non-aromatic ring which may contain one or two further nitrogen atoms or a sulfur atom or oxygen atom as ring member (ie R 5 and R 6 or R 7 and R 8 together with the nitrogen atom to which they are attached, represent an over N bonded 5- or 6-membered unsaturated aromatic or non-aromatic ring which may contain one or two further nitrogen atoms or a sulfur atom or oxygen atom as a ring member);
  • R 9 and R 10 and / or R 12 and R 13 each hen together represent C2-Cs alkylene STE, wherein a methylene group (ie a group Ch in the alkylene chain) may be optionally replaced by a carbonyl group;
  • R 9 and R 12 together represent C2-Cs-alkylene, wherein a methylene group (ie a group Ch in the alkylene chain) may optionally be replaced by a carbonyl group;
  • R 9 and R 10 and / or R 12 and R 13 each together with the nitrogen atom to which they are attached form a 5- or 6-membered unsaturated aromatic or non-aromatic ring additionally containing another nitrogen atom, sulfur atom or oxygen atom Ring member may contain (ie R 9 and R 10 or R 12 and R 13 together with the nitrogen atom to which they are bound, for a bonded via N 5- or 6-membered unsaturated aromatic or non-aromatic ring, the or may contain two other nitrogen atoms or a sulfur atom or oxygen atom as a ring member); and
  • Carbonic acid esters of the formula R 14 -O-CO-O-R 15 wherein R 14 and R 15 are independently selected from Ci-Ci2-alkyl, aryl and aryl-Ci-C4-alkyl or
  • R 14 and R 15 together represent C2-Cs-alkylene.
  • R 2 and R 4 are hydrogen and R 1 and R 3 are the same or different and are C 1 -C 12 -alkyl, aryl or aryl-C 1 -C 4 -alkyl.
  • R 1 and R 3 are the same or different and are C 1 -C 12 -alkyl, aryl or aryl-C 1 -C 4 -alkyl. Examples are N, N'-dimethylurea,
  • R 1 , R 2 , R 3 and R 4 are identical and stand for linear C 1 -C 4 -alkyl. Examples of these are ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylurea and N, N, N', N'-tetra ethyl hernstoff.
  • R 1 and R 2 and R 3 and R 4 in each case together represent C 2 -C 8 -alkylene, where a methylene group (CH 2) in the alkylene chain may be replaced by a carbonyl group (CO); that is, R 1 and R 2 together form a C 2 -C 8 -alkylene group in which a methylene group (CH 2) in the alkylene chain may be replaced by a carbonyl group (CO), and R 3 and R 4 together form a C 2 -C 5 s Alkylene group in which a methylene group (CH2) in the alkylene chain may be replaced by a carbonyl group (CO). Examples of these are di- (tetrahydro-1H-pyrrol-1-yl) -methanone, bis (pentamethylene) urea and carbonylbis- caprolactam.
  • R 2 and R 4 are hydrogen and R 1 and R 3 together form a C 2 -C 8 -alkylene group, where a methylene group may be replaced by a carbonyl group. Examples of these are ethyleneurea and 1, 2 or 1, 3-propyleneurea.
  • R 1 and R 2 and R 3 and R 4 together with the nitrogen atom to which they are attached form an unsaturated aromatic or non-aromatic heterocycle as defined above.
  • examples of these are carbonyldipyrazole and carbonyldiimidazole.
  • R 6 and R 8 in the substituted thioureas are hydrogen and R 5 and R 7 are identical or different and are C 1 -C 12 -alkyl, aryl or aryl-C 1 -C 4 -alkyl.
  • R 5 , R 6 , R 7 and R 8 are the same and are linear Ci-C4-alkyl. Examples of these are ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylthiourea and ⁇ , ⁇ , ⁇ ', ⁇ '-tetraethylthiourea.
  • R 5 and R 6 and R 7 and R 8 each case together are C2-Cs alkylene, wherein a methylene group (Ch) in the alkylene chain may be replaced by a carbonyl group (CO); That is, R 5 and R 6 together form a C 2 -C 8 -alkylene group in which a methylene group (Ch) in the alkylene chain may be replaced by a carbonyl group (CO), and R 7 and R 8 together form a C 2 -Cs-alkylene group in which a methylene group (Ch) in the alkylene chain may be replaced by a carbonyl group (CO).
  • CO carbonyl group
  • R 6 and R 8 are hydrogen and R 5 and R 7 together form a C 2 -C 8 -alkylene group, where a methylene group may be replaced by a thiocarbonyl group. Examples include ethylene thiourea and 1, 2 or 1, 3-propylene thiourea.
  • R 5 and R 6 and R 7 and R 8 together with the nitrogen atom to which they are attached form an unsaturated aromatic or non-aromatic heterocycle as defined above.
  • Guanidine may also be used in the form of a guanidine salt, such as guanidine nitrate or guanidine carbonate in particular.
  • R 10 , R 11 and R 13 are hydrogen and R 9 and R 12 are identical or different and are C 1 -C 12 -alkyl, aryl or aryl-C 1 -C 4 -alkyl.
  • R 9 , R 10 , R 12 and R 13 are the same and are linear C 1 -C 4 -alkyl and R 11 is H or methyl and especially H. Examples of these are ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylguanidine and ⁇ , ⁇ , ⁇ ', ⁇ '-tetraethylguanidine.
