CA1159990A - Process for the manufacture of hardenable copolymers and the use thereof - Google Patents
Process for the manufacture of hardenable copolymers and the use thereofInfo
- Publication number
- CA1159990A CA1159990A CA000378601A CA378601A CA1159990A CA 1159990 A CA1159990 A CA 1159990A CA 000378601 A CA000378601 A CA 000378601A CA 378601 A CA378601 A CA 378601A CA 1159990 A CA1159990 A CA 1159990A
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- Prior art keywords
- diester
- groups
- weight
- unsaturated
- hardenable
- Prior art date
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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
- C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
ABSTRACT
A process for the manufacture of hardenable copoly-mers which comprises reacting in a first single stage an olefinically unsaturated dicarboxylic acid anhydride with a polyhydric alcohol and a monoepoxy compound to form I) an olerinically unsaturated diester containing OH-groups and copolymerizing diester in a second stage with II) at least one unsaturated copolymerisable monomer free from COOH-groups and a hardenable binder for lacquers or coatings containing at least one co-polymer prepared according to said process.
A process for the manufacture of hardenable copoly-mers which comprises reacting in a first single stage an olefinically unsaturated dicarboxylic acid anhydride with a polyhydric alcohol and a monoepoxy compound to form I) an olerinically unsaturated diester containing OH-groups and copolymerizing diester in a second stage with II) at least one unsaturated copolymerisable monomer free from COOH-groups and a hardenable binder for lacquers or coatings containing at least one co-polymer prepared according to said process.
Description
9~0 A process for preparing copolymers by polymerisation of olefinically unsaturated diesters containing OH
groups with unsaturated monomers containing no free COOH groups has already been proposed, wherein the unsaturated diester used is a diester having two hydroxyalkyl groups, obtained in a previous first stage by reacting an anhydride of an olefinically unsaturated dicarboxylic acid with a polyhydric alcohol, to form a half-ester with free OH groups and further reacting the half-ester, in a second step, with a monoepoxide compound in the form of a glycidol, glycidyl ether or glycidyl ester, and wherein the hardenable reaction product thus obtained is isolated or is cured by the action of a curing agent. The use of the products manufactured by this method as hardenable binders for lacquers and/or coatings is also described.
This process and the products manufactured by the process have proved generally satisfactory.
However, there is a need to improve the process further.
This invention provides a process for the manufacture of hardenable copolymers by polymerisation of unsaturated esters with unsaturated polymerisable monomers which do not contain any free COOH groups, wherein the unsaturated ester used is an olefinically unsaturated diester containing OH groups, which is obtained by reacting an anhydride of an olefinica~ly unsaturated dicarboxylic acid with a polyhydric alcohol and with a monoepoxide compound, the olefinically unsaturated diester containing OH groups being obtained beforehand in a single stage by reacting an anhydride of the olefinically unsaturated dicarboxylic acid, the poly~ydric alcohol and the ~onoepoxide compound.
According to one ~articular embodiment o~ the invention, the reaction product containing the diester ~ 9 ~
which has OH groups may be mixed with an organic solvent which is inert under the reaction conditions, without any preliminary isolation of the diester, then heated to the desired polymerisation temperature and then copolymerised, in at least one further stage, with unsaturated polymerisable monomers, preferably with the addition of polymerisation initiators and possibly chain stoppers.
This invention simplifies the process considerably and saves not only work but also energy.
Examples of dicarboxylic acid anhydrides for the preparation of the diesters include the anhydrides of itaconic, citraconic, dimethylmaleic acid, and preferably the anhydride of maleic acid.
Examples of alcohols which may be used include those listed hereinafter.
Examples of epoxy compounds which may be used include alkylene oxides, such as ethylene oxide or propylene oxide; glycidol; glycidyl ethers of phenols, such as that of phenol itself, cresols or tert.-butyl-phenol;
glycidyl esters of saturated carboxylic acids; and preferably glycidyl esters of branched fatty acids of general formula H2C~-&H-CH2-0-C-R, O O
wherein R is the radical of a fatty acid branched in the ~-position, said acid having 8 to 16, preferably 4Be to 12 carbon atoms.
The molecular weight of the diesters is generally within the range of 250 to 1500, preferably 400 to 1250 and the OH number is within the range 280 to 450.
The temperature at which the diester formation is effected is generally 50 to 200, preferably 100 to 170C.
