EP0428553A1 - Copolymerisats renfermant des groupes amino, procede pour leur fabrication, ainsi que leur emploi dans des agents d'enduction - Google Patents

Copolymerisats renfermant des groupes amino, procede pour leur fabrication, ainsi que leur emploi dans des agents d'enduction

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Publication number
EP0428553A1
EP0428553A1 EP89908409A EP89908409A EP0428553A1 EP 0428553 A1 EP0428553 A1 EP 0428553A1 EP 89908409 A EP89908409 A EP 89908409A EP 89908409 A EP89908409 A EP 89908409A EP 0428553 A1 EP0428553 A1 EP 0428553A1
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EP
European Patent Office
Prior art keywords
weight
component
copolymer
amount
components
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP89908409A
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German (de)
English (en)
Inventor
Werner Alfons Jung
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Farben und Fasern AG
Original Assignee
BASF Lacke und Farben AG
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Publication date
Application filed by BASF Lacke und Farben AG filed Critical BASF Lacke und Farben AG
Publication of EP0428553A1 publication Critical patent/EP0428553A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines

Definitions

  • the invention relates to copolymers which contain amino groups and which are soluble in organic solvents and which can be prepared from copolymers containing alkyl ester groups by aminolysis, prepared by means of free radical solution polymerization, processes for their preparation and their use in coating compositions.
  • the very high residual monomer content ie the amount of unreacted starting monomer, expressed in% by weight, based on the total amount of this monomer originally used
  • the solvent load in the environment when drying the paint films is the high solvent content of the coating agents caused by the high viscosity of the binder solutions.
  • the invention was therefore based on the object of making available copolymers containing amino groups which can be prepared by means of a simple process and which also include Use of a high vinyl aromatic content of up to 50% by weight, based on the total amount of monomers, in the preparation of the intermediate stage of the copolymers containing alkyl ester groups has a low residual monomer content ( ⁇ 10% by weight) of vinyl ester monomers and the clear solutions give.
  • the solutions of the copolymers containing amino groups obtained should have the lowest possible viscosity.
  • the coating compositions produced using these copolymers should have the highest possible solids content, with a viscosity of 16 to 20 s, which is favorable for processing, measured in the outlet cup according to DIN 4, should show good pigmentability and should have coatings with good technological properties Properties, especially good hardness and gasoline resistance.
  • an amino group-containing copolymer (B) which can be prepared by aminolysis of copolymers (A) containing alkyl ester groups - prepared by means of free-radical solution polymerization and which is characterized in that the copolymer (B) containing amino groups can be prepared, by doing
  • a copolymer (A) containing alkyl ester groups has been synthesized by radical solution polymerization at temperatures from 130 to 200 ° C., preferably 150 to 180 ° C., by
  • Remainder of component al are metered in within a monomer addition period of the same length for all components such that
  • Vinyl esters of monocarboxylic acids preferably vinyl esters of monocarboxylic acids having 5 to 15 carbon atoms per molecule and branched in the o position, are used as component a1.
  • the branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be cracked products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins.
  • olefins When such olefins are reacted with formic acid or with carbon monoxide and water, a mixture of carboxylic acids is formed in which the carboxyl group is predominantly located on a quaternary carbon atom.
  • Other olefinic starting materials are e.g. Propylene trimer, propylene tetramer and diisobutylene.
  • the vinyl esters can also be prepared from the acids in a manner known per se, e.g. by allowing the acids to react with acetylene.
  • vinyl esters of saturated aliphatic monocarboxylic acids with 9 to 11 carbon atoms which are branched on the eC-carbon atom are particularly preferred.
  • the vinyl ester of p-tertiary butyl benzoic acid is also particularly preferred.
  • Examples of other suitable vinyl esters are vinyl acetate and vinyl propionate.
  • Component a2 is a monovinyl aromatic compound. It preferably contains 8 to 9 carbon atoms per molecule. Examples of suitable compounds are styrene, vinyltoluenes, ⁇ C-methylstyrene, chlorostyrenes, o-, m- or p-methylstyrene, 2,5-dimethylstyrene, p-methoxystyrene, p-tert.-butylstyrene, p-dimethylaminostyrene, p-acetamidostyrene and m-vinylphenol. Vinyl toluenes and styrene in particular are preferably used. The amount of component a2 is 10 to 50% by weight, preferably 20 to 45% by weight.
