DE102011008399A1 - Polynitrone based on polysekundamines for crosslinking and / or modification of unsaturated polymers - Google Patents

Abstract

The invention relates to polynitron produced by oxidation of secondary amines and their use for crosslinking unsaturated polymers, as well as a curable composition comprising (a) a polynitron based on the addition of a primary amine to a suitable component with subsequent oxidation, (b) a unsaturated polymer or a mixture of polymers, where at least one polymer contains unsaturated functions or has functional groups which can react with the polynitron, (b) optionally fillers, (c) optionally pigments, (d) optionally additives, e.g. B. plasticizers, stabilizers or photoinitiators and (e) optionally other crosslinkers such as polyisocyanates, bisdienes, polyoxaziridines, and their use as adhesives, rubber, filler, sprayable thick-film filling, ink, paint, powder coating, water-based or solvent-based paint. The invention also relates to crosslinking products obtainable by curing the curable composition according to the invention.

Description

The invention is in the field of crosslinkers for polymers. These are molecules that contain more than two functional groups that can be used to connect linear or branched macromolecules to form three-dimensional networks. Proposed for this use Polynitrone, which are based on the addition of a primary amine to a suitable component followed by oxidation.

Crosslinkers have a variety of technical applications, since, for example, the mechanical properties of polymers are highly dependent on the degree of crosslinking. Crosslinkers are of particular importance in the production of solid coatings from coating formulations. In lacquer technology, the component which has the lower molecular weight and is present in a smaller amount is usually regarded as the crosslinker. Crosslinkers have a strong influence on the production, storage, application and the processing properties of coatings such as extrusion temperature, storage stability, curing time, curing temperature, flow properties, impact resistance, hardness, weather resistance and chemical resistance. Examples of crosslinked polymers are paints.

Paints can be divided into solvent-based paints, water-based paints and powder coatings after use of the solvent. Modern paints are increasingly solvent-reduced or even solvent-free, reducing the amount of volatile organic solvents (VOCs) that are emitted into the environment. They thus reduce the amount of waste and avoid exposing people to critical air mixtures. For the reasons mentioned, solvent-based systems are increasingly substituted by environmentally friendly paints such as powder coatings.

Conventional powder coatings have a considerable limitation in use because they require high temperatures to cure from 160 to 230 ° C. These high baking temperatures mean that only substrates with high heat resistance can be used. The coating of wood and plastics, but also of metallic alloys with special properties is therefore limited with thermosetting powder coatings possible. The need for low temperature powder coatings that cure at low temperature is therefore very high. The only powder coatings available on the market which cure at temperatures below 150 ° C. are so-called low-temperature epoxy resins. However, these do not allow coatings of satisfactory quality, as they are e.g. B. have low light resistance and low scratch resistance. ¹ Curing of powder coatings usually takes place by reaction of an epoxide with an acid, an acid anhydride, an amine, a phenol or a Lewis base or by adding an isocyanate to an alcohol. Most commercially available crosslinkers contain identical reactive ends, such as epoxies, amines, phenols or isocyanates. In addition, reference is made to Powder Coatings Chemistry and Technology by Pieter Gillis de Lange, Vincentz Network 2003.

Paints, in particular powder coatings, often contain unsaturated polymers as binders. For example, unsaturated polyesters or acrylates are used. Crosslinkers which cause crosslinking via unsaturated functions are scarcely known. Curing by radical polymerization (eg by means of styrene) requires initiators and usually harmful heavy metal catalysts. In addition, it has practical significance only for radiation-curing paints. The radical production takes place by an initiator, which is decomposed into radicals. Radiation-curing paints have some unresolved problems that often result from the limited layer thicknesses. This limitation is caused by the UV radiation having to penetrate the substrate completely. For example, many techniques that thermally curable coatings are structured and modified, for. As with pigments, fillers or solid additives, are used only to a limited extent. In addition, the uniform hardening of three-dimensional edges is a problem.

In addition to the crosslinking of unsaturated polymers by means of radical polymerization, crosslinking via cycloaddition is known, which does not require any initiators and harmful heavy metal catalysts.

WO 2009/074310 A1 describes Polynitrone and their use as crosslinking and matting agents, preferably for the production of stable molding compounds, fillers, their use in paints, coatings and adhesives. This crosslinking reaction takes place at a comparatively low stoving temperature by cycloaddition between polynitrone and unsaturated polymer. The polynitrone according to WO 2009/074310 A1 are synthesized by reaction of a dialdehyde with N-alkyl or N-arylhydroxylamine. The variation of the structure of the polynitrone takes place mostly via a change in the structure of the dialdehydes. These usually have to be synthesized beforehand in several steps.

Furthermore, the synthesis is limited by the limited accessibility of the hydroxylamines Judith Pietschmann, Industrial Powder Coating, 3rd Edition 2010, JOT Reference Book (H. Mitsui, S.-i. Zenki, T. Shiota, S. Murahashi, Journal of the Chemical Society, Chemical Communications 1984, 874-875) , Only a few hydroxylamines such as N-methylhydroxylamine hydrochloride and benzylhydroxylamine hydrochloride are commercially available, which limits the variation of the polynitron structure. As a result, the properties of the Polynitrone such as melting point and the crosslinking products such as glass transition temperature can be varied only limited. In addition, the high cost of hydroxylamines complicate an economical industrial application.

Furthermore, it is known that Polynitrone arise in the oxidation of polyimines. However, this method is limited use, since depending on the substituents on the imine group different products such as amides, formamides, oxaziridines or nitrones arise. In addition, a certain proportion of aldehyde is often formed by decomposition of imine, oxazirdine or nitrone. In most cases, therefore, one obtains a product mixture from which the nitrone must be laboriously isolated. Furthermore, the nitrone is produced only as a major product in the oxidation of polyimines with a particular substitution pattern. Due to the limitation to certain substituted polyimines and the numerous side reactions, an economical Polynitronsynthese by oxidation of polyimines is limited. However, the yields of nitrone can be increased by first hydrogenating the polyimines to polyamines and then oxidizing them. The hydrogenation of polyimines usually occurs with molecular hydrogen in the presence of a metal catalyst. It is important to keep in mind that molecular hydrogen is a low-molecular-weight flammable gas and therefore has high diffusibility. Especially because of the formation of explosive hydrogen-air mixtures, working with the gas represents a considerable potential hazard and therefore costly and expensive protective measures must be taken in the hydrogenation.

The object of this invention was to develop a method for the synthesis of polynitrons, which is risk-free and economically feasible in large quantities.

It has been found by chance that poly-secondary amines obtained by addition of a primary amine to a suitable component with e.g. B. one or more double bonds or epoxide groups are prepared, can be oxidized in good yields to polynitrons. In the art, the oxidation of monofunctional secondary amines to nitrones is known. The synthesis of polysekundäraminen by addition of an amine to a suitable component, for example, epoxy groups and / or double bonds, in particular activated double bonds, containing subsequent oxidation to polynitrons is unknown in the art.

The invention thus relates to the synthesis of monofunctional and polyfunctional polynitrons by oxidation of polysekundäraminen, which are based on the addition of a primary amine to a suitable component.

• (a) ein Polynitron, wobei die endständigen Substituenten am N-Atom des Polynitrons in beta-Position eine Hydroxygruppe oder in gamma-Position eine Carbonylgruppe enthalten
• (b) ein ungesättigtes Polymer oder eine Mischung an Polymeren, wobei mindestens ein Polymer ungesättigte Funktionen enthält bzw. funktionelle Gruppen aufweist, die mit dem Polynitron reagieren können,
• (c) gegebenenfalls Füllstoffe,
• (d) gegebenenfalls Pigmente,
• (e) gegebenenfalls Zusatzstoffe z. B. Weichmacher, Stabilisatoren und/oder Photoinitiatoren sowie
• (f) gegebenenfalls weitere Vernetzer wie Polyisocyanate, Bisdiene und/oder Polyoxaziridine.

