DD298937A5 - HYDROXYL, EPOXY AND SAEUREANHYDRIDE GROUPS CONTAINING COPOLYMERISATE, A PROCESS FOR THEIR PREPARATION AND THEIR USE AS A BINDER OR BINDER COMPONENT - Google Patents

Abstract

Copolymers which are made from olefinically unsaturated compounds, have a molecular weight in the range from 1,500 to 75,000 and simultaneously contain from 0.2 to 6.0% by weight of free hydroxyl groups, from 1 to 30% by weight of carboxylic anhydride groups and from 0.4 to 13% by weight of epoxide groups in chemically bonded form are prepared by copolymerising olefinically unsaturated compounds in the presence of olefinically unsaturated alcohols, olefinically unsaturated acid anhydrides and olefinically unsaturated epoxides and are used as binders in thermocurable coating compositions or sealants or as the binder component in room-temperature-curable two-component coating compositions or sealants.

Description

Dio present invention relates to novel copolymers, dio in addition to free hydroxyl, free epoxide and intramolekuljre Carboxylic anhydride group in chemically incorporated form, a method for producing dioser copolymers

and their use as a binder or binder component in single or two-component boilers or sealants.

The use of combinations of organic compounds with at least two intramolecular Carboxylic anhydride groups per molecule, especially of succinic anhydride copolymers! and Polyhydroxy compounds as binders for paints and coating compositions are already known. FR-A-2392092 describes boron-coating compositions consisting of hydroxyl-functional polymers uni. ' one Ester anhydride having at least two anhydride groups per molecule, wherein the Estoranhydrid an oligomer of Trimellitic anhydride. The disadvantage here is the very poor solubility of the anhydride in Lacküblichon Solvents, as well as the incompatibility with the hydroxyl-functional polymers. EP-A-48128 describes coating composition consisting of a hydroxyl component having at least two Hydroxyl groups per molecule, an anhydride component having at least two anhydride groups per molecule and

optionally an amine component acting as a catalyst. The catalytically active amino groups may already be present in the hydroxyl component. The described use of monomeron amino alcohols such. B.

Triethanolamine, as a pre-netting agent, acts as a dissolute substance on the fortlgon locko solvent foetlgkoit,

When a sufficiently long life has been reached, it must be possible, for a sufficiently long period of several hours, only for Koston olnor goiingon Vornotzungedichte orzlolt can be, with films orhalton wordon, the dioxin solutions are not soiitiolboetäncllg. Also boi prewonding of höhormolokuloron Polyolon, it is hardly possible oino for the practice sufficiently lango life dor systems to orziolone, which also zustoilig significant, that höhormolokularo Polyolo are often incompatible with the anhydrldgrupponholtigon Copolymorisaton.

Both boi room thermorigid härtondo and Einbronnbirulomittnl on dose of carboxyl groups and Epoxidgruppon

onthaltondon Bindomittolkompononten are already bokonnt.

Dio DE-OS 2635177 and DE-OS 2728459 boschroibon lösungsmlttolarmo Einbronnlacko bostohond from β) olnom

carboxyl group-containing acrylic resin, b) olnom epoxy resin with mindostons two epoxide group per molecule and c) olnom

Lösungsmittolgomisch. Dio EP-A-123738 and EP-A-150210 Buschroibon Boi Raumtomporotur Hardenable resin composition for Boschichtungon and Adhesives bostehund oinor Kompononto a) the carboxyl and torliäro Aminogruppori contains, and oinor component b) dio Epoxidgruppon aufwoist. Dio Kompononto α) is characterized orhalton that a Copolymorisat, the carboxylic acid and Corbonsäuroonhydridgruppon contains, with oinor Vorbindung gobracht is reacted, dio olne tertiary Aminogruppo and oino

active hydrogen atom contains a group which can negate dio with the anhydride groups. The dioso Wolso from the Anhydridgruppon erzougton Carbonsfluregruppen stand together with the directly into the polymer oingoführton

Corboxylic acid group as opposed to the epoxy group dor component b) reactive groupiorungone for provision. However, such systems have a disadvantage in that they give rise to unprecedented colton between don boidon components a) and b)

can what uniulängj opticalo Eigonschafton dor Lockfilmo has the consequence. Another disadvantage is the fact that it is possible to use Lackfilmo with diosystems only after Ί Tagon oinigermaßon solvent-resistant,

Dio EP-A-134691 describes room-temperature or low-temperature-curable compositions of bostohond from

oinor component with mindostons two hydroxyl groups per molecule, b) oinor component with mindostons two

Carboxylic acid hydride group per molecule and c) ooror component with at least two epoxide groups per molecule. Also

in this case, os can lead to incompatibilities of the components n), b) and c), which results in poor opto-film aortics.