  • alkyl esters of aliphatic, olefinically unsaturated carboxylic acids with 1 to 6 C atoms, preferably 1 to 4 C atoms, are used in the alkyl radical.
  • Examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, isoamyl ( meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate and the corresponding esters of maleic, fumaric, crotonic, isoerotonic, vinyl acetic and itaconic acid.
  • Component a3 is used in an amount of 10 to 40% by weight, preferably 15 to 35% by weight.
  • component a4 0 to 40% by weight of other, ethylenically unsaturated, copolymerizable monomers (component a4) can also be used to build up the copolymer (A) containing hydroxyl groups.
  • the selection of these monomers is not particularly critical. However, care must be taken that the incorporation of these monomers does not lead to undesirable properties of the copolymer.
  • the choice of component a4 largely depends on the desired properties of the curable composition with regard to elasticity, hardness, compatibility and polarity.
  • amides of acrylic and methacrylic acid and their derivatives such as, for example, acrylamide, methacrylamide, N-alkylamides such as, for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl ( meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-pentyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-dodecyl (meth) acrylamide and N-decyl (meth) acrylamide.
  • Long-chain al yl-substituted acrylic and methacrylamide derivatives are preferred, dodecyl meth
  • component a4 are aminolysis-resistant compounds such as N-vinyl pyrrolidone.
  • Unsaturated nitriles such as e.g. (Meth) acrylonitriles and compounds such as e.g. (Meth) acrylic acid, vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride.
  • the polymerization of the monomer components a1 to a4 is preferably carried out in the absence of oxygen, e.g. by working in a nitrogen atmosphere.
  • the reactor is equipped with appropriate stirring, heating and cooling devices and with a reflux condenser in which volatile constituents, e.g. Styrene are retained, equipped.
  • the polymerization reaction is carried out at temperatures from 130 to 200.degree. C., preferably 150 to 180.degree. C., using polymerization initiators and, if appropriate, polymerization regulators.
  • Suitable free radical initiators are organic peroxides, e.g. Dibenzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide,
  • aliphatic azo compounds such as azobiscyclohexanenitrile can also be used.
  • azo compounds there is a risk of yellowing of the polymers which, depending on the intended use of the polymers, can be disruptive, so that in these cases other initiators must be used.
  • the amount of initiator is in most cases 0.1 to 5% by weight, based on the amount of monomers to be processed, but it can also be higher if necessary.
  • the initiator, dissolved in part of the solvent used for the polymerization, is gradually metered in during the polymerization reaction.
  • the initiator feed preferably takes about 1 to 2 hours longer than the monomer feed in order to achieve a good effect during the post-polymerization phase. If initiators with only a low decomposition rate are used under the present reaction conditions, it is also possible to introduce the initiator.
  • the reaction is preferably carried out in the presence of polymerization regulators, since this results in a narrower molecular weight distribution and clouding of the polymer solutions can be better avoided.
  • Polymerization regulators are preferably suitable as regulators, mercaptoethanol being particularly preferably used.
  • Other possible regulators are, for example, alkyl mercaptans, such as, for example, t-dodecyl mercaptan, octyl mercaptan, phenyl mercaptan, octyldecyl mercaptan, butyl mercaptan, thiocarboxylic acids, such as thioacetic acid or thiolactic acid.
  • These regulators are used in an amount of up to 2% by weight, based on the amount of monomers to be processed. They are preferably dissolved in one of the monomer feeds and added with the monomers. The amount of regulator added is preferably constant over time.
  • the polymerization is carried out in a high-boiling, organic solvent which is inert towards the monomers used.
  • suitable solvents are high-boiling alcohols, e.g. n-hexanol, 2-ethylhexanol, isooctyl alcohol, isononyl alcohol, isodecyl alcohol, isotridecyl alcohol, cyclohexanol, methylcyclohexanol, benzyl alcohol, methylbenzyl alcohol, tetrahydrofufuryl alcohol, diactone alcohol, 2,6-dimethyl-4-2-heptanol, 4 pentanol,
  • high-boiling alcohols e.g. n-hexanol, 2-ethylhexanol, isooctyl alcohol, isononyl alcohol, isodecyl alcohol, isotridecyl alcohol, cyclohexanol, methylcycl