  • R 9 and R 10 and R 12 and R 13 are each taken together to be C 2 -C 8 -alkylene, where a methylene group (Ch) may be replaced by a carbonyl group (CO); that is, R 9 and R 10 together form a C 2 -C 5 alkylene group in which a methylene group (Ch) may be replaced by a carbonyl group (CO), and R 12 and R 13 together form a C 2 -C 8 alkylene group in which a methylene group (Ch) may be replaced by a carbonyl group (CO), and R 11 is H or methyl and especially H. Examples of these are di- (tetrahydro-1H-pyrrol-1-yl) -imine, Bis (pentamethylene) guanidine and iminobiscaprolactam.
  • R 10 , R 11 and R 13 are hydrogen and R 9 and R 12 together form a C 2 -C 8 -alkylene group, where a methylene group may optionally be replaced by a carbonyl group.
  • R 9 and R 12 are hydrogen and R 9 and R 12 together form a C 2 -C 8 -alkylene group, where a methylene group may optionally be replaced by a carbonyl group. Examples of these are ethylene guanidine and 1, 2 or 1, 3-Propylenguanidin.
  • R 9 and R 10 and R 12 and R 13 together with the nitrogen atom to which they are attached form an unsaturated aromatic or non-aromatic heterocycle as defined above, and R 11 is H or methyl and especially for H.
  • R 11 is H or methyl and especially for H.
  • iminodipyrazole and iminodiimidazole are iminodipyrazole and iminodiimidazole.
  • R 14 and R 15 are C 1 -C 4 -alkyl. Particularly preferably, both radicals are identical. Examples of these are dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, di-sec-butyl carbonate, diisobutyl carbonate and di-tert-butyl carbonate. Preference is given here to dimethyl carbonate and diethyl carbonate.
  • R 14 and R 15 together are C 2 -C 5 -alkylene and preferably C 2 -C 3 -alkylene.
  • Examples of such carbonates are ethylene carbonate and 1, 2 and 1, 3-propylene carbonate.
  • the substituted ureas, thiourea, the substituted thioureas, guanidine (also in the form of the guanidinium salts), the substituted guanidines and the carbonic acid esters are preferred. More preferred are the substituted ureas, thiourea, guanidine (also in the form of the guanidinium salts) and the carbonic acid esters.
  • thiourea ⁇ , ⁇ '-dimethylurea, ⁇ , ⁇ '-diethylurea, N, N'-di-n-butylurea, ⁇ , ⁇ '-diisobutylurea, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylurea
  • guanidine especially in the form of Guanidine carbonate, dimethyl carbonate, diethyl carbonate, ethylene carbonate and
  • substituted ureas and guanidine v.a. in the form of guanidine carbonate.
  • substituted ureas preference is given to N, N'-dimethylurea, ⁇ , ⁇ '-diethylurea, N, N'-di-n-butylurea, ⁇ , ⁇ '-diisobutylurea and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylurea.
  • R 1 and R 3 are preferably H or C 1 -C 4 -alkyl, especially methyl or ethyl, and R 2 and R 4 are C 1 -C 4 -alkyl, especially methyl or ethyl.
  • urea itself is used as component (ii-1), (iü-2), (v-1) and (vi-2), optionally in combination with one of the aforementioned urea derivatives, and especially only urea.
  • the at least one further amine (i-3), (iii-4), (iv-3) and (vi 4) are preferably amines having a primary amino group, amines having at least three primary amino groups or mixtures thereof.
  • the use of amines with only one primary amino function is particularly useful when the degree of branching of the polymers (i) and (iii) should be lower.
  • the amines having a primary amino group are an amine having a single primary amino function and optionally one or more secondary and / or tertiary amino groups.
  • Examples of primary amines without further secondary / tertiary amino functions are compounds of the formula R-NH 2, in which R is an aliphatic, alicyclic, aliphatic-alicyclic, aromatic or araliphatic radical which of course contains no amino groups.
  • Examples of these are methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine, tert-butylamine, pentylamine, hexylamine, ethanolamine, propanolamine, isopropanolamine, pentanolamine, (2-methoxyethyl) -amine,
  • amines having a single primary amino function and one or more secondary and / or tertiary amino functions are N-methylethylene-1,2-diamine, N, N-dimethylethylene-1,2-diamine , N-ethylethylene-1,2-diamine, N, N-diethylethylene-1,2-diamine, N-methylpropylene
  • N-methylhexylene-1,6-diamine N, N-dimethylhexylene-1,6-diamine, N-methyldiethylenetriamine, ⁇ , ⁇ -dimethyldiethylenetriamine, N-methyltriethylenetetramine,
  • amines having at least three primary amino function is particularly useful when the degree of branching of the polymers (i) and (iii) is to be increased.
  • Examples of such compounds are the abovementioned amines of the formulas II and III, but R d , R e , R f and at least three of the radicals R ', Ri, R k and R' are H, with the exception of melamine and melamine derivatives ,
  • Examples of amines having at least three primary and / or secondary amino groups of the formulas II and III are N, N-bis (3-aminopropyl) -propane-1,3-diamine, N, N-bis (3-aminopropyl) - butane-1,4-diamine, N, N, N'N'-tetra- (3-aminopropyl) -ethylenediamine, N, N, N'N'-tetra- (3-aminopropyl) -1, 4-butylenediamine, Tris (2-aminoethyl) amine,
  • Tris (6-aminohexyl) amine, trisaminohexane, trisaminononane, 4-aminomethyl-1,8-octamethylenediamine, and the like.
  • the at least one further amine (ii-3) and (v-3) used optionally in the preparation of polymers and oligomers (ii) and (v) are preferably amines having a primary amino group. Suitable amines having a primary amino group correspond to those mentioned above for components (i-3), (iii-4), (iv-3) and (vi-4).