It was the problem underlying the invention to steal nano binder sterols for boil-up, boi doron curing

Dio between carboxylic acid anhydride, hydroxyl or epoxy group in the sense of addition reactions occurring

Vorstotzungsroaktionon take place, and not with don Nochtoilon dor Systomo dos aufgozoigton Booth of the technology bohaftot This task could be solved by dio Beroitstollung dor hereinafter closer to chiarobonon copolymers, which

simultaneously contain free hydroxyl, free epoxide and intramolecular Cerbonsäureanhydridgruppon in chemically incorporated form. Such copolymers are not yet known gewordon; their particular advantage is to be seen in the circumstance that boi dor formulation of the coating agent does not lead to incompatibilities under vorf chiodonon

Bindomittol Komponenton kommon kenn and thus Lackfilmo result, the dio insbosondoro extremely good optical Eigonschafton

respectively.

Another advantage of orfindungsgemäßon copolymers in the circumstance to see that it is vorbesvorondondo Handolt systems that can cure after a double-cure Mochanism. First, anhydride group reacts with hydroxyl groups, then the resulting in this reaction Carboxyl groups with don Epoxidgruppon abreagioron. This will increase the number of free carboxyl groups in the coating

reduced and thereby high Vernelzungsdichten orziolt. Hoho requirements regarding solvent and

Chomikfllienbeständigkoit can be met. The invention relates to copolymers having a weight average molecular weight of from 1500 to 75,000

of olefinically unsaturated compounds, characterized gokennzeichnot that dio copolymers simultaneously

(i) 0.2 to 6.0% by weight of free hydroxyl groups,

(ii) 1 to 30 wt% of carboxylic anhydride groups (calculated as C ₄ H ₂ Oj) and (iii) 0.4 to 13 wt% of epoxy groups (calculated as C ₂ H ₂ O)

chemically bound.

Subject Erfindu ^"-: st a Vorfehron for the production of these copolymers by copolymerization of Mixture of olefinically unsaturated compounds boi 60 to 12O ⁰ C in the presence of, the polymerization reaction

initiating compounds, characterized in that one uses such a mixture of olefinically unsaturated compounds which in addition to hydroxyl, epoxy and acid anhydride group-free monomers Ii) olefinically unsaturated alcohols, (ii) olefinically unsaturated acid anhydrides and (iii) olefinically unsaturated epoxides

in such an amount that in the monomer mixture 0.2 to 6.0% by weight of hydroxyl groups, 1 to 30% by weight of carboxylic acid anhydride group (calculated as C ₄ H ₂ O ₃ ) and 0.4 to 13% by weight of epoxy group ( calculated as C ₂ H ₂ O). Finally, the invention also relates to the use of these copolymers as binders or binder component in one- or two-component coating compositions or sealants, which may comprise, as further binder component, organic amine compounds as catalysts.

The copolymers according to the invention have a molecular weight (weight average) determinable by the method of gel permeation chromatography of from 1500 to 75,000, preferably from 2,000 to 60,000 and more preferably from 3,000 to 40,000. In addition to chemically incorporated free hydroxyl groups, the copolymers have from 0.2 to 6.0% by weight, preferably from 0.4 to 4.0% by weight, of chemically incorporated intramolecular, cyclic carboxylic anhydride groups of formol

-CH-CH-I I

in an amount of 1 to 30 wt .-%, preferably 2 to 25 Gow .-% (boroclot as C ₄ H ₁ O)), as well as chemically olngobauto epoxy groups of the formol

-CH-CH-

in an amount of 0.4 to 13% by weight, preferably 0.5 to 10% by weight (calculated as C] H) O).

The copolymers are those based on preferably mono-olefinically unsaturated monomoron. For the preparation of the copolymers, i. as Ausgangsmatorlallon in erfindungsgnmäßon ancestor four groups of olefinically unsaturated monomers are used, namely β) hydroxyl-containing, olefinisch ungosättigto Monomore, H intramolecular Carbonsäuroanhydridgruppon containing, olefinisch ungosättigto Monomoro, c) Epoxidgruppon containing, olefinisch ungosättigto monomers and d) olefinisch ungosättigto Monomoro, the koino have such reactive groups and are inortic against such Reoktivgruppon.