Another object of the invention are curable compositions comprising

• (a) a polynitrone, wherein the terminal substituents on the N-atom of the polynitrone in beta position contain a hydroxy group or in the gamma position a carbonyl group
• (b) an unsaturated polymer or a mixture of polymers, wherein at least one polymer contains unsaturated functions or has functional groups that can react with the polynitrone,
• (c) optionally fillers,
• (d) optionally pigments,
• (e) optionally additives such. As plasticizers, stabilizers and / or photoinitiators and
• (f) optionally further crosslinkers such as polyisocyanates, bisdienes and / or polyoxaziridines.

Nitrones are usually compounds with the structural element C (R ¹ ) (R ² ) = NO (R ³ ) wherein the double bond is between C and N and the radical R ^{3 is} attached to the nitrogen and wherein the radicals R ¹ , R ² and R ^{3 represent} hydrogen or any alkyl or aryl radicals which may also be substituted, provided that at least one radical is not hydrogen.

According to the invention, monofunctional and polyfunctional polynitrons are used. For the purposes of the invention, these are understood as meaning compounds whose molecules contain at least one, preferably 1 to 20, nitron groups, in particular 1 to 6 nitron groups. They may be C side, so bound to each other via the radical R ¹ or R ² or N side, so be bound to each other via the radical R ³ .

Starting compounds are poly-secondary amines, which are oxidized to polynitrons under conditions familiar to the organic chemist. The polysekundary amines used according to the invention are prepared by addition reaction of a primary amine to a suitable component, preferably an unsaturated compound. Particularly preferred as a suitable component activated unsaturated compounds such. As alpha, beta-unsaturated carbonyl, nitrile or carboxamide (Michael acceptors) and / or epoxides used. For the purposes of the invention therefore serve as starting components primary amines and more preferably epoxides and / or Michael acceptors. In addition to monofunctional polynitrones, N-bridged polynitrone from polyfunctional amines is just as preferred as C-bridged polynitrone from polyfunctional Michael acceptors or epoxides.

It is advantageous that primary amines, epoxides and unsaturated compounds in countless variants are commercially available and thus result in almost unlimited variations of Polynitron structures.

The polynitrone used according to the invention may contain aromatic radicals. These are understood to mean any, even substituted, radicals having at least one aromatic group. Suitable aromatic radicals may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen. The term "aromatic radical" (or "aromatic radical") as used herein includes, without limitation, phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene and biphenyl radicals. As stated, the aromatic radical contains at least one aromatic group. The aromatic group is invariably a cyclic structure with 4n + 2 "delocalized" electrons, where "n" is an integer equal to 1 or more, such as phenyl groups (n = 1), thienyl groups (n = 1), furanyl groups (n = 1), naphthyl groups (n = 2), azulenyl groups (n = 2), anthracenyl groups (n = 3) and the like. The aromatic moiety may also include non-aromatic moieties. So, z. For example, a benzyl group is an aromatic group comprising a phenyl ring (the aromatic group) and a methylene group (the non-aromatic component). Similarly, a tetrahydronaphthyl radical is an aromatic radical comprising an aromatic group (C ₆ H ₃ ) fused to a non-aromatic component - (CH ₂ ) ₄ -. For convenience, the term "aromatic radical" is defined herein as comprising a wide range of functional groups, such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, haloaromatic groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (e.g. Carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, sulfonyl groups, sulfamyl groups, phosphinoyl group and the like. So, z. B., the 4-methylphenyl radical, an aromatic C ₇ radical comprising a methyl group, the methyl group being a functional group which is an alkyl group. Similarly, the 2-nitrophenyl group is an aromatic C ₆ radical comprising a nitro group, the nitro group being a functional group. Aromatic radicals include halogenated aromatic radicals such as 4-trifluoromethylphenyl, hexafluoroisopropylidenebis (4-phen-1-yloxy) (ie, -OPhC (CF ₃ ) ₂ PhO-), 4-chloromethylphen-1-yl, 3-trifluorovinyl-2 thienyl, 3-trichloromethylphen-1-yl (ie, 3-CCl ₃ Ph-), 4- (3-bromoprop-1-yl) phen-1-yl (ie, 4-BrCH ₂ CH ₂ CH ₂ Ph-) and similar ones. Further examples of aromatic radicals include 4-allyloxyphen-1-oxy, 4-aminophen-1-yl (ie, 4-H ₂ NPh-), 3-aminocarbonyl-phen-1-yl (ie, NH ₂ COPh-), dicyanomethylidene bis (4-phen-1-yloxy) (ie, -OPhC (CN) ₂ PhO-), 4-benzoylphen-1-yl, 3-methylphen-1-yl, methylenebis (4-phen-1-yloxy) (ie , -OPhCH ₂ PhO-), 2-ethylphen-1-yl, phenylethenyl, fluorenyl, 3-formyl-2-thienyl, 2-hexyl-5-furanyl, hexamethylene-1,6-bis (4-phen-1) yloxy) (ie, -OPh (CH ₂ ) ₆ PhO-), benzenesulfonyl (ie, PhSO ₂ -), 4-hydroxymethylphen-1-yl (ie, 4-HOCH ₂ Ph-), 4-mercaptomethylphen-1-yl (ie, 4-HSCH ₂ Ph-), 4-methylthiophene-1-yl (ie, 4-CH ₃ SPh-), 3-methoxyphen-1-yl, 2-methoxycarbonylphen-1-yloxy (e.g., methyl salicyl ), 2-nitromethylphen-1-yl (ie, 2-NO ₂ CH ₂ Ph), 3-trimethylsilylphen-1-yl, 4-t-butyldimethylsilylphenyl-1-yl, 4-vinylphen-1-yl, vinylidene bis (phenyl ) and similar. The term "an aromatic C ₃ -C ₁₀ radical" includes aromatic radicals containing at least three but not more than 10 carbon atoms. The aromatic radical 1-imidazolyl (C ₃ H ₂ N ₂ -) represents an aromatic C ₃ radical. The benzyl radical (C ₇ H ₇ -) represents an aromatic C ₇ radical.

The polynitrone according to the invention may also contain cycloaliphatic radicals.

