WO2011085793A2

WO2011085793A2 - Polyoxaziridines and use thereof as a cross-linking agent, especially in coating materials and adhesives

Info

Publication number: WO2011085793A2
Application number: PCT/EP2010/007847
Authority: WO
Inventors: Marcus Dickmeis; Hakan Cinar; Helmut Ritter
Original assignee: Marcus Dickmeis; Hakan Cinar; Helmut Ritter
Priority date: 2009-12-21
Filing date: 2010-12-21
Publication date: 2011-07-21
Also published as: EP2516532A2; DE102009060105A1; WO2011085793A3

Abstract

The invention relates to polyoxaziridines, to the use thereof for cross-linking unsaturated polymers, and to a hardenable composition comprising (a) a polyoxaziridine, (b) an unsaturated polymer or a mixture of polymers, at least one polymer containing unsaturated functions or functional groups that can react with the polyoxaziridine, (c) optionally fillers, (d) optionally pigments, (e) optionally additives e.g. plasticisers, stabilisers, or photoinitiators, and (f) optionally other cross-linking agents such as polyisocyanates, bisdienes, and polynitrones. The invention also relates to the use thereof as an adhesive, a rubber, a filling material, a sprayable thick layer filling, a film, ink, paint, a powder coating, water-based paint, radiation-hardening paint or solvent-based paint. The invention further relates to cross-linking products that can be obtained by hardening the hardenable composition according to the invention.

Description

Polyoxaziridines and their use as crosslinking agents, in particular in

Coating materials and adhesives

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. For this purpose, polyfunctional oxaziridines are proposed. 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.

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 particularly high. The curing of powder coatings is usually carried out by reaction of an epoxide with an acid, an acid anhydride, an amine, a phenol or a Lewis base or by addition of an isocyanate to an alcohol. Most commercially available crosslinkers therefore 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 free-radical polymerization (e.g., styrene) requires initiators and mostly noxious heavy metal catalysts. In addition, it only has practical significance 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 by which thermosetting paints are structured and modified, e.g. with pigments, fillers or solid additives, only limited use. 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 preparation of stable molding compounds, fillers, their use in paints, coatings and adhesives. This crosslinking reaction occurs at low temperature by cycloaddition between polynitrone and unsaturated polymer. The stable, electron-rich nitrones add up at high speed preferably to electron-poor systems such as unsaturated polyesters. Compared to electron-rich double bonds or triple bonds, such as in isoprene rubber, propargyl methacrylate, unsaturated fatty acids or acrylates, they have only a low reactivity. Therefore, the use of polynitrons is limited to the use of unsaturated polymers with electron-poor double bonds. Additional information on the reactivity of nitrones can be found in R. Huisgen, H. Seidl, I. Brüning, Chemische Berichte, 1969, 102, 102-1016.

Another disadvantage of Polynitrone is that it is crystalline and refractory solids that are difficult to homogenize during the curing process. They are not stable in the liquid state and decompose at temperatures above the melting point. As a result of poor solubility, Polynitrone can only be used in limited amounts in the paint. Therefore, they are added to achieve additional effects complementary to an existing hardening process. WO 2009/074310 A1 describes, for example, the use of polynitrons as a matting agent.

The art of cycloaddition of monofunctional oxaziridines to unsaturated low molecular weight compounds such as alkynes, alkenes and heterocumulenes is known in the art. The cycloaddition of oxaziridines to unsaturated polymers is unknown in the art, especially the cycloaddition of polyoxaziridines to unsaturated polymers.

The object of this invention was to find new crosslinkers, which have the positive properties of Polynitrone, without their disadvantages such. B. have high melting points or decomposition during melting.

The invention thus relates to the use of polyoxaziridines for crosslinking unsaturated polymers. Another object of the invention are curable compositions comprising

(a) a polyoxaziridine,

(b) an unsaturated polymer or a mixture of polymers, wherein at least one polymer contains unsaturated functions or has functional groups which can react with the polyoxaziridine,

(c) optionally fillers and

(d) optionally pigments

(e) optionally additives such. As plasticizers, stabilizers or photoinitiators

(f) optionally further crosslinkers such as polyisocyanates, bisdienes, polynitrone. Oxaziridines are usually compounds with the structural element

wherein the radicals R, 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, polyoxaziridines are used. For the purposes of the invention, these are understood to mean compounds whose molecules contain more than one, preferably 2 to 20 and in particular 3 to 6, oxaziridine rings. The preparation of monofunctional oxaziridines is known to the person skilled in the art and has been transferred to polyoxaziridines in the context of this invention. Starting compounds are polyimines, which are oxidized under mild conditions to Polyoxaziridinen. Polyimines in turn can be by reaction of polyfunctional aldehydes or ketones with monofunctional primary amines or polyfunctional primary amines with monofunctional aldehydes or ketones obtained. For the purposes of the invention, polyoxaziridines of polyfunctional amines are preferred. These compounds are called N-linked polyoxaziridines because of their structure. In a further embodiment, polyoxaziridines of polyfunctional aldehydes or ketones are preferred. These compounds are called C-linked polyoxaziridines because of their structure.

In a further embodiment, polyoxaziridines of polyfunctional amines and polyfunctional aldehydes or ketones are preferred.

It is advantageous that primary amines and carbonyl compounds in countless variants are commercially available and thus result in almost unlimited variation of the Polyoxaziridin structures.