Dio Monomeron a) are in allgomoinon in einor Mongo from 1 to 50, preferably 2 to 40 Gow.-Teile, the Monomeron b) in oinor Mongo from 1 to 30, preferably 2 to 25 Gow.-Tollen, dio Monomoron c) in a mongo of from 1 to 40, preferably from 2 to 35, parts by weight of toilon, and the monomers d) generally in oinor amount of from 1 to 50, preferably from 2 to 40, gow.-Toilon, the sum of the parts by weight of the monomer a) to d) gives 100. It should also be noted that the proportions of one-monomoron in the mixture to be added to the copolymerization have been such that in the case of copolymorisotes the above mentioned monogenes are chemically incorporated into hydroxyl, carboxylic anhydrides and epoxide groups. The content of the copolymers in these groups has been determined by the content of the monomor mixture in the golioch groups, since it has been assumed that the copolymer is dioxin; with respect to their chemical composition of the chemical composition of the Monomorongemischs entsproclum.

Incidentally, Art and Mongonverhültnisco dor Mono iron vorzugswoiso so dimensioned that in the resulting Copolymerisaton for each Carbonsäuroanhydridgruppo 0.2 to Θ, vorzugswoiso 0.4 to 4 hydroxyl groups and 0.2 to 8, preferably 0.4 to 4 epoxy groups vorliogon.

The manufacturability of such copolymers with hydroxyl, carboxylic anhydride and epoxide groups was by no means predictable because carboxylic acid anhydride groups are reactive at higher temperatures to hydroxyl groups and the boi of this reaction ontstohondon carboxylic acid group can react with epoxy group in an addition reaction with heat.

Nevertheless, by applying the process according to the invention, these novel copolymers can be prepared in organic solvents by free-radical copolymerization.

The monomers a) are monoolefinically unsaturated alcohols which preferably have a molecular weight of from 58 to 500 and preferably aliphatically bonded hydroxyl groups. Well suited, for example, conventional hydroxyalkyl esters of acrylic and methacrylic acid such as. Hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; Hydroxyalkyl vinylethane, e.g. Hydroxyethyl vinyl ether or hydroxybutyl vinylethane; allyl alcohol; Hydroxy derivatives of (Moth) acrylamide, e.g. N- (3-hydroxy-2,2-dimethylpropyl) - (meth) acrylamide; Reaction products of glycidyl (moth) acrylate with monocarboxylic acids; Reaction products of (meth) acrylic acid with mono-oxide compound; as well as reaction products of the previously mentioned OH-functional olefinically unsaturated compounds with e-caprolactone or butyrolactone.

Typical examples of monomers b) are z. For example, itaconic anhydride or maleic anhydride, with maleic anhydride being preferred.

Good suitable monomers c) are z. B. glycidyl acrylate or glycidyl methacrylate.

The monomers d) generally have a molecular weight of from 86 to 400. These are dio conventional hydroxyl, acid anhydride, and epoxy groups-free, preferably monoolefinically unsaturated monomers, as they have already been used as monomors in the method of the aforementioned prior art. Typical examples are esters of acrylic and methacrylic acid such as methylarrylate, ethylacrylate, n-butylacrylate, isobutylacrylate, tert-butylacrylate, 2-ethylhexylacrylate, cyclohexylmethacrylate, methylmethacrylate, n-butylmethacrylate, isobutylmethacrylate or 2-ethylhexylmethacrylate; Vinylaromatics wio, for example, styrene, vinyl toluene, a-methyl styrene, a-ethyl styrene, nucleus-substituted, optionally Iscmorengemischo performing diethylstyrenes, isopropylstyrenes, butylstyrenes and methoxystyrenes; Vinyl ethers such as ethyl vinyl ether, N-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; Vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate.

When carrying out the copolymerization, it is of course possible to use any mixtures of the monomers a) to d) exemplified.

The preparation of the copolymers, that is, the process according to the invention can be carried out by copolymerization of the monomers a) to d) exemplified by conventional free-radical polymerization, such as bulk or solution polymerization.

The monomers are copolymerized at temperatures of 60 to 120 ° C, preferably 80 to 115 ⁰ C in the presence of radical formers and optionally molecular weight regulators.