The term "cycloaliphatic radical" (or "cycloaliphatic radical") as used herein refers to a radical having a valence of at least 1 and includes a number of atoms which is cyclic but not aromatic. As defined herein, a "cycloaliphatic residue" does not contain an aromatic group. A "cycloaliphatic radical" may include one or more non-cyclic moieties. So, z. For example, a cyclohexylmethyl group (C ₆ H ₁₁ CH ₂ -) is a cycloaliphatic radical comprising a cyclohexyl ring (the series of atoms which is cyclic but not aromatic) and a methylene group (the non-cyclic component). The cycloaliphatic radical may include heteroatoms, such as nitrogen, Sulfur, selenium, silicon and oxygen, or it may be composed solely of carbon and hydrogen. For convenience, the term "cycloaliphatic radical" is defined herein as comprising a wide range of functional groups, such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (e.g., carboxylic acid derivatives, such as esters and amides), amine groups, nitro groups, sulfonyl groups, sulfamyl groups, phosphinoyl group and the like. So, z. For example, the 4-methylcyclopent-1-yl radical is a cycloaliphatic C ₆ radical comprising a methyl group wherein the methyl group is a functional group which is an alkyl group. Similarly, the 2-nitrocyclobut-1-yl moiety is a cycloaliphatic C ₄ moiety comprising a nitro group wherein the nitro group is a functional group. A cycloaliphatic radical may comprise one or more halogen atoms, which may be the same or different. Close halogen atoms, z. B., fluorine, chlorine, bromine and death. Cycloaliphatic radicals having one or more halogen atoms include 2-trifluoromethylcyclohex-1-yl, 4-bromodifluoromethylcyclooct-1-yl, 2-chlorodifluoromethylcyclohex-1-yl, hexafluoroisopropylidene-2,2-bis (cyclohex-4-yl) (ie C ₆ H ₁₀ C (CF ₃ ) ₂ C ₆ H ₁₀ -), 2-chloromethylcyclohex-1-yl, 3-difluoromethylene-cyclohex-1-yl, 4-trichloromethylcyclohexyl-1-yloxy, 4-bromodichloromethylcyclohex-1 -ylthio, 2-bromoethylcyclopent-1-yl, 2-bromopropylcyclohex-1-yloxy (e.g., CH ₃ CHBrCH ₂ C ₆ H ₁₀ O-) and the like. Further examples of cycloaliphatic radicals include 4-allyloxycyclohex-1-yl, 4-aminocyclohex-1-yl (ie, H ₂ NC ₆ H ₁₀ -), 4-aminocarbonylcyclopent-1-yl (ie, NH ₂ COC ₅ H ₈ -) , 4-acetyloxycyclohex-1-yl, 2,2-dicyanisopropylidenebis (cyclohex-4-yloxy) (ie, -OC ₆ H ₁₀ C (CN) ₂ C ₆ H ₁₀ O-), 3-methylcyclohex-1-yl, methylene bis (cyclohex-4-yloxy) (ie, -OC6H ₁₀ CH ₂ C ₆ H ₁₀ O-), 1-Ethylcyclobut-1-yl, 3-formyl-2-tetrahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl, Cyclopropylethenyl, Hexamethylene-1,6-bis (cyclohex-4-yloxy) (ie, -OC ₆ H ₁₀ (CH ₂ ) ₆ C ₆ H ₁₀ O-), 4-hydroxymethylcyclohex-1-yl (ie, 4-HOCH ₂ C) ₆ H ₁₀ -), 4-mercaptomethylcyclohex-1-yl (ie, 4-HSCH ₂ C ₆ H ₁₀ -), 4-methylthiocyclohex-1-yl (ie, 4-CH ₃ SC ₆ H ₁₀ -), 4- Methoxycyclohex-1-yl, 2-methoxycarbonylcyclohex-1-yloxy (2-CH ₃ OCOC ₆ H ₁₀ -), 4-nitromethylcyclohex-1-yl (ie, NO ₂ CH ₂ C ₆ H ₁₀ -), 3-trimethylsilylcyclohex- 1-yl, 2-tert-butyldimethylsilylcyclopent-1-yl, 4-trimethoxysilylethylcyclohex-1-yl (e.g., (CH ₃ O) ₃ SiCH ₂ CH ₂ C ₆ H ₁₀ -), 4-vinylcyclohexen-1-yl, vinylidene bis (cyclohexyl) and the like. The term "a cycloaliphatic C ₃ -C ₁₀ radical includes cycloaliphatic radicals containing at least three but not more than 10 carbon atoms. The cycloaliphatic radical 2-tetrahydrofuranyl (C ₄ H ₇ O-) represents a cycloaliphatic C ₄ radical. The cyclohexylmethyl radical (C ₆ H ₁₁ CH ₂ -) represents a cycloaliphatic C ₇ radical.

The Poynitrone invention can also contain aliphatic radicals. As used herein, the term "aliphatic radical" (or "aliphatic radical") refers to an organic radical having a valence of at least 1 consisting of a linear or branched array of atoms that is not cyclic. Aliphatic radicals are defined as comprising at least one carbon atom. The array of atoms comprising the aliphatic moiety may include heteroatoms such as nitrogen, sulfur, silicon, selenium, and oxygen, or may be composed solely of carbon and hydrogen. For convenience, the term "aliphatic radical" is defined herein to include a wide range of functional groups, such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, conjugated dienyl groups, as part of the "linear or branched arrangement of atoms which is not cyclic" , Alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (eg, carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, sulfonyl groups, sulfamyl groups, phosphinoyl group, and the like. So, z. For example, the 4-methylpent-1-yl radical is an aliphatic C ₆ radical comprising a methyl group wherein the methyl group is a functional group which is an alkyl group. Similarly, the 4-nitrobut-1-yl group is an aliphatic C ₄ radical comprising a nitro group, the nitro group being a functional group. An aliphatic radical may be a haloalkyl group comprising one or more halogen atoms, which may be the same or different. Close halogen atoms, z. As, fluorine, chlorine, bromine and iodine. Aliphatic radicals comprising one or more halogen atoms include the alkyl halides trifluoromethyl, bromodifluoromethyl, chlorodifluoromethyl, hexafluoroisopropylidene, chloromethyl, difluorovinylidene, trichloromethyl, bromodichloromethyl, bromoethyl, 2-bromotrimethylene (e.g., -CH ₂ CHBrCH ₂ -), and the like. Further examples of aliphatic radicals include allyl, aminocarbonyl (ie, -CONH ₂ ), carbonyl, 2,2-dicyanisopropylidene (ie, -CH ₂ C (CN) ₂ CH ₂ -), methyl (ie, -CH ₃ ), methylene ( ie, -CH ₂ -), ethyl, ethylene, formyl (ie, -CHO), hexyl, hexamethylene, hydroxymethyl (ie, -CH ₂ OH), mercaptomethyl (ie, -CH ₂ SH), methylthio (ie, -SCH ₃ ), methylthiomethyl (ie, -CH ₂ SCH ₃ ), methoxy, methoxycarbonyl (ie, CH ₃ OCO-), nitromethyl (ie, -CH ₂ NO ₂ ), thiocarbonyl, trimethylsilyl (ie, (CH ₃ ) ₃ Si). ), tert-butyldimethylsilyl, 3-trimethyloxysilylpropyl (ie, (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ -), vinyl, vinylidene and the like. As another example, a C ₁ -C ₁₀ aliphatic radical contains at least one but not more than 10 carbon atoms. A methyl group (ie, CH ₃ -) is an example of an aliphatic C ₁ radical. A decyl group (ie, CH ₃ (CH ₂ ) ₉ -) is an example of a C ₁₀ aliphatic radical.

Preferred polynitrone correspond to a general formula [Z (-X) n] m in which X is an optionally substituted nitron group attached via the carbon atom or the nitrogen atom, Z is an intermediate group having n bond equivalents and n and m is an integer> 0

Here are Polynitrone with more than one attached via the carbon nitrone groups as C-bridged Polynitrone referred to and Polynitrone with more than one attached via the nitrogen atom nitrone group as N-bridged Polynitrone.

Z is preferably a polyfunctional aliphatic, cycloaliphatic, aromatic, substituted or unsubstituted intermediate group which may also contain heteroatoms and / or may be a polymer.

Preferred intermediate groups Z are derived from the following structures:
Mononuclear or polynuclear aromatic, cycloaliphatic groups, or alkyl chains:
The groups may be arbitrarily substituted and preferably have at least one hydroxyl, imide, ester, amide, ether, urea and / or urethane function. Particularly suitable are compounds which are derived from the following structures:

Z ₁ , Z ₂ , Y and X ₁ to X ₆ are preferably an aliphatic, cycloaliphatic, aromatic, substituted or unsubstituted group, which may also contain heteroatoms and / or may be a polymer. The substituents may also arbitrarily form a ring with each other. More preferably, X ₁ to X _{6 are} hydrogen, hydroxy, methyl, amide or ester, Z _{2 is} aromatic, and Z _{1 is} carbonyl, sulfone, alkylene, arylene, polyamide, polyester, polyurethane, and the following Groups.

Y is an aliphatic, cycloaliphatic, aromatic, substituted or unsubstituted group, which may also contain heteroatoms and / or may be a polymer. Y is particularly preferably an alkylene group, polyether, polyester, polyurethane and / or polyamide.

Particularly preferred intermediate groups Z have the following structures:

According to a particularly preferred embodiment of the invention, one of the following units occurs at least once in the polynitrone:

In another embodiment, the terminal substituents of the nitrone are independently hydrogen, an aryl group (especially phenyl, naphthyl), a heteroaryl group (especially pyridinyl, furyl, thienyl, thiazolyl or benzothiazolyl), an alkyl group, a cycloalkyl group or combination thereof. According to a further particularly preferred embodiment, the terminal substituents on the N atom in the beta position contain a hydroxy group or in the gamma position a carbonyl group.

The polynitrone according to the invention are prepared by oxidation of secondary polyamines.

Preferred Polysekundäramine correspond to a general formula [Z (-NHX) n] m in which H is hydrogen, N is nitrogen and X is an optionally substituted group. Z is an optionally polyfunctional intermediate group having n bond equivalents and n and m is an integer> 0.

X and Z are preferably an aliphatic, cycloaliphatic, aromatic, substituted or unsubstituted group which may also contain heteroatoms and / or may be a polymer, and n and m are an integer greater than 0.