The polyoxaziridines 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, but is not limited to, phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene and biphenyl radicals. 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. 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 group is an aromatic group comprising an aromatic group (C ₆ H ₃ ), condensed 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, keto 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 a C6 aromatic radical comprising a nitro group wherein the nitro group is 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-CC Ph-), 4- (3-bromoprop-1-yl) phen-1-yl (ie, 4-BrCH ₂ CH ₂ CH ₂ Ph-) and the like. Other examples of aromatic radicals include

4-allyloxyphen-1-oxy, 4-aminophen-1-yl (ie, 4-H ₂ NPh-),

3-aminocarbonylphen-1-yl (ie, NH ₂ COPh-), dicyanomethylidenebis (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 (eg methylsalicyl), 2-nitromethylphen-1-yl (ie, 2-N0 ₂ CH ₂ Ph),

3-trimethylsilylphen-1-yl, 4-tert-butyldimethylsilylphenyl-1-yl, 4-vinylphen-1-yl, vinylidene bis (phenyl) and the like. 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 -) represents an aromatic C radical. The polyoxaziridines according to the invention may also contain cycloaliphatic radicals. As used herein, the term "cycloaliphatic radical" (or "cycloaliphatic radical") refers to a radical having a valence of at least 1 and comprising a series of atoms that is cyclic but not aromatic. For example, a cyclohexylmethyl group (C6H-11CH2-) is a cycloaliphatic radical that has a cyclohexyl ring (the .alpha A 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 may be solely carbon and hydrogen For the sake of simplicity, the term "cycloaliphatic radical" is defined herein broadly as a wide range of functional groups t, such as alkyl, alkenyl, alkynyl, haloalkyl, conjugated dienyl, alcohol, ether, aldehyde, ketone, carboxylic, acyl (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 C6 radical comprising a methyl group, wherein the methyl group is a functional group which is an alkyl group. Similarly, the 2-nitrocyclobut-1-yl radical is a cycloaliphatic C4 radical comprising a nitro group, the nitro group being a functional group. A cycloaliphatic radical may comprise one or more halogen atoms, which may be the same or different. Close halogen atoms, z. For example, fluorine, chlorine, bromine and iodine. Cycloaliphatic radicals having one or more halogen atoms include 2-trifluoromethylcyclohex-1-yl,

4-bromodifluoromethylcyclooct-1-yl, 2-chlorodifluoromethylcyclohex-1-yl, 2-chloromethylcyclohex-1-yl, hexafluoroisopropylidene-2,2-bis (cyclohex-4-yl) (ie, -C ₆ HioC (CF 3) 2 C ₆ Hio), 3-difluoromethylenecyclohex-1-yl,

4-bromodichloromethylcyclohex-1-ylthio, 4-trichloromethylcyclohexyl-1-ylxy, 2-bromopropylcyclohex-1-yloxy (eg CH ₃ CHBrCH ₂ C6HioO-), 2-bromoethylcyclopent-1-yl and the like. Further examples of cycloaliphatic radicals include 4-allyloxycyclohex-1-yl, 4-aminocyclohex-1-yl (ie, H ₂ NC 6Hi ₀ -), 4-aminocarbonylcyclopent-1-yl (ie, NH ₂ COC ₅ H ₈ -), 4 -Acetyloxycyclohex-1-yl, 2,2-dicyanisopropylidenebis (cyclohex-4-yloxy) (ie, -OC6HioC (CN) 2C6HioO-), 3-methylcyclohex-1-yl, methylenebis (cyclohex-4-yloxy) (ie, -OC ₆ H ₁₀ CH ₂ C ₆ HioO-),

1-ethylcyclobut-1-yl, cyclopropylethenyl, 3-formyl-2-tetrahydrofuranyl,

2-hexyl-5-tetrahydrofuranyl, hexamethylene-1, 6-bis (cyclohex-4-yloxy) (ie, -OC ₆ Hio (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 C6Hio), 4-methylthiocyclohex-1-yl (ie, 4-CH ₃ SC ₆ Hio), 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 Hio),

2-tert-butyldimethylsilylcyclopent-1-yl, 3-trimethylsilylcyclohex-1-yl, 4-trimethoxysilylethylcyclohex-1-yl (e.g., (CHaO ^ SiCh ChkCeH-), 4-vinylcyclohexen-1-yl, vinylidene bis (cyclohexyl) and the like The term "a cycloaliphatic C 3 -doester includes cycloaliphatic radicals containing at least three but not more than 10. The cycloaliphatic radical 2-tetrahydrofuranyl (C ₄ H ₇ O-) represents a cycloaliphatic C ₄ The cyclohexylmethyl radical (C6H11CH2-) represents a cycloaliphatic C ₇ radical.

The polyoxaziridines according to the invention may also contain aliphatic radicals. As used herein, the term "aliphatic radical" (or "aliphatic radical") refers to an organic radical having a valency of at least 1 consisting of a linear or branched array of atoms that is not cyclic The array of atoms comprising the aliphatic radical 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 herein defined as including as part of the "linear or branched arrangement of atoms which is not cyclic" 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 (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 a C6 aliphatic 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 Cj residue comprising a nitro group wherein the nitro group is 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. For example, 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-butyl Butyldimethylsilyl, 3-trimethyloxysilylpropyl (ie, (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ -), vinyl, vinylidene and the like. As another example, an aliphatic C 1 -C 10 radical contains at least one but not more than 10 carbon atoms. A methyl group (ie, CH ₃ -) is an example of an aliphatic Ci residue. A decyl group (ie, _CH3 (CH2) 9-) is an example of an aliphatic Cio residue.