The process according to the invention is preferably carried out in inert solvents. Suitable solvents are, for example, aromatics such as benzene, toluene, xylene; Esters, such as ethyl acetate, butyl acetate, hexyl acetate, heptyl acetate,

Mothylglycolflcotet.Ethylylycolacetate, Methoxypropylorotate, Erythorotoluhydrofuran.Dioxene.Dlothylonglycolimothylothor; Kotono wio acetone, methyl ethyl ketone, molylsobutyl ketone, Mothyln omylketon, Molhyl lsoamylkoton. The oratory-like ancestor could be continuous or discontinuous. Typically, in the polymorylation reactor, the monomorphine rotation and the initiator oindosiort and gloichzoite clio corresponding Mongo polymerizate are continuously and continuously measured. Preferencewould probably have been made so chemically almost oinhoitlicho copolymers. Chomisch nearly uniform Copolymoro can also be horgostollt, iiuloni men dlo reaction mixture at constant speed in olon Rührkossol oinlaufon leaves, without dissipating the polymer. You can also e ^; Part of dor Monomoron boispiolsolso in solvents of the type mentioned above, and the rustproof monomers and auxiliaries separately or together in dioso template boi dor r.oaktionstomporotur. In general, the polymerization is carried out under atmospheric pressure, but also boiling point Drückon has been carried out up to 2Obar. The initiators were generally in Mongone from 0.05 to 16 Gow.-V preferably 0.1 to 10 Gow .-%, based on the total amount dor Monomoron eingosotzt.

Gooignoto initiators are common radical starters. For example, aliphatic azo compounds wio azodiisobutyric acid nitrile, azo-bis-2-mothylvaloronitrile, 1,1'-azobis-i-cyclohoxanenitrile, and 2,2 '· blo bls-ieboboric acid alkylostorus; symmetrical diacyl peroxides, e.g. Acetyl, propanyl or butyrylporoxide, bromo-, nitro-, methyl- or mothoxy-substituted benzoylporoxides, laurylporoxido; symmetrical peroxydicarbonato, e.g. Diethyl, Dilsopropyl-, Dicyclohoxyl and Bonzoylporoxidicarbonat; tert-Butylporoxy-2-ethylhexanoate, tert-Butylperbonzoat or tert-Butylphonylporocotat and Peroxycnrbonato wio z. T-butyl-N- (phenylperoxy) carbonate or tert-butyl N- (2-, 3- or 4-chlorophonylperoxy) carbonate; Hydroperoxides such as tertiary butyl hydroperoxide, cumene hydroperoxide; Dlalkylporoxide such as di-cumyl peroxide; tort-butyl-cumylporoxide or di-tert-butylporoxide.

To regulate the molecular weight of the copolymers, it is usually possible to use a reglor boi dor preparation wordon. Boispiolhii. gonan are tort.-Dodecylmercaptan, n-Dodocylmorcaptan or Diisopropylxanthogondisulfid. Dio-Reglor can be added in quantities of up to 10% by weight, preferably 0.5 to 5% by weight, based on the amount of monosorbent monomoron.

The solutions of the copolymers obtained in the copolymerization reaction can then be fed olino-woofero workup of the use according to the invention. Of course, it is also possible to supply the copolymers by distillation from Gogobenenfalls remaining residual monomer to unreacted monomers and solvents to bofroion and present as a distillation residue Copolymerissto dor inventive use. The copolymorisato stellon according to the invention valuable Bindomittol odor Bindomittolkomponenten for one-odor Zweikompononton-Boschichtungsmittol or -Sichtmasson. Einorsoits is boi the Copolymerisaton wegon dor reactivity of cyclic Carbonsäureanhydridgruppon gogonübor hydroxyl groups in the heat and dor Roaktionsfreudigkeit the resulting in this reaction carboxylic acid group gogonüber epoxy groups Heißvernotzbaro one-component-Bindomittol, which is Bodouton, that coating agent and sealing mass, which are cured in the Hitzo, in addition to the copolymers according to the invention no further binder component must be incorporated. On the other hand, the copolymorisato according to the invention, at room temperature, even in conventional lacquer solvents, are largely storage-stable and can be converted into room temperature curing systems by adding a further "binder component", namely a suitable catalyst, in which case it is justified to use binder components for Zwoikompononton-coating agent odor -Sichtmassen "to speak. In this latter variant, the curing of the novel copolymers, it is essential to increase by adding a catalyst components, the reactivity of the acid anhydride groups to the hydroxyl groups so far that even at low temperatures, wio z. B. room temperature, uses a crosslinking reaction. Such catalysts are preferably compounds containing tertiary amino groups. These may be compounds which are either inert toward acid anhydride groups or which, in addition to the tertiary amino group, have a group reactive toward acid anhydride groups (hydroxyl group, primary or secondary amino group). In the second case, the catalyst component is chemically incorporated into the binder moiety component by reacting its reactive group with acid anhydride or epoxide group (in the case of primary or secondary amino groups) to form halo, semiamid, and tertiary amine moieties, respectively Formation of an additional hydroxyl group (from the epoxide group).