  • component (i-1) and component (i-2) are used in a total weight ratio of preferably 1: 1 to 1:20, particularly preferably 1: 1, 5 to 1:10 and in particular 1: 2 to 1: 5, for example 1: 2 to 1: 4 or 1: 2 to 1: 3.5, used.
  • the weight ratio of component (i-2) to component (i-3) is preferably 2: 1 to 100: 1, particularly preferably 5: 1 to 100: 1 and in particular 10: 1 to 50: 1.
  • component (ii-2) additionally contains, in addition to the at least one amine having at least three primary and / or secondary amino groups, at least one amine having two primary and / or secondary amino groups, then the overall weight ratio of the at least one amine with at least three primary and tertiary amines or secondary amino groups for at least one amine having two primary and / or secondary amino groups preferably 1: 1 to 1: 20, more preferably 1: 1, 5 to 1: 10 and in particular 1: 2 to 1: 5 used.
  • the weight ratio of component (ii-2) to component (ii-3) is preferably 2: 1 to 100: 1, particularly preferably 5: 1 to 100: 1 and in particular 10: 1 to 50: 1.
  • the total weight ratio of component (iii-1) and component (iii-3) is preferably 1: 1 to 1:20, more preferably 1: 1, 5 to 1:10 and in particular 1: 2 to 1: 5.
  • the weight ratio of component (iii-3) to component (iii-4) is preferably 2: 1 to 100: 1, particularly preferably 5: 1 to 100: 1 and in particular 10: 1 to 50: 1.
  • the components are preferably used in the weight ratios specified for the polymer (i).
  • the components are preferably used in the weight ratios specified for the polymer (ii).
  • the components are preferably used in the weight ratios indicated for the polymer (iii).
  • the preparation is generally carried out by reaction of the specified components at elevated temperature.
  • the reaction temperature is 40 to 300 ° C, more preferably 100 to 250 ° C and especially 150 to 230 ° C.
  • Suitable catalysts are bases, such as alkali metal and alkaline earth metal hydroxides, z.
  • bases such as alkali metal and alkaline earth metal hydroxides, z.
  • DBU diazabicyclo-undecene
  • DBN diazabicyclononene
  • DABCO diazabicyclooctane
  • nitrogen-containing heterocycles such as imidazole, 1- and 2-methylimidazole, 1, 2- Dimethylimidazole, pyridine, lutidine and the like.
  • Suitable catalysts are aluminum, tin, zinc, titanium, zirconium and bismuth organic compounds such as titanium tetrabutoxide, dibutyltin oxide, dibutyltin dilaurate, tin dioctoate, zirconium acetylacetonate and mixtures thereof.
  • Suitable Brönsted acids are both inorganic acids, such as mineral acids, e.g. As hydrofluoric acid, hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid or sulfamic acid, but also ammonium salts such as ammonium fluoride, ammonium chloride, ammonium bromide or ammonium sulfate, as well as organic acids such as methanesulfonic acid, acetic acid, trifluoro- acetic acid and p-toluenesulfonic acid.
  • mineral acids e.g. As hydrofluoric acid, hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid, phosphorous acid or sulfamic acid, but also ammonium salts such as ammonium fluoride, ammonium chloride, ammonium bromide or ammonium sulfate, as well as organic acids such as methan
  • Suitable Bronsted acids are also the ammonium salts of organic amines, such as ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, aniline, benzylamine or melamine, and also the ammonium salts of urea.
  • organic amines such as ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, aniline, benzylamine or melamine, and also the ammonium salts of urea.
  • Suitable Lewis acids are any metal or semimetallic halides in which the metal or metalloid has an electron pair gap. Examples of these are BF 3 , BCl 3 , BBr 3 , AIF 3 , AICI 3 , AIBr 3 , ethylaluminum dichloride, diethylaluminum chloride, TiF 4 , TiCl 4 , TiBr 4 , VCIs, FeF 3 , FeCl 3 , FeBr 3 , ZnF 2 , ZnCl 2 , ZnBr 2 , Cu ( l) F, Cu (I) Cl, Cu (I) Br, Cu (II) F 2 , Cu (II) Cl 2 , Cu (II) Br 2 , Sb (III) F 3 , Sb (V) F 5 , Sb (III) Cl 3 , Sb (V) Cl 5 , Nb (V) Cl 5 , Sn (II) F 2 , Sn (II) Cl 2 ,
  • the condensation is carried out in the absence of a catalyst or using a halogen-free mineral acid (Bronsted inorganic acid) as a catalyst.
  • Suitable halogen-free mineral acids are nitric acid, sulfuric acid, phosphoric acid, phosphorous acid and amidosulfonic acid and mixtures thereof.
  • phosphoric acid, phosphorous acid and especially mixtures thereof are used.
  • the weight ratio thereof is preferably 20: 1 to 1:20, more preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and most preferably 3: 1 to 1 3.
  • the condensation is preferably carried out in the absence of halogen-containing compounds.
  • the reaction can be carried out both at atmospheric pressure and at elevated pressure, for. B. at a pressure of 1 to 20 bar or 1 to 15 bar or 10 to 15 bar.
  • the pressure is often exclusively due to the ammonia liberated in the course of the reaction during the condensation of the components (if as component (ii-1) or (iii-2) urea, thiourea, Guanidine and / or biuret); that is, the pressure increases with the progress of the reaction and can then be adjusted to the desired value.
