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WO2012095425A1 - Polynitrones à base de polyamines secondaires, pour la réticulation et/ou la modification de polymères insaturés - Google Patents

Polynitrones à base de polyamines secondaires, pour la réticulation et/ou la modification de polymères insaturés Download PDF

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Publication number
WO2012095425A1
WO2012095425A1 PCT/EP2012/050313 EP2012050313W WO2012095425A1 WO 2012095425 A1 WO2012095425 A1 WO 2012095425A1 EP 2012050313 W EP2012050313 W EP 2012050313W WO 2012095425 A1 WO2012095425 A1 WO 2012095425A1
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unsaturated
polynitrone
group
groups
polymer
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Hakan Cinar
Helmut Ritter
Marcus Dickmeis
Oliver GOERZ
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen

Definitions

  • 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.
  • VOCs volatile organic solvents
  • solvent-based systems are increasingly substituted by environmentally friendly paints such as powder coatings.
  • 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 contain identical reactive ends, such as epoxies, amines, phenols or isocyanates.
  • unsaturated polyesters or acrylates are used.
  • Crosslinkers which cause crosslinking via unsaturated functions are scarcely known.
  • Curing by free-radical polymerization e.g., styrene
  • 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.
  • many techniques by which thermosetting paints are structured and modified, e.g. with pigments, fillers or solid additives only limited use.
  • the uniform hardening of three-dimensional edges is a problem.
  • 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 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 reacting a dialdehyde with / V-alkyl- or W-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.
  • 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.
  • poly-secondary amines obtained by addition of a primary amine to a suitable component with e.g. one or more double bonds or epoxide groups are prepared, can be oxidized in good yields to polynitrons.
  • 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.
  • compositions comprising
  • additives e.g. Plasticizers, stabilizers and / or photoinitiators as well
  • crosslinkers such as polyisocyanates, bisdienes and / or polyoxaziridines.
  • Nitrones are usually compounds with the structural element
  • 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.
  • monofunctional and polyfunctional polynitrons are used.
  • 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.
  • a suitable component preferably an unsaturated compound.
  • unsaturated compounds which are activated as a suitable component, such as, for example, alpha, beta unsaturated carbonyl, nitri or Carbonklareamidtheticen (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.
  • N-bridged polynitrone from polyfunctional amines is just as preferred as C-bridged polynitrone from polyfunctional Michael acceptors or epoxides.
  • 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.
  • 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 moiety may also include non-aromatic moieties.
  • a benzyl group is an aromatic group comprising a phenyl ring (the aromatic group) and a methylene group (the non-aromatic component)
  • a tetrahydronaphthyl group is an aromatic group comprising an aromatic group (C 6 H 3 ) Condensed to a Non-Aromatic Component - (CH 2) 4-
  • 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 such as esters and amides
  • nitro groups such as sulfonyl groups, sulfamyl groups, phosphinoyl group and the like.
  • 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 (i.e., 3-CCI 3 Ph-), 4- (3-bromoprop-1-yl) phen-1-yl (ie, 4-BrCH 2 CH 2 CH 2 Ph-), and the like.
  • Further examples of aromatic radicals include 4-allyloxyphen-1 -oxy, 4-aminophen-1-yl (ie, 4-H 2 NPh-),
  • an aromatic C 3 -C 0 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.
  • 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.
  • a cyclohexylmethyl group (CeHnCH) is a cycloaliphatic radical having 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 exclusively of carbon and hydrogen.
  • cycloaliphatic radical is defined herein as comprising a wide range of functional groups, 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.
  • functional groups 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
  • 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.
  • the 2-nitrocyclobut-1-yl radical is a C 4 cycloaliphatic radical comprising a nitro group, the nitro group is a functional Group is.
  • 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, hexafluoroisopropylidene-2,2-bis (cyclohex-4-yl) (ie C 6 H oC (CF 3) 2 C 6 H 1 o-)
  • 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 1 oC (CN) 2C 6 H 1 oO-),
  • a cycloaliphatic C 3 -C 0 radical includes cycloaliphatic radicals containing at least three but no more than 10 carbon atoms.
  • the cycloaliphatic radical 2-tetrahydrofuranyl (C 4 H 7 0-) represents a cycloaliphatic C 4 radical
  • the cyclohexylmethyl radical (C 6 HnCH 2 -) represents a cycloaliphatic C 7 radical.
  • the Poynitrone invention can also contain aliphatic radicals.
  • 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
  • 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 (e.g., carboxylic acid derivatives such as esters and amides), amine groups, nitro
  • 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.
  • 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. 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.
  • 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 (i.e., -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-butyldi
  • an aliphatic C 1 -C 0 radical contains at least one but not more than 10 carbon atoms.
  • a methyl group ie, CH 3 -
  • a decyl group ie, CH 3 (CH 2 ) 9 -
  • a C 10 aliphatic radical is an example of a C 10 aliphatic radical.
  • Preferred polynitrone correspond to a general formula
  • 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
  • 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 Xi 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.
  • X 1 to X 6 are hydrogen, a hydroxy group, a methyl group, an amide group or an ester group
  • Z 2 is an aromatic group
  • Z i is a group selected from 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:
  • one of the following units occurs at least once in the polynitrone:
  • the terminal substituents of the nitrone are independently of one another are hydrogen, an aryl group (in particular phenyl, naphthyl), a heteroaryl group (in particular pyridinyl, furyl, thienyl, thiazolyl or benzothiazolyl), an alkyl group, a cycloalkyl group or a combination thereof.
  • 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
  • H hydrogen
  • N nitrogen
  • 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.
  • Polyseismemikines 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.
  • polysecine amine can be accomplished by numerous methods known to the organic chemist.