  • Tridecanol Tridecanol; Glycols and glycol derivatives, such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,4-butanediol, hexylene glycol, 2-ethylhexanediol-1,3, diethylene glycol, triethylene glycol, dipropylene glycol, methyl diglycol, ethyl diglycol kol, butyl diglycol, hexyl diglycol, tripropylene glycol methyl ether, methoxy triglycol, ethyl glycol acetate, butyl glycol acetate, ethyl diglycol acetate, ethylene glycol diacetate; more highly substituted aromatics, such as, for example, solvent naphtha ***** ** , heavy benzene, various types of Solvesso ⁇ , various types of Shellsol ⁇ and Deaso - * - as well as higher-boil
  • At least 60% by weight, preferably 100% by weight, of the total amount of component a1 to be used together with part of the total amount of solvent to be used are initially introduced into the reactor and to the particular amount Reaction temperature heated. As already described, the remaining amount of the solvent is preferably added gradually together with the catalyst. Any remaining amount of component a1 and the other monomers (components a2, a3 and a4) are added within a monomer addition period of the same length for all components (generally 2-10 h, as is customary for acrylate copolymerizations) metered in to the component presented as follows:
  • component a1 is preferably metered in together with components a3 and a4.
  • the amount of component a2 added per unit of time is varied within the monomer addition period such that the total amount of component a2 added within the first third of the monomer addition period is 15 to 30% by weight, preferably 18 to 26% by weight. %, the total amount of component a2.
  • the amount of component a2 added per unit of time there are various possibilities for varying the amount of component a2 added per unit of time, the only thing that is decisive is that the amounts indicated in total in each third * are observed. For example, there is the possibility of a gradual change in the amount of component a2 added per unit of time.
  • the number of stages at which the addition amount is changed can be chosen as desired. For example, the amount added per unit of time of component a2 can only be increased at the beginning of the second and / or at the beginning of the third third. The amount added per unit of time then remains constant within the third. However, it is also possible to continuously change the amount of component a2 added per unit of time, in accordance with the limit of an infinite number of stages.
  • the copolymers (A) are converted into the amino group-containing copolymers (B) by reaction with a polyamine.
  • Polyamines with at least one primary amino group are preferably used for the aminolysis.
  • Diprimary diamines such as e.g. Ethylenediamine, tri, tetra, penta-, hexa-,
  • aromatic diprimary diamines such as, for example, benzidine, diaminodiphenylmethane, phenylenediamines, toluenediamines, xylylenediamines and diamines with 3 benzene nuclei in the molecule, such as bis (4-aminophenyl) - « ⁇ £., ⁇ *.
  • polyamines with at least one primary and at least one further amino group such as, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetraamine, tetrapropylenepentamine, tris- (2-aminoethyl) amine and N- (2-aminoethyl) ) ethanol.
  • reaction of the polyamine with the alkyl ester-containing polymer (A) takes place at temperatures between 50 and
  • the polymer (A) contains methacrylate ester groups to be aminolyzed, it is preferred to work at temperatures between 120 and 160 ° C, in the case of acrylate ester groups at temperatures between 100 and 125 ° C.
  • reaction is in the presence of 0.01 to 1.0
  • Metal alkoxides are suitable, e.g. Sodium methoxide, potassium t-butoxide; Metal hydroxides, e.g. Sodium and potassium hydroxide; Ammonium salts, e.g. Ammonium chloride or bifunctional catalysts such as e.g. 2-hydroxypyridine.
  • the amount of polyamine used is chosen so that the resulting copolymer (B) has an amine number of 30 to
  • the average molecular weight (number average) of the copolymer (B) is between 1500 and 8000.
  • the invention also relates to a process for the preparation of copolymers containing amino groups by aminolysis of copolymers (A) containing alkyl ester groups, prepared by means of free-radical solution polymerization, which is characterized in that (A)
  • the amount of component a2 added within the first third of the monomer addition period is 15 to 30% by weight, preferably 18 to 26% by weight, of the total amount of component a2, within the second third 25 to 40% by weight, preferably 30 to
  • the copolymer (A) is reacted with polyamines to give an amino group-containing copolymer (B) with an amine number of 30 to 150 mg KOH / g and an average molecular weight (number average) of the copolymer (B) of 1500 to 8000 .
  • the present invention furthermore relates to coating compositions which contain the copolymers (B) according to the invention as a binder component.
  • Suitable hardener components in these coating compositions are aminoplast resins, epoxies, compounds or resins which carry double bonds capable of Michael addition, polyisocyanates and compounds which are capable of amide and / or imide formation, carboxylic acid and / or carboxylic ester. and / or carboxylic anhydride groups.