  • the pressure may also be achieved via an inert gas, eg. B.
  • the reaction is from the beginning, ie before any appreciable pressure through the formed ammonia may occur, to be carried out under elevated pressure.
  • the reaction pressure is determined in particular by the type of amines used.
  • the reaction can be carried out at atmospheric pressure, if the at least one amine used has a boiling point which is above the reaction temperature. On the other hand, if the boiling point is below the reaction temperature, it is of course advantageous to carry out the reaction at elevated pressure. However, even with amines having a boiling point above the reaction temperature, it may be advantageous under certain circumstances to carry out the reaction under excess pressure, for example in order to achieve a higher reaction rate.
  • the reaction can be carried out in a suitable solvent.
  • suitable solvents are inert, ie they do not react with the starting materials, intermediates or products under the given reaction conditions and are not degraded even under the given reaction conditions, for example by thermal decomposition.
  • suitable solvents are chlorinated aliphatic or aromatic hydrocarbons, such as methylene chloride, chloroform, dichloroethane, trichloroethane, chlorobenzene, chlorotoluene and o-dichlorobenzene, open-chain and cyclic ethers, such as diethyl ether, dipropyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, tetrahydrofuran and 1, 4-dioxane, polar aprotic solvents such as N, N-dimethylformamide, ⁇ , ⁇ -dimethylacetamide, dimethylsulfoxide and acetonitrile, and polar protic solvents, eg.
  • chlorinated aliphatic or aromatic hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, chlorobenzene, chlorotolu
  • polyols or polyether polyols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol or polyethylene glycol.
  • Preferred solvents are the abovementioned polyols or polyether polyols. Specially used is ethylene glycol.
  • the reaction can also be carried out in bulk, ie without additional solvent. In this case, an amine is often used as a solvent, especially if it is liquid and used in excess.
  • the implementation is preferably carried out in a solvent, in particular in one of the abovementioned preferred solvents.
  • the reaction may be carried out by mixing all components and reacting by heating to the desired reaction temperature. Alternatively, some of the components may also be added first and the remaining ingredients gradually added, the order of addition being of minor importance. It has proven, however, sparingly soluble
  • Components such as urea or melamine, not completely present, but gradually fed continuously or in portions.
  • the addition of the individual reactants is done in such a way that their complete is guaranteed, so that their implementation in the condensation reaction is as complete as possible.
  • reaction is generally carried out in reaction vessels customary for such condensation reactions, for example in heatable stirred reactors, stirred pressure vessels or stirred autoclave.
  • the reaction mixture is usually allowed to react until a desired maximum viscosity is reached.
  • the viscosity can be determined by sampling and determination by conventional methods, for example with a viscometer; However, it often appears optically in the course of the reaction when the viscosity increases greatly, for example as a result of foaming of the reaction mixture.
  • the reaction is stopped when the reaction mixture has reached a certain desired viscosity, e.g. a viscosity of a maximum of 150,000 mPas, z.
  • the reaction is stopped.
  • the reaction is preferably stopped by lowering the temperature, preferably by lowering the temperature to ⁇ 100 °, z. B. 20 to ⁇ 100 °, preferably to ⁇ 50 ° C, for. B. to 20 to ⁇ 50 ° C.
  • the workup / purification can be carried out by conventional methods, for example by deactivating or removing the catalyst and / or by removing solvent and unreacted educts. In general, however, the degree of purity of the resulting polycondensates is sufficient so that no further work-up or purification must be carried out and the product can be fed directly to its further intended use as a hardener.
  • the polymers (i), (ii) and (iii) are highly branched and substantially non-crosslinked.
  • the oligomers (iv), (v) and (vi) can be prepared according to conventional condensation methods, for example according to the methods described for the polymers (i), (ii) and (iii).
  • the oligomers (iv), (v) and (vi) also arise as by-products in the preparation of the polymers (i), (ii) or (iii) and can be isolated from their reaction mixture, for example by extraction with a solvent, in which the polymer (i), (ii) or (iii) is not soluble.
  • the preparation of the oligomers used according to the invention is preferably carried out in the absence of a catalyst or by using a halogen-free mineral acid (inorganic Brönsted acid) as a catalyst.
  • a halogen-free mineral acid inorganic Brönsted acid
  • suitable and more preferably halogen-free mineral acid reference is made to the above statements.
  • the preparation of the oligomers used according to the invention is preferably carried out in the total absence of halogen-containing compounds.
  • the highly branched polymers (i) are preferred.
  • the highly branched polymers (i) are preferably obtainable by the condensation of
  • each B is independently C2-C3 alkylene and preferably 1, 2-ethylene or 1,3-propylene;
  • m is a number from 1 to 20, preferably from 1 to 10, particularly preferably from 1 to 6 and in particular from 1 to 4;
  • (i-3) optionally at least one amine having a primary amino group and / or at least one amine having at least three primary amino groups other than melamine and the at least one melamine derivative; and in particular of
  • each B is independently 1, 2-ethylene or 1, 3-propylene
  • n is a number from 1 to 1, preferably from 1 to 6 and especially from 1 to 4;
  • (i-3) optionally at least one amine having a primary amino group and / or at least one amine having at least three primary amino groups other than melamine and the at least one melamine derivative; and especially of
  • (i-3) optionally at least one amine having a primary amino group
  • (i-3) optionally at least one amine having a primary amino group and / or at least one amine having at least three primary amino groups other than melamine and the at least one melamine derivative.
  • the weight ratio of melamine to the total of at least one is Melamine derivative preferably 1: 2 to 1000: 1, more preferably 1: 1 to 500: 1 and in particular 2: 1 to 100: 1.