Polysekunderamines according to the invention are compounds whose molecules contain at least one secondary amine group, preferably 1 to 20 secondary amine groups, in particular 1 to 6 secondary amine groups. The polysecurity amines used according to the invention may contain aromatic, aliphatic and / or cycloaliphatic groups.

The synthesis of polysecine amine can be accomplished by numerous methods known to the organic chemist. Preferably, the poly-secondary amine is prepared by adding a monofunctional or polyfunctional amine to an epoxide or to a double bond.

The reaction of epoxides with amines to form Polysekundäraminen usually solvent-free and without catalyst at room temperature. An acceleration of the reaction can be carried out by elevated temperatures or catalysts such as transition metal-based Lewis acids.

The addition of an amine to a double bond is preferably carried out on activated double bonds, but can also with the aid of catalysts such. B. cobalt salts to non-activated double bonds. The addition of an amine to an activated double bond is referred to as Michael addition and as an activated double bond component, all known to the organic chemist monofunctional or polyfunctional Michael acceptors can be used. Preferred Michael acceptors are alpha, beta-unsaturated carbonyl compounds such as acrylates, methacrylates, crotonates, unsaturated aldehydes, ketones, esters, nitriles or carboxamides. The reaction can be catalyzed by, for example, water or basic catalysts such as piperidine, diethylamine or sodium alcoholate.

Without limiting the process according to the invention to this, the following starting compounds can be used for the synthesis of the polysekundary amines:
As amines: benzylamine, 2-picolylamine, 3-picolylamine, 4-picolylamine, o-, m-, p-xylylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, diaminoalkanes such as 1,6-diaminohexane, 1,5-diaminopentane or 1,4 Diaminobutane, phenylenediamines, toluenediamines, diaminodiphenylmethanes, methylenebis (cyclohexylamine), 4-aminophenylsulfone, isophoronediamine, 1,5-naphthylenediamine, melamine, benzoguanimine, 1,3,5-tris (aminomethyl) -cyclohexane, 1,3,5- Tris (aminomethyl) benzene, m- and p-tetramethylxylenediamine, polyethyleneimine, dicyandiamide, polymeric diphenylmethanediamine, polymeric methylenebis (cyclohexylamine), tetramethylbenzidine, o-, m- and p-diaminodiphenyl, lysine, 4- (4-aminophenoxy) benzamine , Benzidine, diphenylin, 4- (4-aminophenylthio) benzamine and / or 1,5-decahydronnaphthylenediamine.

According to a further, particularly preferred embodiment of the invention, the crosslinkers according to the invention are based on polymers having primary amine groups, for example polyvinylamines, polyamides, polyurethanes, urea melamine resins or modified copolymers of other origin which are then reacted, for example with Michael acceptors or epoxides, to form polysekundaryamines.

As Michael acceptors: acrylonitrile, acrylamide, 1-cyclohexene-1-carboxaldehyde, 2-cyclohexen-1-one, 2-butenal, 2-methyl-2-propenal, 2-propenal, 3-methyl-3-buten-2 -on, 3-buten-2-one, 1-penten-3-one, 3-penten-2-one, 1-hexen-3-one, 4-hexen-3-one, 1-hepten-4-one , Methyl methacrylate, ethyl crotonate, methyl crotonate, tert-butyl crotonate, ethylene diacrylate, hexamethylene diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, ethylene glycol diacrylate, glycerol-1,3-diglycerolate diacrylate, pentaerythritol diacrylate, bisphenol A ethoxylate diacrylate, bisphenol A glycerolate diacrylate, bisphenol A propoxylate diacrylate, bisphenol ethoxylate diacrylate, di (ethylene glycol) diacrylate, fluorescein O, O'-diacrylate, neopentyl glycol diacrylate, poly (propylene glycol) diacrylate, propylene glycol glycol diacrylate, tetra (ethylene glycol) diacrylate, tri (propylene glycol) diacrylate, tri (propylene glycol) glycerolatdiacrylat, Trimethylolpropanbenzoatdiacrylat, Neopentylglycolethoxylatdiacrylat, neopentyl glycol propoxylate diacrylate, Trimethylolpropanethoxylatmethyletherdiacrylat, 1.24 Tetradecandioldimethacrylat, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 4,4-Isopropylidendiphenoldimethacrylat, bisphenol A dimethacrylate, ethylene glycol dimethacrylate, glycerol dimethacrylate, poly (ethylene glycol) dimethacrylate, bisphenol A ethoxylate dimethacrylate, bisphenol A glycerolate dimethacrylate, di (ethylene glycol) dimethacrylate, fluorescein O, O'-dimethacrylate, neopentyl glycol dimethacrylate, poly (propylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, triethylene glycol dimethacrylate, unsaturated polyesters, glycidyl polyacrylate, 2,3-epoxypropyl acrylate, glycidyl methacrylate and / or quinones.

As epoxides: ethylene oxide, cyclohexene oxide, 1,3-butadiene diepoxide, bisphenol A and bisphenol F resins such as bisphenol A and bisphenol F-epichlorohydrin resins, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate , Triglycidylisocyanurat, methyl-substituted triglycidyl isocyanurate, aromatic and aliphatic glycidyl esters such. B. 1,23-propanetriol, butyl, allyl, isopropyl, butanediol, furfuryl, 2-biphenylyl, diethylene glycol, phenyl, bisphenol A and bisphenol F diglycidyl ethers, epoxidized fatty acid esters, 2, 3-epoxypropyl acrylate, glycidyl methacrylate, polyglycidyl methacrylate, polyglycidyl acrylate, glycidyl novolaks, tetrabromobisphenol A-containing diglycidyl ethers, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, epoxidized rubber, epoxidized fatty acids and oils and / or epoxidized alkenes.

• (i) molekularem Sauerstoff (in Verbindung mit einem geeigneten Katalysator),
• (ii) Persäuren, besonders bevorzugt meta-Chlorperbenzoesäure,
• (iii) Dimethyldioxiran, besonders bevorzugt durch Reaktion von Aceton mit Oxone hergestellt,
• (iv) Kaliumpermanganat,
• (v) Wasserstoffperoxid, auch in Form von komplexeren Systemen wie Nitril-Wasserstoffperoxid-Systemen oder Harnstoff-Wasserstoffperoxid-Addukten, in Verbindung mit einem geeigneten Katalysator wie Selendioxid oder Natriumwolframat
• (vi) Alkylhydroperoxide wie z. B. Cumolhydroperoxid oder tert-Butylhydroperoxid in der Gegenwart eines geeigneten Katalysators, besonders bevorzugt Titanisopropoxid,
• (vii) und weitere geeignete Oxidationsmittel.

The oxidizing agent is, for example, preferably selected from

• (i) molecular oxygen (in conjunction with a suitable catalyst),
• (ii) peracids, more preferably meta-chloroperbenzoic acid,
• (iii) dimethyldioxirane, more preferably prepared by reaction of acetone with oxone,
• (iv) potassium permanganate,
• (v) hydrogen peroxide, even in the form of more complex systems such as nitrile-hydrogen peroxide systems or urea-hydrogen peroxide adducts, in conjunction with a suitable catalyst such as selenium dioxide or sodium tungstate
• (vi) alkyl hydroperoxides such as. B. cumene hydroperoxide or tert-butyl hydroperoxide in the presence of a suitable catalyst, more preferably titanium isopropoxide,
• (vii) and other suitable oxidizing agents.

The above-mentioned polynitrone are used for crosslinking unsaturated polymers. The term "unsaturated polymer" is usually understood as meaning a polymer having one or more unsaturated carbon-carbon bonds in the polymer chain.

The degree of unsaturated carbon-carbon bonds can be increased by DIN53241 determined and expressed by the unit "meq / g". Usually, the unsaturated polymers have 0.1 to 50, preferably 1 to 20 meq / g.