  • the hardener is added in such an amount that the molar ratio of the amino groups of the copolymer (B) to the reactive groups of the crosslinking agent is between 0.3: 1 and 3: 1.
  • Aminoplast resins suitable as hardener components are preferably melamine and / or benzoguanamine resins. These are etherified melamine or benzoguanamine formaldehyde condensation products.
  • the compatibility of the resins with other film formers and solvents is influenced by the chain length of the etherification alcohol and the degree of etherification.
  • the main etherification components are n- and isobutanol and methanol. Hexamethoxymethylmelamine resins are very important. However, they have the disadvantage that such combinations only harden at temperatures above 150 ° C. and that an addition of acidic catalysts is often necessary.
  • crosslinkers are aliphatic polyepoxide compounds of epoxidized oils, e.g. epoxidized linseed oil or epoxidized soybean oil, epoxidized cyclic compounds such as vinylcyclohexene diepoxide, glycidyl ether of hydrogenated bisphenol A, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, epoxy resins based on epichlorohydrin and polyhydric alcohols such as pentaerythritol,
  • Trimethylolpropane or sorbitol aromatic epoxy resins, such as polyglycidyl ethers of polyhydric phenols, for example glycidyl ethers of 4,4-diphenylol methane or propane or polyglycidyl ethers of novolaks, glycidyl esters of aliphatic or aromatic polycarboxylic acids, for example terephthalic acid or glycidyl methacrylate, glycidyl ester.
  • aromatic epoxy resins such as polyglycidyl ethers of polyhydric phenols, for example glycidyl ethers of 4,4-diphenylol methane or propane or polyglycidyl ethers of novolaks, glycidyl esters of aliphatic or aromatic polycarboxylic acids, for example terephthalic acid or glycidyl methacrylate, glycidyl ester.
  • Examples of compounds or resins which carry double bonds capable of Michael addition are, for example in question acrylic and / or methacrylic acid esters of polyhydric alcohols, such as trimethylolethane or trimethylolpropane triacrylate and / or the corresponding methacrylic acid esters, butanediol diacrylate and / or unsaturated polyesters based on fumaric and / or maleic acid.
  • acrylic and / or methacrylic acid esters of polyhydric alcohols such as trimethylolethane or trimethylolpropane triacrylate and / or the corresponding methacrylic acid esters, butanediol diacrylate and / or unsaturated polyesters based on fumaric and / or maleic acid.
  • polyesters can additionally contain up to 70%, preferably up to 30%, of saturated, at least dibasic carboxylic acid units in the carboxylic acid component which do not contain any double bonds capable of Michael addition, such as ortho-, iso- or terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid - re, adipic acid.
  • the corresponding anhydrides can of course also be used in the manufacture of the polyesters.
  • Suitable alcohols for the preparation of the unsaturated polyesters are preferably diols such as ethylene glycol, 1,2- and 1,3-propanediol, diethylene glycol and / or dipropylene glycol.
  • Combinations of polymer resins according to the invention with at least trifunctional acrylic esters such as glycerol, trimethylolethane or propane triacrylate, pentaerythritol tetracrylate are particularly reactive. Such combinations harden very quickly even below room temperature.
  • polyisocyanates with at least 2 isocyanate groups per molecule.
  • Aromatic Suitable, for example: Aromatic, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids
  • Isocyanates such as 2,4-, 2,6-tolylene diisocyanate and their mixtures, 4,4'-diphenylmethane diisocyanate, m-phenylene, p-phenylene, 4,4'-diphenyl, 1,5-naphthalene, 1 , 4-naphthalene, 4, '-Toluidin-, xylylene diisocyanate and substituted aromatic systems such as, for example, dianisidine diisocyanates, 4,4'-diphenyl ether diisocyanates or chlorodiphenylene diisocyanates and higher-functionality aromatic isocyanates such as, for example, 1,3,5-triisocyanatobenzene, 4,4 '-, 4 "-triisocyanate triphenyl methane, 2,4,6-triisocyanatotoluene and 4,4'-diphenyldimethylmethane-2,2 ', 5,5'-tetraisocyanate; cycl
  • Polyisocyanate prepolymers are also suitable. These include adducts of tolylene diisocyanate and trimethylolpropane, a biuret formed from 3 molecules of hexamethylene diisocyanate and the trimers of hexamethylene diisocyanate and 3,5,5-trimethyl-l-isocyanato-3-isocyanato-methylcyclohexane. Combinations with polyisocyanates or resins containing isocyanate groups crosslink very quickly, even at temperatures below 0 ° C.
  • Suitable hardeners are also compounds or resins which contain carboxylic acid and / or carboxylic acid ester and / or carboxylic acid anhydride groups and which react with the polymers according to the invention via amide or imide formation.
  • the curing temperature depends on the reactivity of the carboxylic acid, carboxylic acid ester or carboxylic acid ester contained in the combination partner Carboxylic anhydride groups.