  • the weight ratio of component (i-2a) to (i-2b) is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, more preferably 2: 1 to 1: 2 and especially 1, 5: 1 to 1: 1, 5.
  • the optionally used at least one amine having at least three primary amino groups of component (i-3) is preferably selected from among amines of formula II and III as defined above.
  • the polymers or oligomers (i) to (vi) are used according to the invention for reducing, preventing or delaying the corrosion of materials susceptible to corrosion.
  • the materials susceptible to corrosion are preferably metals susceptible to corrosion.
  • the metals are preferably selected from iron, zinc, aluminum, copper, tin, lead, manganese, nickel and alloys thereof, and more preferably from iron, zinc, aluminum and their alloys.
  • the iron alloys are preferably steel or cast iron.
  • the steels are preferably black steel (non-alloyed, non-electrogalvanised steel), carbon steel (0.2-1.7% carbon), Invar steel (35.5%).
  • Nickel content manganese steel ("ferromanganese”, 75-98% iron + 0.8-25% manganese + 0.5% silicon + 0.1 -1, 5% carbon), silicon steel ("ferrosilicon”; 85-98% Iron + 0.5-15% silicon + 0.1 -1, 7% carbon), or tungsten steel ("Ferro tungsten";
  • metal composites eg. As galvanized sheets or galvanized steel.
  • the metals are particularly preferably selected from iron and iron alloys and, in particular, from iron and steels, in particular iron and the abovementioned steels.
  • the materials to be protected can be present in any form, for example in the form of precursors z. B. as films, sheets or so-called coils (rolled metal strips), or in the form of semi-finished and finished goods, eg. As pipes, components, structures, tools, automotive parts, body parts, equipment panels, cladding, ceiling panels, window profiles and more
  • the reduction, prevention or delay of the corrosion is preferably achieved by using the polymers or oligomers used according to the invention as corrosion inhibitors or as corrosion inhibitors.
  • corrosion inhibitors are compounds which are applied in or as coating agents to the materials to be protected against corrosion, ie the compounds form, optionally together with further substances, a protective film on the materials to be protected.
  • corrosion inhibitor refers to compounds which are added to the corrosive medium in order to react there with the corrosion-causing or corrosion-promoting substances and to reduce or even completely suppress their aggressiveness.
  • the polymers (i) to (iii) are used as corrosion inhibitors.
  • the oligomers (iv) to (vi) can be used both as a corrosion inhibitor and as a corrosion inhibitor.
  • the polymers and oligomers used according to the invention can be used as corrosion inhibitors both in acidic and in neutral or basic media.
  • the polymers and oligomers used according to the invention are used as corrosion inhibitors, they can be used in all forms that are common for anticorrosion agents, for example in the form of paints (for example paints) or in dip baths (for example for simple dipping, but also for cathodic dip painting (KTL)).
  • paints for example paints
  • dip baths for example for simple dipping, but also for cathodic dip painting (KTL)
  • the materials to be treated are usually brought into contact with a preparation which contains at least one of the polymers or oligomers used according to the invention.
  • the contacting For example, by spraying or applying a preparation, eg. As a paint or spray containing at least one of the inventively used polymers or oligomers, on the material to be protected, for example, in the coil coating method. These methods are suitable for both light and medium or heavy corrosion protection.
  • the polymers used according to the invention in immersion baths, for. B. in simple dip baths or in the KTL are used.
  • After contacting the applied layer is usually cured, which can be done for example under atmospheric conditions, but also with additional heating or irradiation.
  • paints to be used according to the invention generally contain at least one binder and optionally further components, such as solvents, crosslinkers, fillers, pigments, reactive diluents, rheology aids, UV absorbers, light stabilizers, radical scavengers, initiators for free-radical polymerization, catalysts for thermal crosslinking, slip additives, polymerization inhibitors, defoamers, emulsifiers, degassing agents, wetting and dispersing agents, adhesion promoters, leveling agents, film-forming auxiliaries, rheology control additives (thickeners), flame retardants, sicactiv, skin-preventing agents or other corrosion inhibitors / corrosion inhibitors.
  • solvents such as solvents, crosslinkers, fillers, pigments, reactive diluents, rheology aids, UV absorbers, light stabilizers, radical scavengers, initiators for free-radical polymerization, catalysts for thermal crosslinking, slip additives, polymer
  • Common binders include, for example, (meth) acrylic acid (c) polymers, e.g. As styrene / acrylic acid copolymers, (meth) acrylate (co) polymers, partially saponified polyvinyl esters, polyesters, alkyd resins, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides or polyurethanes or mixtures thereof from.
  • Conventional binders may be aqueous-soluble or organic-soluble binder systems. They are preferably water-based binder systems.
  • Binders which are suitable for aqueous systems are, for example, epoxy resins, polyacrylates, styrene-acrylic acid polymers, styrene-acrylate polymers, polyesters, alkyd resins, polyurethanes of the styrene-butadiene polymers.
  • the optionally contained solvents serve to dissolve and / or disperse the remaining components of the paint to allow uniform application to the material to be treated.
  • a solvent Suitable solvents are those which are able to dissolve, disperse, suspend or emulsify the polymers or oligomers used according to the invention.
  • These may be organic solvents, water or aqueous ammoniacal solutions. Of course, mixtures of different organic solvents or mixtures of organic solvents with water can be used.