Preferred polyoxaziridines correspond to a general formula

[X-Z (-X) n] m

in which X is an optionally substituted oxaziridine ring, Z is an intermediate group with n-1 bonding equivalents and n and m is an integer> 0.

X is preferably an especially substituted via the nitrogen atom attached oxaziridine ring, Z is a 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 greater than or equal to 1.

In another embodiment, X represents an oxaziridine ring attached in particular via the carbon atom. The oxaziridine ring attached via the carbon atom may optionally additionally be attached via the nitrogen atom.

The individual oxaziridine groups can be present as Z-isomer or as E-isomer.

Preferred intermediate groups Z are derived from the following structures:

Mononuclear or polynuclear aromatic, cycloaliphatic groups, or alkyl chains, which may be substituted as desired. Particularly suitable are the following compounds or combinations of the following compounds, which may be linked together as desired, in particular via an ester, amide, ether, urea or urethane function:

V is particularly preferably a group selected from methine, nitrogen, phosphorus, phosphine oxide.

W is a natural number greater than or equal to zero, preferably six.



X ¹ is preferably an aliphatic, cycloaliphatic, aromatic, substituted or unsubstituted group which may also contain heteroatoms and / or may be a polymer. Particularly preferably, X ^{1 is} a group selected from Methylene, oxygen, sulfur, carbonyl, sulfone, tertiary amine, alkylene, arylene and the following groups. X ² is preferably an aliphatic, cycloaliphatic, aromatic, substituted or unsubstituted intermediate group, which may also contain heteroatoms and / or may be a polymer. X ² is particularly preferably a linear or branched alkyl chain, in particular hexyl or butyl.

Particularly preferred intermediate groups Z have the following structure:

According to a particularly preferred embodiment of the invention, the substituent attached to the N atom of the oxaziridine is a branched alkyl group (especially tert-butyl, ferf-octyl, isopropyl or adamantyl), a cycloalkyl group (especially cyclohexyl), a carbonyl group

(In particular benzoyl) or a sulfonyl group (especially benzenesulfonyl, para-toluenesulfonyl, methylsulfonyl, ethylsulfonyl). The substituents on the C atom of the oxaziridine are particularly preferably independently of one another hydrogen, an alkyl group, an aryl group (especially phenyl, naphthyl), a heteroaryl group (in particular pyridinyl, furyl, thiazolyl or benzothiazolyl), a cycloalkyl group or a combination thereof. According to a further embodiment, the substituents of the oxaziridine ring particularly preferably form a ring in turn.

The polyoxaziridines according to the invention are preferably prepared by oxidation of a polyimine. The present invention thus further relates to a process for the preparation of polyoxaziridines by oxidation of a polyimine.

The polyimine can be prepared by reaction of an aldehyde or a ketone with an amine, wherein at least one component has a plurality of functional groups. In contrast to the condensation of an amine with an aldehyde, the reaction of an amine with a ketone often requires a Bronsted or Lewis acid catalyst (eg, titanium tetrachloride). Without limiting the method according to the invention to this, it is possible to do so use the following starting compounds for the synthesis of the polyimines:

As aldehydes: formaldehyde, vaniline, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, oenantal, ethyl-2-hexanal, cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, hexahydrobenzaldehyde, benzaldehyde, o-, m-, p-anisaldehyde, salicylaldehyde, p-tolualdehyde, o-, m-, p-aminoaldehyde, o-, m-p-dimethylaminobenzaldehyde monochlorobenzaldehyde, o-, m-, p-nitrobenzaldehyde, beta-methoxypropionaldehyde, beta-ethyloxypropionaldehyde, malondialdehyde, glyoxal, glycolaldehyde, glyceraldehyde, malonic, succinic, glutaric acid -, adipic aldehydes, 1, 10-di (4-formylphenoxy) decane, 1, 4-di (4-formylphenoxy) butane, 1, 6-di (4-formylphenoxy) hexane, 1, 10-di (4- formyl benzoate) decane, 1,4-di (4-formylbenzoate) butane, 10-di (4-formylbenzoate) hexane,

Bis (4-formylphenyl) succinate, bis (4-formylphenyl) glutarate, bis (4-formylphenyl) heptanedioate, bis (4-formylphenyl) adipate, bis (4-formylphenyl) nonadioate, bis (4-formylphenyl) decanedioate, N ¹ , N ¹⁰ -Bis (4-formylphenyl) decanediamide, citronellal, N ¹ , N ⁹ -Bis (4-formylphenyl) nonadiamide, N ¹ , N ⁷ -Bis (4-formylphenyl) heptanediamide, N ¹ , N ⁶ -Bis ( 4-formylphenyl) adipamide, N ¹ , N -Bis (4-formylphenyl) succinamide, terephthalic aldehyde, phthalaldehyde, isophthalaldehyde, acrolein, crotonaldehyde, isoquistaldehyde, tris (4-formylphenyl) amine, citral, tris (4-formylphenyl) methane , 4- (4-Formylphenoxy) benzaldehyde, indole-3-carbaldehyde, 4- (4-formylphenylthio) benzaldehyde, 2,4-dimethoxybenzaldehyde, 4-methoxynaphthalene-1-carbaldehyde, etc ...