  • polyfunctional compounds or resins which carry reactive ester bonds of malonic acid or acetoacetic acid it is possible to provide coating compositions which crosslink at 80-120 ° C., while when using saturated alkyd resins, curing temperatures are available above 120 ° C, preferably even above 150 ° C, are required.
  • the coating compositions according to the invention can furthermore also contain customary pigments and fillers in customary amounts, preferably 0 to 60% by weight, based on the total composition, and other customary auxiliaries and additives, such as, for example, Leveling agents, silicone oils, plasticizers such as phosphoric acid esters and phthalic acid esters, viscosity-controlling additives, matting agents, UV absorbers and light stabilizers in customary amounts, preferably 0.2 to 10% by weight, based on the total composition.
  • customary pigments and fillers in customary amounts, preferably 0 to 60% by weight, based on the total composition
  • other customary auxiliaries and additives such as, for example, Leveling agents, silicone oils, plasticizers such as phosphoric acid esters and phthalic acid esters, viscosity-controlling additives, matting agents, UV absorbers and light stabilizers in customary amounts, preferably 0.2 to 10% by weight, based on the total composition.
  • These coating agents can be sprayed, flooded,
  • Dipping, rolling, knife coating or brushing can be applied to a substrate in the form of a film, the film then being hardened to form a firmly adhering coating.
  • the coating compositions of the invention are suitable - if, by appropriate choice of the hardener component, low curing temperatures between 20 and 80 ° C. can be used (see above) - for the refinishing of motor vehicles and in particular for use as a primer and filler material.
  • Shellsol ⁇ mixture of C3-C4-alkyl-substituted aromatics
  • the template is heated to 160-170 ° C.
  • the contents of monomer tank I and the initiator tank are evenly dosed into the boiler within 4.5 hours.
  • the content of the monomer tank II is metered in over the course of 4.5 hours such that 1/6 of the amount of styrene in the first 90 minutes, 2/6 of the amount of styrene from the 91st to the 180th minute and half of the total amount of styrene in the remaining feed time be added.
  • the residual content of free vinyl ester monomer in the solution was determined by gas chromatography to be 0.5% by weight. This corresponds to a residual monomer content of 3.77% by weight, based on the total amount of vinyl ester monomer used.
  • the copolymer solution 1 obtained in this way has a solids content of 62.7% (1 h 130 ° C.), a viscosity (50% in butanol) of 8.7 dPas (23 ° C.) and an amine equivalent weight of 452.4 (based on 62.7% solids). After 9 months of storage at room temperature, the viscosity of the copolymer solution 1 was measured again: after dilution with butanol to a solids content of 50%, it was 10.4 dPas (23 ° C.).
  • this copolymer solution 1 30 parts are mixed with 20 parts of an aliphatic epoxy resin with a molecular weight of approx. 1200 and an epoxy equivalent weight of approx. 300 and diluted with 7.5 parts of butyl acetate.
  • Basis of The epoxy resin used is a two-core melamine resin, reacted with acrylamide and subsequent epoxidation of the acrylic double bonds (trade name LSE 4103 from Monsanto).
  • LSE 4103 trade name from Monsanto
  • a clearcoat 2 30 parts of the copolymer solution 1 described above are mixed with 15.2 parts of a commercially available epoxidized novolac (commercial product DEN 444 from Dow Chemical) with an epoxy equivalent weight of 228, a viscosity of> 40 dPas and an average functionality of 3 to 4 mixed and diluted with 7.5 parts of butyl acetate.
  • This clear coat 2 is knife-coated on glass sheets, baked, and analog clear coat 1, the resulting coating is examined in the same way as clear coat 1. The test results are shown in Table 1.
  • Flakes of felt (0.5 cm) impregnated with commercially available premium gasoline are left covered on the film for 5 minutes.
  • the copolymer solution A * thus obtained has a solids content of 79.6% (1 h at 130 ° C.) and a viscosity (50% in butyl acetate) of 1.25 dPas (23 ° C.).
  • the mixture is diluted to a theoretical solid of 65% with butyl glycol.
  • the copolymer solution A obtained had a solids content of 68% (15 min at 180 ° C.) and a viscosity of> 40 dPas (50% in butanol) and 16-17 dPas (35% in butanol). After 3 months 'storage at RT, solution A' was no longer soluble in butanol when dissolved.
  • a comparison of the copolymer solution A obtained in Example 1 with the copolymer solution A 'obtained in the comparative example shows that the solution of the copolymer A according to the invention with 8.7 dPas (23 ° C., 50% in butanol) is essentially Has lower viscosity than the solution of the copolymer A 'prepared according to US Pat. No. 4,120,839 with 16-17 dPas (23 ° C., 35% in butanol).