  • organic solvents examples include hydrocarbons such as toluene, the xylenes, the Solvesso® grades, especially Solvesso® 100, 150 and 200, as well as the Shellspell® grades from Shell, or blends such as are obtained in the refining of crude oil such as hydrocarbon fractions of certain boiling ranges, ethers such as THF or polyethers such as polyethylene glycol, ether alcohols such as ethylene glycol mono-n-butyl ether (butyl glycol), propylene glycol monoethyl ether, dipropylene glycol monomethyl ether or propylene glycol monomethyl ether, ether glycol acetates such as butyl glycol acetate or propylene glycol monomethyl ether acetate, ketones such as acetone, alcohols such as methanol, Ethanol or propanol, or lactams, such as N-methylpyrrolidone, N-ethylpyrrolidone, N- (n-buty
  • water or a predominantly aqueous solvent mixture can be used. These are understood as meaning mixtures which comprise at least 50% by weight, preferably at least 65% by weight and particularly preferably at least 80% by weight of water.
  • Other components are water-miscible solvents. Examples include monoalcohols such as methanol, ethanol or propanol, higher alcohols such as ethylene glycol or polyether polyols and ether alcohols such as butyl glycol or methoxypropanol.
  • the crosslinkers can be both thermally and photochemically curing crosslinkers.
  • Suitable thermal crosslinkers are, for example, crosslinkers based on epoxides, in which two or more epoxide groups are linked to one another by means of a linking group. Examples include low molecular weight compounds having two epoxide groups such as hexanediol diglycidyl ether, phthalic acid diglycidyl ether or cycloaliphatic compounds such as 3,4-Epoxicyclohexancarbonklare 3 ', 4'-epoxycyclo-hexylmethylester.
  • crosslinkers include crosslinkers based on aminoplast resins, for example melamine-formaldehyde resins, urea-formaldehyde resins or tris (alkoxycarbonyl) triazines.
  • blocked polyisocyanates are suitable crosslinkers. In blocking, the isocyanate group is reversibly reacted with a blocking agent. The blocking agent is at Heating to higher temperatures split off again.
  • Suitable blocking agents are described in DE-A 199 14 896 and in DA Wieks, ZW Wieks, Progress in Organic Coatings, 36, 148-172 (1999), 41, 1-83 (2001) and 43, 131-140 ( 2001) and are, for example, phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxybenzoic acid esters, secondary amines, lactams, CH-acidic cyclic ketones, malonic esters or alkyl acetoacetates.
  • the fillers are usually inorganic finely divided fillers. However, these can comprise an additional organic coating, for example for hydrophobing or hydrophilization.
  • the filler should not exceed an average particle size of 10 ⁇ .
  • the average particle size is 10 nm to 8 ⁇ , with this statement referring to the longest axis of the particles.
  • particle size is meant the primary particle size, because the skilled person is of course aware that finely divided solids often agglomerate to larger particles that must be dispersed intensively for use.
  • Fillers can be used to influence the properties of the coating, such as, for example, hardness, rheology or the orientation of the effect pigments possibly contained in the coating material. Fillers are often coloristically ineffective; d. H. they have a low intrinsic absorption and the refractive index is similar to the refractive index of the coating medium.
  • Examples of fillers include talc, calcium carbonate, kaolin, barium sulfate, magnesium silicate, aluminum silicate, crystalline or nanoparticulate silica, amorphous silica, alumina, microspheres or hollow microspheres, for example.
  • any solid inert organic particles such.
  • urea-formaldehyde condensation products micronized polyolefin wax or micronized amide wax used.
  • the inert fillers can also be used in each case in a mixture. Preferably, however, only one filler is used in each case.
  • the pigments may in particular be anti-corrosion pigments. They can be both active and passive anticorrosive pigments.
  • active anticorrosion pigments include in particular phosphates, phosphate-containing or modified phosphates such as zinc phosphate-based pigments, zinc aluminum orthophosphate, zinc molybdenum orthophosphate, zinc aluminum molybdenum orthophosphate, calcium hydrogen phosphate, zinc calcium strontium orthophosphate silicate, zinc aluminum Polyphosphate, strontium-aluminum Polyphosphate, zinc-calcium-aluminum-strontium-orthophosphate-polyphosphate-silicate, calcium-aluminum-polyphosphate-silicate.
  • inorganic phosphates with sparingly soluble electrochemically active organic corrosion inhibitors such as zinc phosphate modified with Zn or Ca salts of 5-nitroisophthalic acid.
  • typical organic anti-corrosive pigments such as, for example, Zn or Ca salts of 5-nitroisophthalic acid.
  • Passive anti-corrosive pigments extend the diffusion paths for corrosive components, thereby increasing corrosion resistance.
  • Examples include, in particular, flake-form or lamellar pigments such as mica, hematite, sheet silicates, linear polysilicates such as wollastonite, talc or metal flakes such as aluminum or iron flakes. Further details on anticorrosive pigments are described, for example, in "Pigments, 4.2 Anticorrosive Pigments" in U-Mannesmann's Encyclopedia of Technical Chemistry, 6th Edition 2000, Electronic Release.
  • the pigments may also be typical dye and / or effect pigments.
  • Effect pigments are to be understood as meaning all pigments which have a platelet-like structure and impart special decorative color effects to a surface coating. Effect pigments are known to the person skilled in the art. Examples include pure metal pigments, such as. As aluminum, iron or copper pigments, interference pigments, such as. Titanium oxide coated mica, iron oxide coated mica, mixed oxide coated mica (eg with titanium dioxide and Fe 2 O 3), metal oxide coated aluminum, or liquid crystal pigments.