  • 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.
  • the addition of an amine to an activated double bond is referred to as Michael addition and as activated double bond component all the organic chemists known monofunctional or polyfunctional ichael acceptors are 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • N, N, N ', N'-tetraglycidyl-4,4'diaminodiphenylmethane epoxidized rubber, epoxidized fatty acids and oils and / or epoxidized alkenes.
  • the oxidizing agent is, for example, preferably selected from
  • alkyl hydroperoxides such as e.g. Cumene hydroperoxide or tert-butyl hydroperoxide in the presence of a suitable catalyst, more preferably titanium isopropoxide,
  • 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 determined by DIN53241 and expressed by the unit “meq / g.”
  • 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,
  • Suitable unsaturated polyesters are generally polycondensation products of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid, esaconic acid and citraconic acid, with polyalcohols, such as ethylene glycol, diethylene glycol, polyethylene glycol, propane, butane, butene, butyric and hexanediols, trimethylolpropane and pentaerythritol, which may also contain residues of saturated carboxylic acids, for example succinic acid, glutaric acid, adipic acid, phthalic acid, tetrachlorophthalic acid, furthermore monofunctional alcohols, such as butanol, tetrahydrofuyo-alcohol and ethylene glycol monobutyl ether, as well as monobasic acids, such as benzoic acid,
  • 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.
  • vinyl compounds such as styrene, vinyltoluene and divinylbenzene
  • vinyl esters such as vinyl acetate
  • unsaturated carboxylic acids and their derivatives such as methacrylic acid, esters and nitrile
  • allyl esters such as allyl acetate, allyl acrylate, diallyl phthalate, triallyl phosphate and triallyl cyanurate.
  • 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.
  • additives e.g. Plasticizers, stabilizers and / or photoinitiators, and
  • crosslinkers such as polyisocyanates, bisdienes and / or polyoxaziridines.
  • 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.
  • the polynitrone (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.
  • the curable composition is a 1-component system.
  • components (a) and (b) are in the form of an unsaturated polymer terminated with more than one nitrone group.
  • components (a) and (b) are united within one compound.
  • the ratio of nitrone 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.
  • the curable composition of the invention may optionally comprise components (c) fillers and (d) pigments.
  • the composition may contain one or more additives such as, for example, plasticizers, Stabilizers and / or photoinitiators include.
  • 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 Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "Fillers", pages 250 to 252.
  • 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.
  • 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.
  • 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.
  • 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.
  • pigments for example, colored pigments or effect pigments can be used.
  • 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.
  • 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.
  • suitable inorganic color pigments are titanium dioxide, iron oxides, and carbon black, in particular carbon black.
  • suitable organic coloring pigments are Thioindigo pigments, Indanthrenblau, Cromophthalrot, Irgazinorange and Heliogengrun, copper phthalocyan.
  • Rompp Lexikon Lacke und Druckmaschine, 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.
  • 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.
  • composition of the invention may contain at least one additive (s).
  • 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, 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-
  • 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.
  • 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.
  • crosslinkers examples include 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, methylolphenols, trimellitic anhydride, pyromellitic dianhydride, melamine, benzoguanimine, glycoluryl, tris (alkoxycarbonylamino) triazine, N, N, N ', N'-tetrakis
  • 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 foil, an electric dip, a radiation-curable varnish, an alkyd resin, a powder coating, a water-based varnish and a solvent-containing varnish 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 by means of electrical heating, IR, UV or MW furnace.
  • the invention therefore also provides a process for the preparation of a crosslinking product comprising the steps
  • 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) 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.
  • 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.
  • 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 are Automotive tires, fiber composite plastics, membranes, tubing, dental materials, household appliances, kitchen tops, general construction industry, structural components, bathtubs, hard hats, sinks, medical devices such as implants, adhesive tapes, adhesives, panels such as boat hulls, glass fiber reinforced polyester parts, and household items.
  • the crosslinking products according to the invention are preferably used as a lacquer layer.
  • 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 I.
  • 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.
  • 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.
  • 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:
  • Uracross P3125 50% by weight of Polynitron PN-5 are heated at 120 ° C. for 30 to 120 minutes with 50% by weight of 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne des polynitrones produits par oxydation d'amines secondaires, et leur utilisation pour la réticulation de polymères insaturés, ainsi qu'une composition durcissable, comprenant (a) un polynitrone, basé sur l'addition d'une amine primaire à un composant approprié, avec oxydation subséquente; (b) un polymère insaturé ou un mélange à des polymères, au moins un polymère renfermant des fonctions insaturées, ou présentant des groupes fonctionnels susceptibles de réagir avec le polynitrone; (b) éventuellement des charges; (c) éventuellement des pigments; (d) éventuellement des produits d'addition, par exemple, des adoucissants, des stabilisants ou des photo-initiateurs; et (e) éventuellement, d'autres agents de réticulation,tels que polyisocyanate, bisdiène, polyoxaziridine, et leur utilisation comme adhésif, gomme, mastic, couche de remplissage pulvérisable épaisse, encre, peinture, peinture en poudre, peinture à l'eau ou peinture au solvant. L'invention concerne en outre des produits de réticulation, obtenus par durcissement de la composition durcissable conforme à l'invention.
PCT/EP2012/050313 2011-01-12 2012-01-10 Polynitrones à base de polyamines secondaires, pour la réticulation et/ou la modification de polymères insaturés Ceased WO2012095425A1 (fr)