Compounds suitable as catalysts are, for example, tort. Amines of molecular weight range 73 to 300 such as ethyldimethylamine, diethylmethylamine, triethylamine, ethyldiisopropylamine, tributylamine, 1-methylpyrrolidine, 1-methylpiperidine, 1,4-dimethylpiperazine, 1,4-diazabicyclo (2,2,2) octane or 1,8 -Diazabicyclo (5,4,0) undec-7-ene, Ν, Ν-dimethylethanolamine, Ν, Ν-diethylpropanolamine, Ν, Ν-dibutylothanolamine, 1-amino-3- (dimethylamino) -propane or 1-amino-2 - (diethylamino) ethane. It can also be any mixtures of the exemplified tort. Amines used to graze.

Furthermore, it is also possible to use organic compounds having at least one tertiary amino groups which have a molecular weight of more than 300. Such substances may e.g. Reaction products of olefinically unsaturated compounds having (meth) acrylate groups with secondary amines, z. As the reaction product of 1 mole of trimethylolpropane triacrylate and 3MoI di-n-butylamine.

But also reaction products of polyisocyanates with Ν, Ν-Dialkylalkanolamineit, wiez. As the Umsotzungsprodukt of 1 mole of biuretized polyisocyanate based on hexamethylene diisocyanate and 3 mol of Ν, Ν-dimethylothanolamine are suitable. Precursors which still contain hydroxyl groups in addition to a tertiary amino group can also be prepared, for example, by reaction of compounds containing epoxide groups with secondary amines; z. B. the reaction product of Ethylhexylglycidylethor and di-n-butylamine or the reaction product of 1,2,7,8-di-epoxyoctane and two molecules of di-n-hexylamine.

In the preparation of room-temperature curing two-component systems, the catalysts are generally used in amounts which tert a content of the gum of copolymer and catalyst. Nitrogen (calculated as N, atomic weight - 14) of 0.001 to 1.0, preferably 0.01 to 0.5 wt .-%, correspond. It is of course also possible to accelerate the curing rate of a room temperature spontaneously curing "two-component system" by heating (60 to 8O ⁰ C).

Coating and thickening agents, which according to the invention are also copolymerized or denominated deltamethanol component (nobon dom catalyst as a second derivative), may also contain aqueous auxiliary and auxiliary / mltol such as boisplelswolsn solvents or diluents, precursors, antioxidants, UV absorbers or pigments onthalton.

The preparation of gobrauchsfortigon coating compositions or Dichtmasson or follows by mixing the Elnzolkomponenton, woboi in the case of prewounding of solvents or diluents insbosondoro also an embodiment is conceivable, derfololgo dioso aids already wuhrond the production of dor Copolymorisato zugogobon soin, wio cMos boroits above in connection with the preparation of the copolymers described wordon is. Basically, os is the solvent or diluent which may be used as a sealant or solubilizer voillogon in order to be solcho dor already exemplarily gonannton species. Siro wordon in general in such Mongon mitvorwondot, dio for adjusting geoignoton Vorarboltungsviskositäton dor orfindungsgomäßon bindomittol are required , Dor Fostgohalt, who gives orformungegomäßon compositions according to the invention, in favor of allgomoinon zwisclion 20 and Θ0 üow .-%. By using goolgnotor nlodermolokularor copolymorisato, however, it is also principally possible to use the solubilizer or diluent or to reduce it.

The ratio of acid anhydride group to hydroxyl groups and epoxide group in the gobrauchsfortigun Boschichtungsmittoln and Dichtmasson corresponds to don it made statements boehr dor diosboigteon composition of the copolymers. If used in Zwolkompononton-Formuliorungen catalysts that aufwoison against acid anhydride or epoxy groups reactive groups and thereby cause an additional pre-use of dorartigon Gruppon, you can consider this gewünschtonfells by increasing the concentration of Säuronnhydrid- or Epoxidgruppon.