  • Color pigments are, in particular, customary organic or inorganic absorption pigments which can be used in the paint industry.
  • organic absorption pigments are azo pigments, phthalocyanine, quinacridone and pyrrolopyrrole pigments.
  • inorganic absorption pigments are iron oxide pigments, titanium dioxide and carbon black.
  • dyes are azo, azine, anthraquinone, acridine, cyanine, oxazine, polymethine, thiazine, triarylmethane dyes. These dyes can be used as basic or cationic dyes, mordant, direct, disperse, development, vat, metal complex, reactive, acid, sulfur, coupling or substantive dyes.
  • the paint used according to the invention contains at least one anticorrosive pigment, of which nanoparticulate silicon dioxide is preferred below (see also below).
  • the polymers and oligomers used according to the invention partly or completely replace the customary binders (for example those based on acrylic acid or acrylate, eg styrene / acrylic acid copolymers) and increase the anticorrosion effect due to their own anticorrosive properties of such formulations or the coatings produced with it significantly.
  • the polymers and oligomers used in accordance with the invention are preferably anti-corrosive pigment formulations, particularly preferably those with oxidic pigments.
  • Preferred oxidic pigments are selected from S1O2, Z2O, ZnO and BaTiO3 pigments and more preferably from SiO2 pigments.
  • Another object of the invention are therefore corrosion inhibitors comprising at least one highly branched polymer and / or at least one oligomer according to the above definition; and (b) at least one anticorrosive pigment selected from silica, titania, zinc (II) oxide and barium titanate (BaTiO-3) and preferably an SiO 2 pigment.
  • the oxidic pigments are preferably nanoparticulate. Nanoparticulate in this context means that none of the dimensions of such particles exceeds 100 nm.
  • Nanoparticulate oxidic pigments are known and commercially available, for example as Aerosil® 200 from Evonik (silicon dioxide particles having an average particle size of 12 nm and a BET surface area of 170 +/- 125 m 2 / g) or Ludox CL-P from Grace ( colloidal silica dispersion).
  • the corrosion inhibitor according to the invention may additionally comprise at least one of the above-mentioned o. optional components for paints included. Preferably, however, it contains no further binder and no further anticorrosive pigment.
  • Coil coatings are coatings of rolled metal strips which are wound up into coils ("coils") after being manufactured for storage and transport. These metal bands are the starting material for most flat metal workpieces, such as automotive parts, body panels, equipment panels, cladding, ceiling panels or window profiles.
  • the suitable metal sheets are formed by means of suitable techniques such as stamping, drilling, folding, profiling and / or deep-drawing. Coil-coating process is the continuous coating of metal strips with mostly liquid coating materials.
  • 0.2 to 2 mm thick and up to 2 m wide metal strips are transported at a rate of up to 200 m / min through a coil coating system and thereby coated.
  • cold-rolled strips made of soft steels or structural steels, electrolytically galvanized thin sheet, fire-galvanized steel strip or strips of aluminum or aluminum alloys can be used.
  • Typical installations include a feed station, a strip accumulator, a cleaning and pretreatment zone, a first coating station together with a baking oven and the following cooling zone, a second coating station with oven, laminating station and cooling, and a belt store and rewinder.
  • Characteristic of coil coatings are thin layers of the coating compositions, which have a dry film thickness of mostly well below 80 ⁇ , often below 60 ⁇ , below 50 ⁇ and even below 40 ⁇ .
  • the sheets are processed with high throughput, which requires short residence times, so after application of the coating drying Increased temperature required to make the coating material quickly loaded.
  • the polymers or oligomers used according to the invention give corrosion protection agents which are used in categories C2 (according to DIN EN ISO 12944) or higher, preferably in corrosivity categories C3 or higher and more preferably in corrosivity categories C4 or higher.
  • the corrosivity categories are defined according to DIN EN ISO 12944 based on the area-related mass loss or on the thickness decrease after the first year of removal as follows for unalloyed steel or for zinc:
  • Zinc mass loss> 15-30 g / m 2
  • Zinc mass loss> 30 - 60 g / m 2
  • the polymers and oligomers used according to the invention are also suitable for use in electrochemical, especially in cathodic dip coating (cathaphoresis) where they can partially or completely replace the phosphating step.
  • the material to be coated (ie, the material to be coated) is immersed in an electrically conductive, aqueous immersion paint and a DC voltage field is applied between the material to be painted and a counterelectrode.
  • particles contained in the dipping paint z.
  • binders on the surface precipitated as an electrode Lackierguts and thus form a closed, adherent paint film.
  • cathodic dip painting the paint is switched as a cathode.
  • phosphating also called bonders or parkerization
  • a so-called conversion layer of firmly adhering metal phosphates is formed by chemical reaction of a metallic surface with aqueous phosphate solutions.
  • the phosphate layer adheres very well to the substrate and, due to the microporous or microcapillary layer structure, allows good anchoring of subsequent coatings. In addition, it makes it difficult to rust on damaged areas of the coating.
  • a disadvantage of phosphating is that one usually heavy metal phosphates, such as iron, zinc or manganese phosphate, used, which makes the disposal of wastewater complex and expensive.
  • the above-described polymers and oligomers can partially or completely replace the phosphates and form similarly well-adhering layers with comparable or even better anti-corrosive properties.
  • the polymer or oligomer is deposited either by simply dipping the substrate to be coated in a solution containing the polymers, or by applying a voltage to the substrate surface. The remaining process steps can then be carried out as in conventional electrochemical dipping.