As ketones: acetone, butanone-2, pentanone-2, pentanone-3, methyl isopropyl ketone, diisopropyl ketone, benzyl methyl ketone, ethyl methyl ketone, 3-oxohexanoic acid, methyl isobutyl ketone, methylcyclohexyl ketone, acetophenone, benzophenone, cyclobutanone, cyclopentanone, cyclohexanone, methyl-2-cyclohexanone, methyl 3-cyclohexanone, methyl 4-cyclohexanone, dimethyl 2,4-cyclohexanone, methyl 4-cyclohexanone, dimethyl 2,4-cyclohexanone, trimethyl 3,3,5-cyclohexanone, cycloheptanone, cyclooctanone, cyclodecanone, cyclododecanone , Cyclohexanediketone-1, 4, isophorone, 9-fluorenone, p-benzoquinone, o-benzoquinone, toluquinone, fumigatin, phtocol, alizarin, Jungion, Rhine, 1, 4, 1, 2, and 2,6-naphthoquinone, 9,10-anthraquinone, 9,10-phenanthrene quinone, menthone, carvone, camphor, etc ...

As amines: methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, amylamines, cyclohexylamine, n-dodecylamn, monoethanolamine, methoxy-2-ethylamine, beta-aminopropionitrile, beta-aminopropionamide, aniline, o -, m-, pToluidin, chloro and dichloroanilines, chloro- and dichlorotoluidines, bromoaniline, fluoroaniline, nitro and dinitroanilines, nitro and Dinitrotoluidine, o-, m- and p-anisidines, o-, m-, p-amino aldehyde , Trifluoromethylaniline, antra nilic acid, sulphanilic acid,

3- (N, N-Dimethylamino) propanamine, alpha-naphthylamine, beta-naphthylamine, 9-aminoanthracene, aminopyridines, ethylenediamine, diethylenetriamine, triethylenetetraamine, diaminoalkanes such as diaminocyclohexanes, 1,2-propylenediamine, 1,3-propanediamine, 1,6 Diaminohexane, 1,8-diaminooctane, 1,5-diaminopentane or 1,4-diaminobutane, diamino-pyridine,

1, 5-diamino-2-methylpentane, 2,2-dimethyl-1,3-propanediamine, phenylenediamines, toluenediamines, diaminodiphenylmethanes, methylenebis (cyclohexylamine),

4-aminophenylsulfone, isophoronediamine, diamino-naphthalenes, 1,5-decahydronaphthylenediamine, 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),

3,3'-Dimethyl-4,4'-diamino-dicyclohexylmethane, tetramethylbenzidine, o-, m- and p-diaminodiphenyl, epsilon-aminoundecanoic acid, benzidine, diphenylin, lysine, epsilon-aminododecanoic acid, 4- (4-sulfonamidophenoxy) benzoic acid sulfonamide , 2-phenylethanamine, 4- (4-aminophenoxy) benzamine, 4- (4-aminophenylthio) benzamine, para-toluenesulfonic acid sulfonamide, benzoic acid sulfonamide, 4- (4-aminophenoxy) benzamine, benzidine,

3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 1, 8-diamino-p-menthane, diamino-anthraquinones, diamino-benzenesulfonic acids, 1, 5-diamino-anthraquinone, diphenylethylenediamine, etc ...

According to a further, particularly preferred embodiment of the invention The crosslinkers according to the invention are based on polymers having aldehyde groups, ketone groups or primary amine groups, for example polyvinylamines, polyamides, polyesters, polyacrylates, polyurethanes, urea-melamine resins or modified copolymers of other origin, which are then converted to the polyoxaziridines.

The oxidizing agent is, for example, preferably selected from

(i) molecular oxygen (in conjunction with a suitable catalyst),

(ii) peracids, more preferably mefa-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

(vi) alkyl hydroperoxides such as e.g. Cumene hydroperoxide or fe / t-butyl hydroperoxide in the presence of a suitable catalyst, more preferably titanium isopropoxide

(vii) And Other Suitable Oxidizing Agents The above-mentioned polyoxaziridines are used for crosslinking unsaturated polymers. The term "unsaturated polymer" is usually understood to mean a polymer having one or more unsaturated carbon-carbon bonds in the polymer chain Alternatively, crosslinking via heterocumulene groups, such as, for example, isocyanate groups, is possible.

The degree of unsaturated carbon-carbon bonds can be determined by DIN53241 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, melamine-phenol-formaldehyde resin, methyl acrylate-butadiene-styrene copolymer, natural rubber, phenol-formaldehyde resin, perfluoroalkoxyalkane, polyacetal, polyacrylate, polyacrylonitrile, polyamide, polyalkylene glycol, polybenzimidazole, polybutylene succinate, polycaprolactone, polycarbonate, polychlorotrifluoroethylene, polyester, polyesteramide, Polyester acrylate, polyether block amide, polyethermide, 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, polyvinylet polyvinylidene fluoride, polyvinylpyrrolidone, silicone rubber,

Styrene-acrylonitrile copolymer, styrene-butadiene rubber, starch, unsaturated polyester, vinyl chloride-ethylene copolymer, cellulose, gelatin, vinyl chloride-ethylene-methacrylate copolymer, polymer-bound para-toluenesulfonic acid, polymer-bound para-toluenesulfonic acid amide, polyurethane acrylate, propargyl methacrylate acrylate -Copolymers, or

Combinations thereof, insofar as these polymers have or are modified with C-C double and / or C-C triple bonds.

Polyolefins, alkyd resins, butadiene rubber, linseed oil, isoprene rubber, butadiene-styrene copolymers, chloroprene rubber, ethylene-propylene-diene rubber, are particularly preferably used. Styrene-butadiene rubber, unsaturated polyesters, unsaturated polyester urethanes and / or polyester urethane acrylates or polyester urethane methacrylates, as described, for example, in US Pat. No. 6,284,321 B1.