The unsaturated polymers are preferably selected from alkyd resin, acrylic ester-styrene-acrylonitrile copolymer, acrylonitrile-butadiene-acrylate copolymer, acrylonitrile-butadiene-styrene copolymer, polyethylene-styrene copolymer, acrylonitrile-methyl methacrylate copolymer, butadiene rubber, butyl rubber , Casein plastic, artificial horn, cellulose acetate, cellulose hydrate, cellulose nitrate, chloroprene rubber, chitin, chitosan, cyclo-olefin copolymer, epoxy resin, ethylene-propylene copolymer, ethylene-propylene-diene rubber, ethylene-vinyl acetate, fluororubber, liquid crystal polymers , Urea-formaldehyde resin, isoprene rubber, lignin, melamine-formaldehyde resin, natural rubber, melamine-phenol-formaldehyde resin, methyl acrylate-butadiene-styrene copolymer, phenol-formaldehyde resin, perfluoroalkoxyalkane, polyacetal, polyacrylate, polyacrylonitrile, polyamide, polyalkylene glycol, polybenzimidazole, polybutylene succinate , Polycaprolactone, polycarbonate, polychlorotrifluoroethylene, polyester, polyesteramide, polyesteracryla t, polyether block amide, polyetherimide, polyether ketone, polyethersulfone, polyethylene, polyethylene terephthalate, polyurea, polyhydroxyalkanoate, polyhydroxybutyrate, polyimide, polyisobutylene, polyisocyanate, polyketone, polylactide, polymethacrylmethylimide, polymethylene terephthalate, polymethacrylate, polymethylpentene, polyolefin, polyoxymethylene, polysaccharide, polyphenylene ether, Polyphenylene sulfide, polyphthalamide, polypropylene, polypropylene oxide, polypyrrole, polysiloxane, polystyrene, polysulfone, polytetrafluoroethylene, polyurethane, polyurethane acrylate, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinylidene fluoride, polyvinylpyrrolidone, silicone rubber, styrene-acrylonitrile copolymer, styrene-butadiene Rubber, starch, vinyl chloride-ethylene copolymer, vinyl chloride-ethylene-methacrylate copolymer, unsaturated polyester, polymer-bound para-toluenesulfonic acid, polymer-bound para-toluenesulfonic acid amide, polyurethane acrylate, propargyl methacrylate Acrylate copolymers, cellulose, gelatin or combinations thereof, as far as these polymers have or are modified with C-C double and / or C-C triple bonds.

Particular preference is given to using unsaturated polyesters, unsaturated polyester urethanes and / or polyester urethane acrylates or polyester urethane methacrylates, as used, for example, in US Pat US 6,284,321 B1 are described.

In the context of the invention it is particularly preferred to crosslink unsaturated polyesters. Suitable unsaturated polyesters are in general polycondensation products of α, β-ethylenically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid, mesaconic acid and citraconic acid, with polyalcohols, such as ethylene glycol, diethylene glycol, polyethylene glycol, propane, butane, butene, butyne and hexanediols, trimethylolpropane and pentaerythritol, which may still residues of saturated carboxylic acids, eg. For example, succinic acid, glutaric acid, adipic acid, phthalic acid, tetrachlorophthalic acid, further monofunctional alcohols such as butanol, tetrahydrofuyl alcohol and ethylene glycol monobutyl ether, and monobasic acids such as benzoic acid, oleic acid, linseed oil fatty acid and ricinene fatty acid may contain.

Suitable monomeric unsaturated compounds which can be copolymerized with the unsaturated polyesters are, for example, vinyl compounds such as styrene, vinyltoluene and divinylbenzene, furthermore vinyl esters such as vinyl acetate, then unsaturated carboxylic acids and their derivatives such as methacrylic acid, esters and nitriles, furthermore, allyl esters such as allyl acetate, allyl acrylate, diallyl phthalate, triallyl phosphate and triallyl cyanurate.

In particular, unsaturated polyesters containing maleate and fumarate groups are used.

The unsaturated polymers usually have a weight-average molecular weight of from 200 to 500,000 g / mol, preferably from 1,000 to 200,000 g / mol, especially from 10,000 to 100,000 g / mol.

• (a) ein Polynitron, wobei die endständigen Substituenten am N-Atom des Polynitrons in beta-Position eine Hydroxygruppe oder in gamma-Position eine Carbonylgruppe enthalten,
• (b) ein ungesättigtes Polymer oder eine Mischung an Polymeren, wobei mindestens ein Polymer ungesättigte Funktionen enthält bzw. funktionelle Gruppen aufweist, die mit dem N-verbrückten Polynitron reagieren können,
• (c) gegebenenfalls Füllstoffe,
• (d) gegebenenfalls Pigmente.
• (e) gegebenenfalls Zusatzstoffe, z. B. Weichmacher, Stabilisatoren und/oder Photoinitiatoren, und
• (f) gegebenenfalls weitere Vernetzer wie Polyisocyanate, Bisdiene und/oder Polyoxaziridine.

The use according to the invention of the polynitrone described above can be carried out within the scope of a curable composition. This can include:

• (a) a polynitrone, wherein the terminal substituents on the N atom of the polynitrone contain a hydroxy group in the beta position or a carbonyl group in the gamma position,
• (b) an unsaturated polymer or a mixture of polymers, wherein at least one polymer contains unsaturated functions or has functional groups that can react with the N-bridged polynitrone,
• (c) optionally fillers,
• (d) optionally pigments.
• (e) optionally additives, e.g. As plasticizers, stabilizers and / or photoinitiators, and
• (f) optionally further crosslinkers such as polyisocyanates, bisdienes and / or polyoxaziridines.

In principle, two preferred embodiments of the curable composition according to the invention are possible.

In a first embodiment, the curable composition of the invention is a 2-component system. This means that components (a) and (b) are in the form of two compounds. Thus, components (a) and (b) are separate compounds that are not covalently linked prior to curing.

In principle, for this first embodiment of the curable composition according to the invention, the explanations of the above-mentioned preferred polynitrons apply. However, it is preferred that Polynitrone be used according to the general formula I, wherein none of the substituents of the nitrone group is bound to a polymer, in particular not to an unsaturated polymer.

Also for this first embodiment, the explanations of the above-mentioned preferred unsaturated polymers application.

In this first embodiment of the curable composition of the invention, the polynitrone (a) is in an amount of from 0.1 to 50% by weight, more preferably from 1 to 20% by weight, especially from 5 to 15% by weight, based on the total weight of the composition.

In a second embodiment of the curable composition of the invention, the curable composition is a 1-component system. This means that components (a) and (b) are in the form of an unsaturated polymer terminated with more than one nitrone group. Thus, components (a) and (b) are united within one compound.

In principle, for this second embodiment of the curable composition according to the invention, the explanations of the above-mentioned preferred polynitrons apply. However, it is necessary to use polyniters which are present as polymers and have CC double and / or triple C bonds in the molecule.

For both embodiments, in the curable composition, the ratio of nitrone groups (from component a) and unsaturated carbon-carbon bonds (from component b) can be 10: 1 to 1:10, preferably 5: 1 to 1: 5, especially 2: 1 to 1: 2.

In addition to components (a) and (b), the curable composition of the invention may optionally comprise components (c) fillers and (d) pigments. Further, the composition may further comprise one or more additives such as plasticizers, stabilizers and / or photoinitiators. Finally, the curable composition may further comprise (f) other crosslinkers.

The components (a) and (b) are contained in the composition of the present invention usually in an amount of from 30 to 100% by weight, preferably from 40 to 99% by weight, more preferably from 55 to 99% by weight, based on the total weight of the composition.

As fillers (c) are in principle all inorganic and organic fillers into consideration, as for example in Rompp Lexikon coatings and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Fillers", pages 250-252 , to be discribed.

Examples of suitable fillers are wood flour, organic or organometallic polymers, inorganic minerals, salts or ceramic materials or organically modified ceramic materials or mixtures of these substances. Inorganic materials are preferably used. These may be natural and synthetic minerals. Examples of suitable minerals are silicon dioxide, aluminum silicates, calcium silicates, magnesium silicates, calcium aluminum silicates, magnesium aluminum silicates, calcium magnesium silicates, beryllium aluminum silicates, aluminum phosphate or calcium phosphate, or mixtures thereof.

In the composition of the invention, fillers (c) are generally present in an amount of from 0 to 50% by weight, preferably from 5 to 40% by weight, more preferably from 10 to 30% by weight, based on the total weight of the composition , contain.

The composition according to the invention may further comprise as component (d) optionally at least one colorant, preferably a pigment. The colorant may be a pigment or a dye. As pigments, for example, colored pigments or effect pigments can be used.