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DE201110008399 DE102011008399A1 (de) 2011-01-12 2011-01-12 Polynitrone auf der Basis von Polysekundäraminen zur Vernetzung und/oder Modifizierung von ungesättigten Polymeren

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FR3011551A1 (fr) * 2013-10-08 2015-04-10 Michelin & Cie Composition de caoutchouc pour bande de roulement comprenant une polynitrone
EP3145909B1 (fr) * 2014-05-23 2023-11-01 Compagnie Générale des Etablissements Michelin Compose 1,3-dipolaire portant une fonction ester d'acide carboxylique et composition de caoutchouc le contenant
CN119842304A (zh) * 2025-03-24 2025-04-18 湖北航聚科技股份有限公司 一种深海耐压壳体防护涂层及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3011551A1 (fr) * 2013-10-08 2015-04-10 Michelin & Cie Composition de caoutchouc pour bande de roulement comprenant une polynitrone
WO2015052131A1 (fr) * 2013-10-08 2015-04-16 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc pour bande de roulement comprenant une polynitrone
EP3145909B1 (fr) * 2014-05-23 2023-11-01 Compagnie Générale des Etablissements Michelin Compose 1,3-dipolaire portant une fonction ester d'acide carboxylique et composition de caoutchouc le contenant
CN119842304A (zh) * 2025-03-24 2025-04-18 湖北航聚科技股份有限公司 一种深海耐压壳体防护涂层及其制备方法

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