In the context of the invention it is particularly preferred to crosslink unsaturated polyesters.

Suitable unsaturated polyesters are generally polycondensation products of .alpha.,. Beta.-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 nitrile, and also 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 200 to 500,000 g / mol, preferably from 1 .000 to 200,000 g / mol, especially from 10,000 to 100,000 g / mol. The use according to the invention of the polyoxaziridines described above can be carried out as part of a curable composition. This can include:

(a) a polyoxaziridine,

(c) optionally fillers and

(d) optionally pigments

(e) optionally additives such. As plasticizers, stabilizers or photoinitiators

(f) optionally further crosslinkers such as polyisocyanates, bisdienes, polynitrone. 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, the explanations of the abovementioned preferred polyoxaziridines apply to this first embodiment of the curable composition according to the invention. However, it is preferred that polyoxaziridines according to the general formula I are used, wherein none of the substituents of the oxaziridine ring is bonded 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 present invention, the polyoxaziridine (a) is in an amount of 0.1 to 50% by weight, more preferably 1 to 20% by weight, especially 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 component system. This means that components (a) and (b) are in the form of a polyoxaziridine-terminated unsaturated polymer. Thus, components (a) and (b) are united within one compound.

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

For both embodiments, in the curable composition, the ratio of oxaziridine groups (from component a) and unsaturated carbon-carbon bonds (from component b) may 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 free-radical or cationic 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. Suitable fillers (c) are in principle all inorganic and organic fillers, as described, for example, in Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Fillers", pages 250 to 252.

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, reference is made to Rompp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, 1998, pages 176, effect pigments and pages 380 and 381 metal oxide mica pigments to metal pigments. 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, reference is made to Rompp 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. 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, free-radical scavengers, free-radical initiators, free-radical or cationic photoinitiators, polymerization inhibitors, discharge agents, primers, reactive diluents, flow control agents, 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, accelerators, chelating additives, chemical resistance improvers, decontaminants, dispersing and grinding 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, surface-active agents, adhesion promoters, hardeners, skin-preventatives, heat-resistant additives, water repellents, water-repellents, Catalysts, coalescence aid, coupling reagent, corrosion inhibiting additives, conductivity increasing 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, desiccants , UV absorbers, light stabilizers, thickeners, rheology additives, thinners,

Viscosity reducers, waxes, water retention improvers, softeners and 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 catalysts.

Examples of suitable catalysts are Lewis acids, e.g. Copper triflate, titanium tetrachloride or scandium triflate. Catalysts can be used in an amount of from 0 to 20% by weight, preferably from 0.01 to 5% by weight, more preferably from 0.4 to 2.0% by weight, based on the total weight of the composition.

In a further 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 polynitrone, 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) benzene, 1,3,5-tris (isocyanatomethyl) cyclohexane, dicyandiamide derivatives, methylolphenols, trimellitic anhydride, pyromellitic dianhydride , Melamine, benzoguanimine, glycoluryl, N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide, N, N, N', N'-tetrakis (2-hydroxypopyl) adipamide, tris (alkoxycarbonylamino) triazine.

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, a printing ink, a fiber, a film, an electrical dip, a radiation-curing paint, an alkyd resin, a powder coating, a water-based paint and a solvent-containing paint comprising the inventive composition. 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 (i.e., by crosslinking) to form a crosslinked product. Curing (i.e., cross-linking) is accomplished by suitable tempering of the curable composition, such as by curing. B. by means of electric heating, IR, UV or MW oven.

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 may be carried out by mixing and optionally tempering the components of the curable composition. The unsaturated polymer (b) and the polyoxaziridine (a) (or alternatively, an unsaturated polyoxazirid-terminated polymer as a 1K 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 polyoxaziridines (optionally together with the components (c) - (f)) are dissolved or dispersed. The ingredients are first converted into a uniform mixture and after removal of the solvent curing / crosslinking is carried out by heating to the desired temperature.

In the process of the present invention, the curing time is usually 10 seconds to 24 hours, preferably 20 seconds to 10 hours, more preferably 30 seconds to 2 hours, more preferably 1 minute to 30 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 preferred polyoxaziridines as such are also an object of the invention, in particular polyoxaziridines prepared from polyesters, polyamides, and / or aliphatic, cycloaliphatic and / or aromatic amines, aldehydes or ketones Functionality on aldehyde, ketone and / or primary amine group, from 2 and higher, preferably from 2 to 20 and especially from 3 to 6.

The invention therefore also relates to polyoxaziridines as exemplified in Table I. One skilled in the art will recognize the relationship between the general structure (I) and the more individual structures of the entries, where V, w, X ¹ and X ^{2 are} as defined above. The radicals R, R ² and R ³ may generally be hydrogen, deuterium, an aliphatic, cycloaliphatic or aromatic radical or act to a polymer chain. R and R ² or R ² and R ³ or R ¹ and R ³ preferably form a ring. More preferably, R ¹ and R ^{2 are} independently hydrogen, an optionally substituted, linear, cyclic or branched aryl group (such as phenyl, naphthyl), a heteroaryl group (such as pyridinyl, furyl, thiazolyl or benzothiazolyl) or an alkyl group (such as methyl). R ³ is more preferably a branched alkyl group (especially ierf-butyl, terf-octyl, isopropyl or adamantyl), a cycloalkyl group (especially cyclohexyl), a carbonyl group

(In particular benzoyl) or a sulfonyl group (especially benzenesulfonyl, para-toluenesulfonyl, methylsulfonyl, ethylsulfonyl).