As effect pigments, it is possible to use metal flake pigments, such as commercial aluminum bronzes, chromatized aluminum bronzes, commercially available high-grade steel bronzes and non-metallic effect pigments, for example pearlescent or interference pigments. In addition, it will open Römpp Lexikon Lacke and printing inks, Georg Thieme Verlag, 1998, pages 176, effect pigments and pages 380 and 381 Metal oxide-mica pigments to metal pigments, referenced.

Examples of suitable inorganic color pigments are titanium dioxide, iron oxides, and carbon black, in particular carbon black. Examples of suitable organic coloring pigments are thioindigo pigments, indanthrene blue, cromophthal red, irgazine orange and heliogen green, copper phthalocyanine. In addition, it will open Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag, 1998, pages 180 and 181, iron blue pigments to iron oxide black, pages 451 to 453 pigments to pigment volume concentration, page 563 thioindigo pigments and page 567 titanium dioxide pigments directed.

In the composition according to the invention, coloring agents, preferably pigments (d), are generally present in an amount of from 0 to 30% by weight, preferably from 1 to 20% by weight, more preferably from 2 to 10% by weight, based on Total weight of the composition, included.

In addition, the composition of the invention may contain at least one additive (s). Examples of suitable additives are additional oligomers and polymeric binders, catalysts, radical scavengers, thermolabile free-radical initiators, free-radical or cationic photoinitiators, polymerization inhibitors, discharge agents, primers, reactive diluents, flow aids, flow control agents, abrasion and scratch resistance improvers, anti-settling agents, anti-flooding agents, anti-caking additives, anti-caking agents. Blocking additives, antiflocculants, deflocculants, antigelling agents, anticratering agents, anticaking agents, anti-mottling additives, antioxidants, antipopping additives, antifoaming agents, emulsifiers, defoamers, antiscrubbers, scratch resistance, anti-silking additives, antislip agents, antistatic agents, reinforcing additives, bactericides, fungicides, Antifouling agents, accelerators, chelating additives, chemical resistance improvers, decontaminating agents, dispersing and milling aids, emulsifiers, degassing agents, deaerators, moisture binders, film formers, flame retardants, flow and leveling agents, formaldehyde reducers, free-flow additives, gloss improvers, lubricity improvers, lubricants, lubricants, Surfactants, Adhesion Promoters, Hardeners, Skin Preventants, Heat Resistant Additives, Water Repellents, Water Repellents, Catalysts, Coalescing Aids, Coupling Reagents, Anti-Corrosive Additives, Cond additive additives, solvent resistance, solubilizers, air entraining agents, matting agents, wetting aids, surface improvers, pH control, abrasion resistance improvers, impact modifiers, silver particles, slip additives, barrier additives, special effect additives, stabilizers, release agents, release additives, release agents, dryers, drying agents, UV absorbers, light stabilizers, thickeners , Rheology additives, thinners, viscosity reducers, waxes, water retention improvers, plasticizers and / or weathering additives.

In the composition according to the invention, additives (e) are generally present in an amount of from 0 to 20% by weight, preferably from 0.1 to 10% by weight, more preferably from 1 to 5% by weight, based on the total weight of the composition.

It is preferred in one embodiment that the curable composition of the invention contains no catalysts that catalyze the crosslinking of the unsaturated carbon-carbon bonds in component (b). In an alternative embodiment, the curable composition of the invention may contain one or more photoinitiators.

An example of a suitable photoinitiator is Irgacure ^®.

Photoinitiators can be used in an amount of from 0 to 5% by weight, preferably from 0.01 to 3% by weight, more preferably from 0.4 to 2.0% by weight, based on the total weight of the composition.

The composition according to the invention may also contain as component (e), if appropriate, at least one further crosslinker. The crosslinker may be, for example, a polyisocyanate, a polyoxaziridine, a polyepoxide, a polyol, a polyphenol, a polyamine or an acid anhydride.

Examples of suitable crosslinkers are triglycidyl isocyanurate, diglycidyl terephthalate, triglycidyl trimellitate, glycidyl methacrylate, caprolactam blocked isophorone diisocyanate derivatives, divinylbenzene, isophorone diisocyanate uretdiones, toluenediisocyanate derivatives, meta- and para-tetramethylxylene diisocyanates, methylenedianiline, 1,3,5-tris (isocyanatomethyl) cyclohexane, 1,3,5-tris (isocyanatomethyl) benzene, dicyandiamide derivatives, methylol phenols, trimellitic anhydride, pyromellitic dianhydride, melamine, benzoguanimine, glycoluryl, tris (alkoxycarbonylamino) triazine, N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide and N, N, N ', N'-tetrakis (2-hydroxypopyl) adipamide.

In the composition of the invention, additional crosslinker (s) are generally present in an amount of from 0 to 30 weight percent, preferably from 1 to 20 weight percent, more preferably from 2 to 10 weight percent, based on the total weight of the composition Composition, included.

The curable composition of the invention is preferably used as a coating, thin or thick film, adhesive, rubber, filler, sprayable thick film filling, insulating, sealing, packaging material, laminating, storage, casting resin, ink, paint, printing ink, fiber, foil, electrical Dipping paint, radiation-curing paint, alkyd resin, powder paint, water-based paint or solvent-based paint. The invention therefore also provides a coating, a film, an adhesive, a rubber, a putty, a sprayable thick-layer filling, a laminating, storage or casting resin, an insulating, sealing or packaging material, an ink, a paint, an ink, a fiber, a foil, an electrical dip, a radiation-curing lacquer, an alkyd resin, a powder lacquer, a water lacquer and a solvent-containing lacquer comprising the composition according to the invention. The composition according to the invention is preferably in the form of a lacquer, in particular as a powder lacquer. The curable composition of the present invention may be processed by curing (ie, by crosslinking) into a crosslinked product. The curing (ie the crosslinking) is carried out by suitable temperature control of the curable composition such as. B. by means of electric heating, IR, UV or MW oven.

• (i) Bereitstellen einer erfindungsgemäßen härtbaren Zusammensetzung und
• (ii) Härten der Zusammensetzung bei Temperaturen von 20 bis 220°C, bevorzugt von 50 bis 150°C, insbesondere 60 bis 120°C.

The invention therefore also provides a process for the preparation of a crosslinking product comprising the steps

• (I) providing a curable composition of the invention and
• (Ii) curing of the composition at temperatures of 20 to 220 ° C, preferably from 50 to 150 ° C, in particular 60 to 120 ° C.

The invention likewise provides a crosslinking product obtainable by the process according to the invention.

The curing / crosslinking can be carried out by mixing and tempering the components of the curable composition. The unsaturated polymer (b) and the polynitrone (a) (or alternatively, an unsaturated polynitron-terminated polymer as a 1-component system) may be ground to a powder, for example, in a conventional mill (optionally together with components (c) - (f)) be mixed. Another possibility of mixing is by means of a solvent system in which both the unsaturated polymer and the polynitrone (optionally together with components (c) - (f)) are dissolved or dispersed. The ingredients are first converted to a uniform mixture, and after removal of the solvent, cure / crosslinking is performed by heating to the desired temperature.

In the process of the present invention, the curing time is usually 10 seconds to 2 hours, preferably 20 seconds to 60 minutes, more preferably 30 seconds to 15 minutes, more preferably 1 minute to 10 minutes.

The crosslinking products according to the invention are usually dependent on the type of unsaturated polymer used. It is preferably elastic soft to hard crosslinking products. These are preferably inert to water and organic solvents.

The crosslinking products of the invention are versatile. Examples include automotive tires, fiber reinforced plastics, membranes, tubing, dental materials, appliances, kitchen tops, general construction, structural components, bathtubs, hard hats, sinks, medical devices such as implants, adhesive tapes, adhesives, panels such as boat hulls, fiberglass reinforced polyester parts, and household items. The crosslinking products according to the invention are preferably used as a lacquer layer.

In addition to the use according to the invention, the curable composition according to the invention and the crosslinking product according to the invention, the preferably suitable polynitrone as such are also an object of the invention, in particular polynitrone prepared from Michael acceptors, epoxides and / or aliphatic, cycloaliphatic or aromatic amines having a functionality on primary amine groups of 1 and higher, preferably from 1 to 20 and especially from 1 to 6.