  • the use of the above-described polymers and oligomers in the electrochemical immersion process and especially in the cathodic immersion process reduces the disposal problem of phosphate-containing wastewaters.
  • the polymers and oligomers described above combine several properties which are of crucial importance for corrosion protection, and are therefore distinguished by a variety of possible uses in corrosion protection.
  • the amine number was determined according to DIN 53176. 1 . Production of hyperbranched polymers
  • Hexamethylenediamine (589.1 g, 5.07 mol) and tetraethylenepentamine (533.9 g, 2.82 mol) were mixed under nitrogen flow in a 4 l four-necked flask with metal stirrer, reflux condenser, heated mushroom and discharge to a sulfuric acid-filled scrubber Ethylene glycol (500 ml) was added. Subsequently, phosphoric acid (48.4 g, 0.49 mol) was added dropwise and phosphorous acid (69.7 g, 0.85 mol) was added and the mixture was heated to 50 ° C.
  • the product had the following properties: M n: 5500; M w : 25,000; PD: 4.6 (GPC in hexafluoroisopropanol).
  • the polymers from Examples 1.1 and 1.2 were dissolved in 60 ° C warm water in such a concentration that each resulted in 10 wt .-% solutions.
  • the pH was adjusted to 5 to 6 with phosphoric acid.
  • a 50% dispersion of a styrene / acrylic acid copolymer (Acronal® S 760 from BASF SE) was used.
  • Dipping baths of the composition shown in Table 1 were prepared from the three polymer solutions with the addition of oxidic nanoparticles (either silica particles (Aerosil® 200 from Evonik) or colloidal silica dispersion (Ludox® CL-P from Grace)
  • Acronal® S 760 from BASF SE The test was carried out by immersing the substrates in the immersion bath and subsequent corrosion test of the substrates coated in this way.
  • the substrates used were steel sheets (Gardobond® OC from Chemetall) and galvanized steel sheets (Gardobond® OMBZ, electrolytically galvanized steel sheets from Chemetall) with a size of 10.5 ⁇ 19 cm.
  • the immersion process is carried out after alkaline cleaning of the test sheets, followed by a rinsing step by complete immersion of the sheets at 50 ° C. After a residence time of 3 minutes, the sheets, after being lifted out and briefly drained, were dried over the edge of the test sheets in a drying oven at 60 ° C.
  • a third sheet after removal from the dipping bath, was immersed briefly in a rinsing bath (demineralized water) before directly applying a cathodic dip paint having a layer thickness of 20 +/- 3 ⁇ m.
  • These sheets were scratched and subjected to the salt spray test in accordance with EN ISO 9227: 2006.
  • the evaluation was carried out according to EN ISO 9227: 2006 by determining the infiltration at the Ritz. For this purpose, after the storage in the salt spray chamber, all loose areas were completely removed with a doctor blade and the released gap or the exposed defects were measured (in mm width).
  • Table 2 rust index Rl according to ISO 10289

Abstract

La présente invention concerne l'utilisation de composés polymères ou oligomères très ramifiés qui sont produits par condensation de (dérivés) de mélamine et/ou de (dérivés) d'urée avec des di ou polyamines pour réduire ou empêcher la corrosion de matériaux menacés de corrosion. L'invention concerne également un procédé pour réduire, retarder ou empêcher la corrosion de matériaux menacés de corrosion, selon lequel on met en contact les matériaux et/ou le milieu corrosif auquel les matériaux sont exposés avec au moins un des ces polymères et/ou oligomères très ramifiés, et un agent de protection anticorrosion qui contient ces polymères et/ou oligomères très ramifiés ainsi qu'un pigment de protection anticorrosion.
PCT/EP2011/056007 2010-04-16 2011-04-15 Polymères d'amine et oligomères d'amine très ramifiés comme agent de protection anticorrosion WO2011128437A1 (fr)

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CN114685931A (zh) * 2021-12-15 2022-07-01 江苏金发科技新材料有限公司 一种聚甲醛复合材料及其制备方法和应用
CN114685932A (zh) * 2021-12-15 2022-07-01 上海金发科技发展有限公司 一种聚甲醛组合物及其制备方法和应用
US11421326B2 (en) 2020-06-22 2022-08-23 Saudi Arabian Oil Company Hyperbranched polymers with active groups as efficient corrosion inhibitors
CN114957658A (zh) * 2022-07-13 2022-08-30 西南林业大学 一种缩聚型热固性树脂预聚体及其应用方法

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11421326B2 (en) 2020-06-22 2022-08-23 Saudi Arabian Oil Company Hyperbranched polymers with active groups as efficient corrosion inhibitors
CN114685931A (zh) * 2021-12-15 2022-07-01 江苏金发科技新材料有限公司 一种聚甲醛复合材料及其制备方法和应用
CN114685932A (zh) * 2021-12-15 2022-07-01 上海金发科技发展有限公司 一种聚甲醛组合物及其制备方法和应用
CN114685931B (zh) * 2021-12-15 2024-02-27 江苏金发科技新材料有限公司 一种聚甲醛复合材料及其制备方法和应用
CN114685932B (zh) * 2021-12-15 2024-03-19 上海金发科技发展有限公司 一种聚甲醛组合物及其制备方法和应用
CN114957658A (zh) * 2022-07-13 2022-08-30 西南林业大学 一种缩聚型热固性树脂预聚体及其应用方法
CN114957658B (zh) * 2022-07-13 2023-02-24 西南林业大学 一种缩聚型热固性树脂预聚体及其应用方法

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