X ¹ particularly preferably contains one or more selected groups from methylene, oxygen, sulfur, carbonyl, sulfone, alkylene, arylene and the following groups, X ² particularly preferably being a linear or branched alkyl chain, in particular hexyl or butyl.

Table 1 Exemplary Polyoxaziridines of the Structure (I) 30

31

32

In summary, it should be noted that the inventive use of Polyoxaziridinen unsaturated polymers can be cured at low temperatures. This results in mechanistically stable polymer networks, usually neither harmful metal catalysts are used nor environmentally harmful cleavage products are formed. The networking is fast and provides thermal and Mechanistically stable products. It is advantageous that polyoxaziridines, in contrast to polynitrons, are not crystalline high-melting substances. They have a low melting point and are partially present at room temperature as a liquid. Moreover, because of their less polar structure, they are more soluble in paint compositions and in liquid form. Therefore, they can be distributed well in the binder during the curing process and also serve as reactive diluents. By reactive diluents the skilled person understands a diluent that becomes part of the binder in the curing process. Polyoxaziridines thus fulfill various tasks, such as those of a crosslinker and of a reactive diluent, and therefore have a wide range of applications. Furthermore, the glass transition temperature of the crosslinked polymer can be controlled almost arbitrarily by the structure of the polyoxaziridine. Polyoxaziridines are more electron-deficient than polynitrone and therefore more reactive to certain classes of substances.

The crosslinking products according to the invention are characterized by their extremely versatile substitution 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, since they have an excellent wetting ability. 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 polyoxaziridines can be exploited to develop new products in the following areas: 1 development of new adhesives (e.g., 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 make it possible to apply very thick layers in one operation possible;

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 (oxaziride-terminated unsaturated polymers);

9 Development of insulating, sealing and packaging materials;

10 Use for impregnations;

1 1 Use for the manufacture of large plates 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:

Example 1: Synthesis of 3,3'-diphenyl-2,2'-methylenebis (cyclohexyl) dioxaziridine (PO-1)

5.00 g (23.7 mmol) of 4,4'-methylene-bis (cyclohexylamine) and 5.3 g (50 mmol) of benzaldehyde are stirred in 30 mL of methanol for 24 hours at room temperature and the solvent is removed under reduced pressure.

Alternative 1: The residue is taken up in 50 ml of dichloromethane. Under Cooling in an ice bath, 13.1 g (55.0 mmol) meta-chloroperbenzoic acid (70 - 75%) are slowly added dropwise in 50 mL dichloromethane. The solution is stirred for two hours in an ice bath and then the resulting meta-chlorobenzoic acid is removed by filtration. The organic phase is washed twice with 50 ml of aqueous sodium sulfite solution (1 M), once with 50 ml of aqueous sodium bicarbonate solution (2M) and twice with 50 ml of water and then dried over magnesium sulfate. Magnesium sulfate is removed by filtration and the solvent removed under reduced pressure. The product can be purified by recrystallization in a suitable solvent mixture such as ethanol / water or dichloromethane / n-hexane.

Alternative 2: The residue is dissolved in a mixture of acetone and dichloromethane and admixed with 16.8 g (200 mmol) of aqueous sodium bicarbonate solution and 1.7 g (5.0 mmol) of tetrabutylammonium hydrogen sulfate. With vigorous stirring, a solution of 37 g (60 mmol) of oxone in water is then added. After one hour, the organic phase is separated off, the aqueous phase is extracted three times with 100 ml of dichloromethane and the combined organic phases are dried over magnesium sulfate. After concentration of the solvent, the product is precipitated in n-hexane and dried under high vacuum.

Example 2: Synthesis of

3,3 '- (3,3'-dipyridinyl) -2,2'-methylenebis (cyclohexyl) dioxaziridine (PO-2)

5.00 g (23.7 mmol) of 4,4'-methylenebis (cyclohexylamine) and 5.3 g (50 mmol) of 3-pyridinecarboxaldehyde are stirred for 24 hours in 30 ml of water at room temperature. The resulting solid is removed by filtration, 50 mL dichloromethane dissolved. While cooling in an ice bath, 13.1 g (55.0 mmol) of meta-chloroperbenzoic acid (70-75%) in 50 mL of dichloromethane become slow dropwise. The solution is stirred for two hours in an ice bath and then the resulting meta-chlorobenzoic acid is removed by filtration. The organic phase is washed twice with 50 ml of aqueous sodium sulfite solution (1 M), once with 50 ml of aqueous sodium bicarbonate solution (2M) and twice with 50 ml of water. It is then dried over magnesium sulfate and the salt is removed by filtration. After removal of the solvent under reduced pressure, the product remains as a solid.

Example 3: Synthesis of 3,3 '- (para-hexanediyldioxydiphenyl) -2,2'-di (terf-butyl) dioxaziridine (PO-3)

12.2 g (50 mmol) of 1,6-dibromohexane, 12.2 g (100.0 mmol) of para-hydroxybenzaldehyde and 6.60 g (100 mL) of potassium hydroxide (85%) are refluxed in 100 mL of dimethylformamide for thirty minutes heated. Then the solution is allowed to cool to room temperature and poured onto water / ice. The solid obtained is dissolved in 50 ml of ethanol and stirred for 24 hours with tert-butylamine 10.2 g (140 mmol) in the presence of 15 g of magnesium sulfate at room temperature. The solvent is removed under reduced pressure and the residue taken up in 70 mL dichloromethane. Magnesium sulfate is removed by filtration. 28.6 g (120 mmol) of meta-chloroperbenzoic acid (70-75%) in 70 ml of dichloromethane are slowly added dropwise to the organic phase while cooling in an ice bath. The solution is stirred for two hours in an ice bath and then the resulting meta-chlorobenzoic acid is removed by filtration. The organic phase is washed twice with 100 ml of aqueous sodium sulfite solution (1 M), once with 100 ml of aqueous sodium bicarbonate solution (2M) and twice with 100 ml of water. It is then dried over magnesium sulfate and the salt is then removed by filtration. After removal of the solvent under reduced pressure, the product remains as a highly viscous liquid back.