The erfindungsgomnßon, preferably dissolved in inorton solution or Vordünm ngemittol coating compositions and sealants are as Einkompunonton-Systomo in universoinon mohroro months lagorsUibil or woison as Zweikompononton-Forming a pot life of several hours on. One-component Systomo harden self-priming at temperatures of about 140 to 200 ⁰ C and two-component Systomo cure already boi Raumtempe atur to coatings with high-quality mechanical and optical film anodization.

The orginungsgomäßon copolymers can be vorwtndot without dirokt without woitero additives for Horstollung Klar & ichtüborzügon. In Rogol, however, the customary in the paint industry auxiliary and Zusatzmittol the already obon example mentioned type mitverwondet. The coating compositions odor sealing mass according to the invention can by known methodon such as spraying, scavenging, diving, flooding, casting, rolling on boliobigo, gobobononfalls already vorbohandelto substrates such. As metal, wood, glass, ceramic, stone, concrete, plastics, Toxtilion, Loder, cardboard and paper oufgetragon werdon.

In the following Boispielon all statements in Prozonten and Toilon, unless otherwise provided, refer to the weight.

Examples

I General preparation instructions for the hydroxyl, anhydride and epoxy groups containing Copolymorisato A, to A ₇ In oinom 3-liter reaction vessel with stirrers, coolers and heaters Part 1 is presented and heated to Roaktionsstemperatur. Then, in parallel, portion II (addition over a period of a total of 2 hours) and Toil III (addition over oinon cell space of a total of 2.5 hours) are added. Subsequently, 2 hours boi the Roaktionstemperatur nachgorührt. Dio reaction temperatures and the compositions of parts I to III are listed in Table I, together with the characteristics of the Copolymorisato obtained.

Table 1 (quantities in g)

copolymers A, 800 A, A ₃ 680 A ₄ 680 A ₆ 600 A ₄ 800 A ₇ 800 TeIII butyl 680 162 methoxypropylacetate 222 268 248 248 TeIIII 215 352 250 194 322 butyl acrylate 215 126 styrene 352 414 methyl methacrylate 322 2-ethylhexyl acrylate 384 2-Ethylhexylmotnacrylat 160 470 206 186 108 182 182 butyl methacrylate 194 194 194 Hydroxypropylmothacrylat 156 174 58 100 150 130 130 Hydroxyothylmethacrylat 108 140 126 glycidyl 58 maleic anhydride 118

Continuation of Tabollo I A, 64 A, 70 A ₁ 70 A ₄ 70 A ₆ 64 A, 64 A, 64 copolymers Tell III 60 78 80 78 tort.-Butylporoxy-2-othylhoxonoat 60 60 60 (70%) 100 100 100 100 105 10b 105 Butylacotot 56.0 59.8 59.1 60.4 65.8 56.0 55.1 Mothoxypropylacetot 13,448 9 162 13415 69 242 25194 27 399 48 878 Polymof isetionstompofuration CC) Fostgeholt (%) 1: 1: 1 3: 3: 1 7: 7; 2 1.9: 1.9: 1 1.9: 1.7: 1 1: 1: 1 1: 1: 1 Viscosity (niPa · s) MolvorhdltnisAnhydrld- / hydroxyl / Epoxldgrupponca.

I Horitollung dor Erflndungsgemlßon coating agent

β) Under Elnbrennbodlängungen

Dio copolymers Ai to A / wonton gogebononfolls by adding oinos organic solvent or diluent adjusted to a workable viscosity. DIo films wordon drawn up with a Filmzlohor on Prüfblocho, wherein the Naßfilmstärko amounts to 150μπι. After 5 minuton at Raumtomporntur wordon dio coated Prüfblocho 30 minuton at 15O ⁰ C golagort. Then wordon sio cooled on RaumtomporaUir. On dioso Woise one receives clear, farbloso, vorotzto films with guton filmoptischon and mechanical words.

The solvent resistance is determined by oinon wiping test with olefin Motliylisobutylketon (MIBK) gotegrenzon Wattobausch goprüft.

Angogobon becomes the number of Doppolhübo, after which the film blooms without any visible change. Mohr as 200 Doppolhübo

per film wurdon not performed.