The invention therefore also relates to polynitrone as exemplified in Table 1. One skilled in the art will recognize the relationship between the general structure (I) and the more individual structures of the entries, where Y and Z are as defined above. The radicals R ¹ , R ² and R ³ may generally be hydrogen, deuterium, an aliphatic, cycloaliphatic or aromatic radical or a polymer chain. More preferably, R ¹ and R ^{2 are} independently hydrogen, an aryl group (especially phenyl, naphthyl), a heteroaryl group (especially pyridinyl, furyl, thienyl, thiazolyl or benzothiazolyl) or an alkyl group (such as methyl). R ³ particularly preferably contains a carbonyl group in the beta position of a hydroxy group or in the gamma position.

Preferred intermediate groups Z are derived as described above from any substituted, mononuclear or polynuclear aromatic, cycloaliphatic groups, or alkyl chains. Z particularly preferably contains one or more selected groups from, carbonyl, sulfone, alkylene, arylene and the following groups.

Table 1 Exemplary Polynitrone of the Structure (I)

In summary, it should be noted that can be cured at low temperatures by the inventive use of polynitrons unsaturated polymers. This results in mechanistically stable polymer networks, usually neither harmful metal catalysts are used nor environmentally harmful cleavage products are formed. The crosslinking is fast and provides thermally and mechanistically stable products. It is advantageous that Polynitrone are available inexpensively from Polysekundäraminen in various modifications. The polysekundernamines can be prepared, for example, in situ from primary amines and Michael acceptors or epoxides. All synthetic steps are efficient and cost-effective at room temperature under mild conditions on a commercial scale feasible. It is advantageous that the starting compounds such as amines, Michael acceptors and epoxides are available inexpensively in countless variants and thus result in almost unlimited variation of the polynitron structure.

The crosslinking products according to the invention are characterized by their extremely versatile usability at a relatively low cost in the production. They are easy to handle, can be used alone or optionally together with smaller amounts of other polymers and can be processed with a large number of fillers.

• 1 Entwicklung neuer Klebstoffe (z. B. Schmelzklebstoffe, Acrylatklebstoffe);
• 2 Verwendung als Laminier-, Kleb-, Lager-, Gieß- und Lackharz;
• 3 Im Möbelsektor: Durch schnelle Aushärtung und praktisch 100% Festkörper ist der Auftrag von sehr dicken Schichten in einem Arbeitsgang möglich;
• 4 Herstellung von schnell härtenden und gut schleifbaren Spachtelmassen (Autoreparatur, holz- und metallverarbeitende Industrie);
• 5 Herstellung von spritzfähigen Dickschichtfüllern (Autoreparatur, Holz- und metallverarbeitende Industrie);
• 6 Produktion von glasfaserverstärkten Polyesterteilen (GFK-Polyester) z. B. im Schiffsbau;
• 7 Entwicklung neuer Wasserlacke, Pulverlacke und Lösemittellacke;
• 8 Entwicklung selbsthärtender Pulverlacken (Nitronterminierte ungesättigte Polymere);
• 9 Entwicklung von Isolier-, Dichtungs-, und Verpackungsmaterial;
• 10 Verwendung für Imprägnierungen;
• 11 Verwendung zur Herstellung großer Platten wie Bootsrümpfe;
• 12 Entwicklung neuer Fasern und Folien sowie von Gewebe;
• 13 Verwendung für Armaturen und Schutzhelme;
• 14 Entwicklung neuer Medizinprodukte wie z. B. Implantate;
• 15 Verwendung für Haushaltsgegenstände und in der Elektrotechnik;
• 16 Entwicklung neuer Druckfarben und Tinten, insbesondere Inkjet-Tinten;
• 17 Verwendung bei photokationischen Polymerisationen, z. B. in der Lithografie.

The crosslinking method according to the invention provides new possibilities for the development of new materials according to an environmentally friendly variant. The combination of an unsaturated polymer and polynitrons can be exploited to develop new products in the following areas:

• 1 development of new adhesives (eg hot-melt adhesives, acrylate adhesives);
• 2 Use as laminating, adhesive, storage, casting and lacquer resin;
• 3 In the furniture sector: Fast curing and virtually 100% solids enable the application of very thick layers in one operation;
• 4 production of fast-hardening and easily sandable fillers (car repair, woodworking and metalworking industry);
• 5 production of sprayable thick-film fillers (car repair, woodworking and metalworking industry);
• 6 Production of glass fiber reinforced polyester parts (GRP polyester) z. In shipbuilding;
• 7 development of new water-based paints, powder coatings and solvent-based paints;
• 8 development of self-curing powder coatings (nitron-terminated unsaturated polymers);
• 9 Development of insulating, sealing and packaging materials;
• 10 Use for impregnations;
• 11 Use for making large panels, such as boat hulls;
• 12 development of new fibers and films as well as fabrics;
• 13 Use for fittings and protective helmets;
• 14 Development of new medical devices such as B. implants;
• 15 Use for household articles and in electrical engineering;
• 16 development of new inks and inks, in particular inkjet inks;
• 17 Use in photocationic polymerizations, eg. B. in lithography.

Examples:

All example compounds were clearly characterized by NMR and IR spectroscopy.

Example 1: Synthesis of N-benzylidene-aspartic acid diethyl ester N-oxide (PN-1)

Alternative 1: In a 50 mL one-necked flask, 1.7 g (10 mmol) of diethyl fumarate and 1.2 g (11 mmol) of benzylamine are stirred in 10 mL of methanol and 2 mL of water. After 48 hours, 0.1 g (1.0 mmol) of selenium dioxide is added. The reaction mixture is cooled with the aid of an ice / water mixture to 0 ° C and then 3.4 g (30 mmol) of 30% strength hydrogen peroxide solution are added dropwise with stirring. After four hours of reaction, the solution is extracted with 20 ml of dichloromethane and then washed with 20 ml of saturated sodium chloride solution. The organic phase is separated from the aqueous, dried and the solvent removed under reduced pressure. For further purification, the crude product is separated by column chromatography (ethyl acetate: hexane = 1: 1).

Alternative 2: In a 50 mL one-necked flask, 1.7 g (10 mmol) diethyl fumarate and 1.2 g (11 mmol) benzylamine are stirred in 10 mL methanol and 2 mL water. After 48 hours, the solvent is removed under reduced pressure and the residue is dissolved in 30 ml of toluene and mixed with 284 mg (10 mol%, 1 mmol) of titanium tetraisopropoxide. Subsequently, 7.61 g (40 mmol) of an 80% cumyl hydroperoxide solution are added and the reaction mixture is heated for 5 hours at 60 ° C oil bath temperature. After the reaction, the solvent is removed under reduced pressure and the crude product is purified by column chromatography (ethyl acetate: hexane = 1: 1).

Example 2: Synthesis of N-benzylidene-β-methyl-β-alanine methyl ester N-oxide (PN-2)

In a 50 mL one-necked flask, 1.0 g (10 mmol) of methyl crotonate and 1.2 g (11 mmol) of benzylamine are stirred in 10 mL of methanol and 2 mL of water. After 48 hours, 0.1 g (1.0 mmol) of selenium dioxide is added. The reaction mixture is cooled with an ice / water mixture to 0 ° C and then 3.4 g (30 mmol) of a 30% strength hydrogen peroxide solution are added dropwise with stirring. After four hours of reaction, the solution is extracted with 20 ml of dichloromethane and then washed with 20 ml of saturated sodium chloride solution. The organic phase is separated from the aqueous, dried and the solvent removed under reduced pressure. Furthermore, the crude product is separated by column chromatography (ethyl acetate: hexane = 1: 1).