Example 4: Synthesis of

3,3 '- (para-hexanediyldicarboxydiphenyl) -2,2'-di (/ ^' soi) uiy /) dioxaziridine (PO-4)

12.2 g (50 mmol) of 1,6-dibromohexane, 15.1 g (100 mmol) of para-carboxybenzaldehyde and 6.60 g (100 mL) of potassium hydroxide (85%) are refluxed in 100 mL dimethylformamide for thirty minutes. Then the solution is allowed to cool to room temperature and poured onto water / ice. The resulting solid was dissolved in 50 mL of ethanol and stirred with 8.28 g (140 mmol) of isopropylamine for 24 hours in the presence of 15 g of magnesium sulfate at room temperature. The solvent is removed under reduced pressure and the residue taken up in 70 mL dichloromethane. Magnesium sulfate is removed by filtration. 28.6 g (120 mmol) of meta-chloroperbenzoic acid (70-75%) in 70 ml of dichloromethane are slowly added dropwise to the organic phase while cooling in an ice bath. The solution is stirred for two hours in an ice bath and then the resulting meta-chlorobenzoic acid is removed by filtration. The organic phase is washed twice with 100 ml of aqueous sodium sulfite solution (1 M), once with 100 ml of aqueous sodium bicarbonate solution (2M) and twice with 100 ml of water and then dried over magnesium sulfate. Magnesium sulfate is removed by filtration and the solvent removed under reduced pressure.

Example 5: Synthesis of

3,3 '- (para-hexanediyldicarboxydiphenyl) -2,2'-di (tert-butyl) dioxaziridine (PO-5)

12.2 g (50 mmol) of 1,6-dibromohexane, 15.1 g (100 mmol) of para-carboxybenzaldehyde and 6.60 g (100 mL) of potassium hydroxide (85%) are refluxed in 100 mL of dimethylformamide for thirty minutes. Then the solution is allowed to cool to room temperature and poured onto water / ice. The solid obtained is dissolved in 50 ml of ethanol for 24 hours and stirred with 10.2 g (140 mmol) of tert-butylamine in the presence of 15 g of magnesium sulfate at room temperature. The solvent is removed under reduced pressure and the residue taken up in 70 mL dichloromethane. Magnesium sulfate is removed by filtration. 28.6 g (120 mmol) of meta-chloroperbenzoic acid (70-75%) in 70 ml of dichloromethane are slowly added dropwise to the organic phase while cooling in an ice bath. The solution is stirred for two hours in an ice bath and then the resulting meta-chlorobenzoic acid is removed by filtration. The organic phase is washed twice with 100 ml of aqueous sodium sulfite solution (1 M), once with 100 ml of aqueous sodium bicarbonate solution (2M) and twice with 100 ml of water and then dried over magnesium sulfate. The solid is removed by filtration and the solvent removed under reduced pressure.

Example 6: Synthesis of

3,3 '- (para-hexanediyldicarboxydiphenyl) -2,2'-methylenebis (cyclohexyl) -polyoxaziridine (PO-6)

12.2 g (50.0 mmol) 1,6-dibromohexane, 15.1 g (100 mmol) Para-carboxybenzaldehyde and 6.60 g (100 mL) of potassium hydroxide (85%) are refluxed in 100 mL of dimethylformamide for thirty minutes. Then the solution is allowed to cool to room temperature and poured onto water / ice. The resulting solid is stirred for 24 hours with 10.5 g (50.0 mmol) of 4,4'-methylene-bis (cyclohexylamine) in 100 mL of ethanol at room temperature and then removed by filtration. The solid is dissolved in 70 mL of dichloromethane and while cooling in an ice bath, 28.6 g (120 mmol) of meta-chloroperbenzoic acid (70-75%) are slowly added dropwise in 70 mL dichloromethane. The solution is stirred for two hours in an ice bath and the resulting meta-chlorobenzoic acid is removed by filtration. The organic phase is washed twice with 100 mL aqueous sodium sulfite solution (1 M), once with 100 mL aqueous Natnumhydrogencarbonatlösung (2M) and twice with 100 mL of water. It is then dried over magnesium sulfate and the salt is removed by filtration. After removal of the solvent under reduced pressure, the product remains as a colorless solid.

Example 7: Synthesis of 3,3 '- (3,3'-dipyridinyl) -2,2' - (1, 8-menthane) dioxaziridine (PO-7)

5.77 g (23.7 mmol) of technical 1, 8-diaminomenthan (70%) and 5.3 g (50 mmol) of benzaldehyde are stirred in 30 mL of water for 24 hours at room temperature and then the aqueous phase is washed with dichloromethane , The organic phase is mixed with 13.1 g (55.0 mmol) of meta-chloroperbenzoic acid (70-75%) in 50 mL dichloromethane with cooling in an ice bath. The solution is stirred for two hours in an ice bath and then the resulting meta-chlorobenzoic acid is removed by filtration. The organic phase is washed twice with 50 ml of aqueous sodium sulfite solution (1 M), once with 50 ml of aqueous sodium bicarbonate solution (2M) and twice with 50 ml of water. Then dried over magnesium sulfate and the salt through Filtration removed. After removal of the solvent under reduced pressure, the product is obtained as a highly viscous liquid.