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

Abstract

L'invention se rapporte à des copolymérisats renfermant des groupes amino et présentant un indice d'amine compris entre 30 et 150 mg KOH/g et un poids moléculaire moyen compris entre 1500 et 8000, qui peuvent être fabriqués à partir de copolymérisats contenant des groupes alkyle ester par aminolyse avec des polyamines. Sont également décrits un procédé pour les fabriquer, ainsi que leur emploi dans des agents d'enduction. Les copolymérisats contenant des groupes alkyle ester peuvent être produits par polymérisation radicalaire en solution à des températures comprises entre 130 et 200°C, de préférence entre 150 et 180°C, de 5 à 25 % en poids d'ester vinylique, 10 à 50 % en poids de vinyle aromatique, 10 à 40 % en poids d'ester d'alkyle d'acides carboxyliques aliphatiques oléfiniquement insaturés comportant 1 à 6 atomes de C dans le résidu alkyle, et éventuellement d'autres monomères. On met l'ester vinylique et on ajoute les autres monomères comme suit dans un intervalle de temps identique pour tous les monomères: 1) la quantité d'ester d'alkyl ajoutée par unité de temps est constante. 2) on ajoute 15 à 30 % en poids de vinyle aromatique dans le premier tiers de l'intervalle de temps prévu pour l'addition des monomères, 25 à 40 % en poids dans le second tiers, et 35 à 60 % en poids dans le dernier tiers, ces pourcentages en poids étant rapportés à la quantité totale de vinyle aromatique.
EP89908409A 1988-08-13 1989-07-20 Copolymerisats renfermant des groupes amino, procede pour leur fabrication, ainsi que leur emploi dans des agents d'enduction Pending EP0428553A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3827587 1988-08-13
DE3827587A DE3827587A1 (de) 1988-08-13 1988-08-13 Aminogruppenhaltige copolymerisate, verfahren zu ihrer herstellung sowie ihre verwendung in beschichtungsmitteln

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EP0428553A1 true EP0428553A1 (fr) 1991-05-29

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EP89908409A Pending EP0428553A1 (fr) 1988-08-13 1989-07-20 Copolymerisats renfermant des groupes amino, procede pour leur fabrication, ainsi que leur emploi dans des agents d'enduction
EP89113346A Expired - Lifetime EP0355408B1 (fr) 1988-08-13 1989-07-20 Copolymères contenant de groupes amino, leur procédé de préparation et leur application aux revêtements

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Country Link
US (1) US5229467A (fr)
EP (2) EP0428553A1 (fr)
AT (1) ATE81658T1 (fr)
BR (1) BR8907602A (fr)
CA (1) CA1329302C (fr)
DE (2) DE3827587A1 (fr)
ES (1) ES2052830T3 (fr)
WO (1) WO1990001502A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE3942592A1 (de) * 1989-12-22 1991-06-27 Basf Lacke & Farben Loesliche vernetzbare copolymerisate auf der basis von vinylester-, vinyaromat- und acrylatmonomeren, verfahren zu ihrer herstellung sowie ihre verwendung in beschichtungsmitteln
DE4342672A1 (de) * 1993-12-15 1995-06-22 Akzo Nobel Nv Haftverbesserer
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ATE81658T1 (de) 1992-11-15
BR8907602A (pt) 1991-07-30
WO1990001502A1 (fr) 1990-02-22
EP0355408B1 (fr) 1992-10-21
DE3827587A1 (de) 1990-03-01
ES2052830T3 (es) 1994-07-16
CA1329302C (fr) 1994-05-03
US5229467A (en) 1993-07-20
DE58902498D1 (de) 1992-11-26
EP0355408A1 (fr) 1990-02-28

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