Example 3: Synthesis of N, N'-dibenzylidene-β, β-dimethyl-β, β'-dialaninehexane-1,6-ester-N, N'-dioxide (PN-3)

7.3 g (60 mmol) of hexanediol and 10 g of sodium carbonate are placed in a flask and then 12.9 g (120 mmol) of crotonic chloride in chloroform are slowly added dropwise. After stirring for 24 hours, the solid is removed by filtration and 12.85 g (120 mmol) of benzylamine are added to the filtrate. For a further 24 hours the solution is stirred at room temperature and the solvent removed under reduced pressure. The residue is dissolved in ethanol, treated with 0.67 g (6.00 mmol) of selenium dioxide, cooled to 0 ° C and then slowly added dropwise 40.8 g (360 mmol) of hydrogen peroxide (30% in water). After four hours of reaction, the solution is extracted with dichloromethane and then washed with saturated sodium chloride solution. The organic phase is separated from the aqueous, dried and dried under reduced pressure. Example 4: Synthesis of N, N'-dibenzylidene-diamine-dihydroxycyclohexylmethylcyclohexanecarboxylate-N, N'-dioxide (PN-4)

4.25 g (39.6 mmol) of benzylamine and 5.00 g (19.8 mmol) of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Uvacure 1500) are stirred at 50 ° C. in a 50 ml single-necked flask. After about 72 hours, 40 mL of methanol and 0.2 g (2.0 mmol) of selenium dioxide are added. The reaction mixture is cooled with the aid of an ice / water mixture to 0 ° C and then 13.5 g (120 mmol) of 30% strength hydrogen peroxide solution are added dropwise with stirring. After four hours of reaction, the solution is extracted with 20 ml of dichloromethane and the product is precipitated in ether and washed with plenty of ether.

Example 5 Synthesis of Uracross P3125 Polynitrone (PN-5)

Alternative 1: 5.0 g of Uracross P3125 and 1.1 g (10 mmol) of benzylamine are stirred in a mixture of THF and water. After two to three days, the solution is concentrated under reduced pressure, the remaining solvent is decanted off and acetone and 0.1 g (1.0 mmol) of selenium dioxide are added. Then, while cooling in an ice bath, 5.7 g (50 mmol) of hydrogen peroxide (30% strength in water) are slowly added dropwise. The solution is stirred overnight in an ice bath and then acetone is removed under reduced pressure and water is added. The precipitated white solid is washed several times with water and dried under high vacuum.

Alternative 2: 5.0 g of Uracross P3125 and 1.1 g (10 mmol) of benzylamine are stirred in a mixture of THF and water. After two to three days, the solution is concentrated under reduced pressure, the remaining solvent is decanted off and the residue is dissolved in 30 ml of toluene and mixed with molecular sieve and 284 mg (10 mol%, 1 mmol) of titanium tetraisopropoxide. Subsequently, 7.61 g (40 mmol) of an 80% cumyl hydroperoxide solution are added and the reaction mixture is heated for 5 hours at 60 ° C oil bath temperature. After the reaction, the solvent is removed under reduced pressure and the crude product is washed with hexane.

Example 6 Crosslinking of the unsaturated polyester Uracross P3125 with PN-5

50% by weight Polynitron PN-5 are heated at 120 ° C. for 30-120 minutes with 50% by weight Uracross P3125. Uracross P3125 is a commercial product of DSM and has unsaturated maleate or fumarate units. By storage for one hour in an oven at 120 ° C, a cross-linked solvent-resistant composition has been formed.

The cross-linking can be recognized by a change in the glass transition temperature of Uracross P3125, which is measured by differential scanning calorimetry (DSC) on a Mettler Toledo DSC822 in a temperature range of -50 ° C to 220 ° C at a heating rate of 10 ° C / min was investigated. The glass transition temperatures were reported as averages from the second and third heat-up, respectively, indicating the temperature at which half of the heat capacity change was achieved. For calibration, tin, indium and zinc standards were used. Uncrosslinked Uracross P3125 has a glass transition temperature of 52 ° C, which increases to 61 ° C by cross-linking.

It was also confirmed by IR spectroscopy that no more unsaturated double bonds are present after crosslinking.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2009/074310 A1 [0007, 0007]
• US 6284321 B1 [0046]

Cited non-patent literature

• Judith Pietschmann, Industrial Powder Coating, 3rd Edition 2010, JOT reference book (H. Mitsui, S.-i. Zenki, T. Shiota, S. Murahashi, Journal of the Chemical Society, Chemical Communications 1984, 874-875) [0008 ]
• DIN53241 [0044]
• Georg Thieme Verlag, Stuttgart, New York, 1998, "Fillers", pages 250 to 252 [0062]
• Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 176, effect pigments and pages 380 and 381 [0066]
• Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 180 and 181, iron blue pigments to iron oxide black, pages 451 to 453 pigments to pigment volume concentration, page 563 thioindigo pigments and page 567 titanium dioxide pigments [0067]

Claims (18)

Process for the preparation of polynitrons by oxidation of secondary polyamines. A method according to claim 1, characterized in that the terminal substituents on the N-atom of the polynitrone in beta position contain a hydroxy group or in the gamma position a carbonyl group. A method according to claim 1 or 2, characterized in that the Polynitrone be used for crosslinking or modification of unsaturated polymers, in particular with polymers which have C-C double bonds, C-C triple bonds and / or heterocumulenes, in particular isocyanate groups. Method according to one of claims 1 to 3, characterized in that the polynitrone is a compound according to the general formula I. [Z (-X) n] m (I), in which X is a preferably substituted nitron group, Z is a preferably polyfunctional aliphatic, cycloaliphatic, aromatic, substituted or unsubstituted intermediate group, which may also contain heteroatoms and / or may be a polymer and n and m is an integer> 0. Method according to one of claims 1 to 4, characterized in that the nitrone groups are bridged on the N side via a polymer. Process according to one of Claims 1 to 4, characterized in that the nitrone groups are bridged on the C-side via a polymer. Method according to one of claims 1 to 6, characterized in that the secondary polyamines are prepared by addition reaction of a primary amine to a suitable component, preferably an unsaturated compound, more preferably an activated unsaturated compound. A method according to claim 7, characterized in that the suitable component is selected from epoxides and / or Michael acceptors. A method according to claim 8, characterized in that the Michael acceptors are selected from carbonyl compounds, nitrile compounds and / or carboxylic acid amide compounds, preferably from acrylates, methacrylates, crotonates or unsaturated polyesters. Method according to one of claims 7 to 9, characterized in that the primary amine is selected from aliphatic, cycloaliphatic and / or aromatic amines having a functionality of primary amine group of 1 and higher, preferably from 1 to 20 and particularly preferably from 1 to 6. Polynitrone, wherein preferably the terminal substituents on the N-atom of the polynitrone in the beta position contain a hydroxy group or in the gamma position a carbonyl group, prepared according to a method according to any one of claims 1 to 10. A curable composition comprising (a) a polynitrone, wherein the terminal substituents on the N atom of the polynitrone contain a hydroxy group in the beta position or a carbonyl group in the gamma position, (b) an unsaturated polymer or a mixture of polymers, wherein at least one polymer contains unsaturated functions or has functional groups that can react with the polynitrone, (c) optionally fillers, (d) optionally pigments, (e) optionally additives, preferably plasticizers, stabilizers and / or photoinitiators and (f) optionally further crosslinkers, preferably polyisocyanates, bisdienes and / or polyoxaziridines. Composition according to Claim 12, characterized in that it is a 2-component system in which components (a) and (b) are in the form of two different compounds. Composition according to Claim 12, characterized in that it is a 1-component system, components (a) and (b) being in the form of a polynitron-terminated unsaturated polymer. Use of one of the compositions according to one of Claims 12 to 14 as a coating, thin or thick film, adhesive, rubber, fiber, foil, filler, sprayable thick-layer filling, insulating, sealing, packaging material, ink, paint, electrical dip coating, radiation-curing lacquer, Alkyd resin, powder coating, water-based paint, solvent-based paint, laminating, storage or casting resin and in lithography. A method of making a crosslinked product comprising the steps (a) providing a curable composition according to any one of claims 12 to 14, (B) curing of the composition at temperatures of 20 to 220 ° C, preferably from 50 to 150 ° C, particularly preferably from 60 to 120 ° C. A crosslinking product obtainable by a process according to claim 16. Use of a crosslinking product according to claim 17 for the production of motor vehicle tires, fiber composite plastics, membranes, tubes, dental materials, household appliances, kitchen tops, bathtubs, sinks, structural components, panels such as boat hulls, medical devices such as implants, protective helmets and glass fiber reinforced polyester parts.