Example 8: Synthesis 3,3'-diphenyl-2,2 '- (1,4-cyclohexyl) dioxaziridine (PO-8)

2.71 g (23.7 mmol) of trans-1,4-diaminocyclohexane and 5.3 g (50 mmol) of benzaldehyde are stirred in 30 mL of methanol for 24 hours at room temperature. The resulting solid is removed by filtration and dissolved in 50 mL dichloromethane. While cooling in an ice bath, 13.1 g (55.0 mmol) of meta-chloroperbenzoic acid (70-75%) in 50 ml of dichloromethane are slowly added dropwise. The solution is stirred for two hours in an ice bath and then the resulting meta-chlorobenzoic acid is removed by filtration. The organic phase is washed twice with 50 ml of aqueous sodium sulfite solution (1 M), once with 50 ml of aqueous sodium bicarbonate solution (2M) and twice with 50 ml of water. Then it is dried over magnesium sulfate and the salt is removed by filtration. After removal of the solvent under reduced pressure, the product remains as a white solid.

Example 9 Crosslinking of the unsaturated polyester Uracross P3125 with polyoxaziridines

10 to 20% by weight of polyoxaziridine are heated at 120 ° C. for 30 to 120 minutes together with 80 to 90% by weight of Uracross P3 25 from DSM. The unsaturated polyester initially homogenized in the molten polyoxaziridine, resulting in a clear, low-viscosity mass. Further heating resulted in a crosslinked, solvent-resistant mass. Crosslinking was determined by DSC measurements (differential scanning calorimetry) on a Mettler Toledo DSC822 in a temperature range of -50 ° C to 220 ° C at a heating rate of 10 ° C / min examined (see Table 2). 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. It is clear from the examples that the glass transition temperature of a crosslinked unsaturated polymer can be controlled within a wide range by the structure of the polyoxaziridine used.

Table 2 Glass temperature of uncrosslinked Uracross P3125 and with

Polyoxaziridine Crosslinked Uracross P3125

Polymer glass transition temperature

Uncured Uracross P3125 52 ° C

Cross-linked with PO-1 Uracross 69 ° C

P3125

Cross-linked with PO-2 Uracross 69 ° C

P3125

Cross-linked with PO-3 Uracross 45 ° C

P3125

Cross-linked with PO-4 Uracross 54 ° C

P3125

Uracross 52 ° C crosslinked with PO-5

P3125

Uracross 61 ° C crosslinked with PO-6

P3125

Cross-linked with PO-7 Uracross 36 ° C

P3125 Uracross 64 ° C crosslinked with PO-8

P3125

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

Claims

claims

1. Use of polyoxaziridines for crosslinking unsaturated polymers.

2. Use according to claim 1, characterized in that polymers with C-C double bonds, C-C triple bonds and / or heterocumulenes, in particular isocyanate groups, are crosslinked.

3. Use according to claim 1 or 2, characterized in that the polyoxaziridine is a compound according to the general formula (I)

[XZ (-X) n] m (I), in which X is a preferably substituted oxaziridine ring, Z is a polyfunctional aliphatic, cycloaliphatic, aromatic, substituted or unsubstituted intermediate group, which may also contain heteroatoms and / or may be a polymer and n and m for an integer> 0.

4. Use according to one of claims 1 to 3, characterized in that the oxaziridine residues are bridged via a polymer.

5. Use according to one of claims 1 to 4, characterized in that the polymer has at least one unsaturated bond in the

Having polymer chain.

6. Use according to one of claims 1 to 5, characterized in that the polyoxaziridine is prepared from a polyimine.

7. A curable composition comprising

(a) a polyoxaziridine,

(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 Polynitrone.

8. The composition according to claim 7, characterized in that it is a 2-component system in which the components (a) and (b) are in the form of two different compounds.

9. A composition according to claim 7, characterized in that it is a 1-component system, wherein the components (a) and (b) are in the form of a polyoxaziridine-terminated unsaturated polymer.

10. Use of one of the compositions according to one of claims 7 to 9 as a coating, thin or thick film, adhesive, rubber, fiber, foil, filler, sprayable thick-film 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.

1 1. A method of making a crosslinked product comprising the steps

Providing a curable composition according to any one of claims 7 to 9,

- Hardening of the composition at temperatures of 20 to 220 ° C, preferably from 50 to 150 ° C, particularly preferably from 60 to 120 ° C.

12. Crosslinking product obtainable by a process according to claim 11.

13. Use of a crosslinking product according to claim 12 for the production of motor vehicle tires, fiber composite plastic, membranes, hose, dental materials, household appliances, kitchen tops, bathtubs, sinks, structural components, plates such as boat hulls, medical devices such as implants, protective helmets and glass fiber reinforced polyester parts.

Polyoxaziridines prepared from polyesters, polyamides, and / or aliphatic, cycloaliphatic and / or aromatic amines, aldehydes and / or ketones having a functionality on primary amine group, aldehyde group or ketone group of 2 and higher, preferably from 2 to 20 and particularly preferably from 3 to 6 ,

Process for the preparation of polyoxaziridines by oxidation of a polyimine.