In the following table Il, the solvents have been added to the films basiorond on the copolymorisate Ai to A? to

Hardening boi 150 ⁰ C angogobon.

Table II Preliminary Boisboole 1 2 3 4 5 6 7

Coating film based on copolymer MIBK wipe test Number of double strokes

b) at room temperature

Dio Copolymers A ₍ to A) are mixed with a tertiary amine at room temperature and optionally adjusted to a workable viscosity by addition of an organic solvent and diluent The films are coated on test panels with a film-puller, the wet film thickness being 150 pm Dio so boi After aging, ie drying at room temperature for about 24 hours, clear, colorless, supernatural films are obtained with guton film-optical and mechanical films

Values.

The applied lacquer mixtures show a stand-alone of Mehreron Stundon.

The solvent resistance is determined wio previously described.

In the following Table III, the compositions of the binder combination and solvent solubility have been used

Degree of networking listed.

A, A ₁ A ₁ A ₄ A ₆ A ' A ₇ 200 140 150 18C 200 200 200

Table III 1 2 3 4 5 6 7 usage example 40, Oga, 40, Oga, 40, OgA ₃ 40, OgA ₄ 40, OgA ₅ 40, OgA ₄ 40, OgA ₇ Component A 0.1g 0.1g 0.1g 0.1 Cj 0.1g 0.1g 0.1g Ν, Ν-dimethylethanolamine 15g 15g 15g 25 g 20 g 20 g 25 g butyl > 1 hour > 2h > 2h > 2h > 1 hour > 1h > 1 hour lifetime MIBK Wischtestnach 24 h room temperature 180 130 150 170 200 200 200 Number of double strokes

Claims (8)

1. Copolymers with olnom olr Gowichtsmittol bostimmton Molokulnrgowicht from 1500 to 75000 of olofinisch ungosättigton compounds, characterized in that the Copolymorisoto simultaneously (i) 0.2 to 6.0% by weight of frolone hydroxyl groups, (H) 1 to 30% by weight of carboxylic acid anhydride group (calculated as C ₄ H ₂ Oa); and (iii) 0.4 to 1 J% by weight of epoxide dione (borochnotalsC ₂ H ₂ O) chomic gobundon onthaltone. 2. ancestors for the preparation of these copolymers by copolymerization of a mixture of olofinisch unsaturation Vorbindungen at 60 to 120 ° C in the presence of, the Polymerisationsroaktion initiiorendon compounds, characterized in that one uses such a mixture on olofinisch ungooftttigton compounds which nobon hydroxyl, epoxy And acid anhydride group-froion monomerone (i) olefinically unsaturated alcohols, (ii) olofinically unsaturated acid anhydride and (iii) olefinically unsaturated epoxides in such an amount that in domonomic monomer 0.2 to 6.0% by weight of hydroxyl groups, 1 to 30% by weight of comorboxylic anhydride group (borochnot as C ₄ H ₂ O 3) and 0.4 to 13% by weight of epoxy groups (calculated as C ₂ H ₂ O). 3. ancestor according to claim 2, characterized in that the dor copolymerization zukomührende monomers a) 1 to 50 grams of Toilon copolymorisiorbarone, hydroxylfunktionollon monomers, b) 1 to 30 parts by weight of copolymerisorbarone, anhydride functional monomers, c) 1 to 40 parts by weight of copolymerizable, epoxide-functional monomers and d) 1 to 50 parts by weight of hydroxyl group, Corbonsäureanhydridgruppen- and Epoxidgrupponfroion inert monomers, where the sum of a) to d) is 100 parts by weight. 4. The method according to claim 2 and 3, characterized in that one uses as hydroxylfunktionello monomers Hydroxyalkylestor dor acrylic or methacrylic acid. 5. The method according to claim 2 to 4, characterized in that one advances as carboxylic acid anhydride-functional monomers maleic anhydride or itaconic anhydride. 6. The method according to claim 2 to 5, characterized in that one uses as epoxide-functional monomers glycidyl acrylate or Glycidylmothacrylat. 7. Use of the copolymers according to claim 1 as a binder in solbstvernetzenden, thermosetting coating compositions or sealants. 8. Use of the copolymers according to claim 1 as a binder component in room temperature curable two-component coating compositions or sealants containing as further Bindemittolkompononto tertiary amino groups, organic compounds which optionally in addition to the tertiary amino groups to carboxylic acid anhydride or epoxy reactive hydroxyl and / or odor Have amino groups.