Copolymerisation of the intermediate products may be effected in one or more, but preferably two, steps, generally at 80 to 220, preferably 130 to 170, more particularly 140 to 160C, possibly without
groups with unsaturated monomers containing no free COOH groups has already been proposed, wherein the unsaturated diester used is a diester having two hydroxyalkyl groups, obtained in a previous first stage by reacting an anhydride of an olefinically unsaturated dicarboxylic acid with a polyhydric alcohol, to form a half-ester with free OH groups and further reacting the half-ester, in a second step, with a monoepoxide compound in the form of a glycidol, glycidyl ether or glycidyl ester, and wherein the hardenable reaction product thus obtained is isolated or is cured by the action of a curing agent. The use of the products manufactured by this method as hardenable binders for lacquers and/or coatings is also described.
This process and the products manufactured by the process have proved generally satisfactory.
However, there is a need to improve the process further.
This invention provides a process for the manufacture of hardenable copolymers by polymerisation of unsaturated esters with unsaturated polymerisable monomers which do not contain any free COOH groups, wherein the unsaturated ester used is an olefinically unsaturated diester containing OH groups, which is obtained by reacting an anhydride of an olefinica~ly unsaturated dicarboxylic acid with a polyhydric alcohol and with a monoepoxide compound, the olefinically unsaturated diester containing OH groups being obtained beforehand in a single stage by reacting an anhydride of the olefinically unsaturated dicarboxylic acid, the poly~ydric alcohol and the ~onoepoxide compound.
According to one ~articular embodiment o~ the invention, the reaction product containing the diester ~ 9 ~
which has OH groups may be mixed with an organic solvent which is inert under the reaction conditions, without any preliminary isolation of the diester, then heated to the desired polymerisation temperature and then copolymerised, in at least one further stage, with unsaturated polymerisable monomers, preferably with the addition of polymerisation initiators and possibly chain stoppers.
This invention simplifies the process considerably and saves not only work but also energy.
Examples of dicarboxylic acid anhydrides for the preparation of the diesters include the anhydrides of itaconic, citraconic, dimethylmaleic acid, and preferably the anhydride of maleic acid.
Examples of alcohols which may be used include those listed hereinafter.
Examples of epoxy compounds which may be used include alkylene oxides, such as ethylene oxide or propylene oxide; glycidol; glycidyl ethers of phenols, such as that of phenol itself, cresols or tert.-butyl-phenol;
glycidyl esters of saturated carboxylic acids; and preferably glycidyl esters of branched fatty acids of general formula H2C~-&H-CH2-0-C-R, O O
wherein R is the radical of a fatty acid branched in the ~-position, said acid having 8 to 16, preferably 4Be to 12 carbon atoms.
The molecular weight of the diesters is generally within the range of 250 to 1500, preferably 400 to 1250 and the OH number is within the range 280 to 450.
The temperature at which the diester formation is effected is generally 50 to 200, preferably 100 to 170C.
Copolymerisation of the intermediate products may be effected in one or more, but preferably two, steps, generally at 80 to 220, preferably 130 to 170, more particularly 140 to 160C, possibly without
- 2 -`11599!~
the co-use of solvents. It may be effected thermally.
Preferably, however, copolymerisation is carried out in the presence of catalysts, especially radical initiators, more particularly peroxides, e.g. di-S tert.-butylperoxide, dibenzoylperoxide, cumyl hydro-peroxide and azo compounds such as azo-bis-isobutyro-nitrile or the like. It is appropriate to use solvents or diluents, which may be put in first. Examples of solvents which may be used include high-boiling aliphatic and/or aromatic solvents having a boiling point of from 140 to 185C, such as mineral oils having a boiling point of 160 to 180~C, xylenes, butyl acetate, ethyleneglycol acetate monoethyl ether or the like. If desired, the copolymerisation may also be effected in the presence of chain stoppers such as, for example, alkanethiols such as n-dodecyl-mercaptan, in order to control the molecular weight.
Examples of copolymerisable monomers which may be employed include aromatic vinyl compounds, such as styrene, a-methylstyrene, the various vinyl-toluenes and divinylbenzenes (although the latter are generally only used in minor amounts); alkyl acrylates or methacrylates with 1 to 6, preferably 1 to 4 carbon atoms in the alkyl group, such as methyl, ethyl, n- or iso-propyl, n-, sec-, iso- or tert.butyl, the various pentyl and hexyl acrylates or methacrylates;
and hydroxy esters with 2 to 6 carbon atoms, such - as hydroxyethyl or hydroxypropyl acrylate and methacrylate, again either individually or in admixture. If polymer-isation is effected with a monomer mixture, thismixture appropriately contains at least 10 mol-%
and preferably not more than 70 mol-% of aromatic vinyl compounds, preferably styrene and/or not more than 20, preferably not more than 10 weight ~ o~ hydroxy-alkyl ester, based on the total monomer mixture.
Copolymerisation is appropriately continueduntil there is a conversion of at least 9~, preferably at least 98%.
In a preferred embodiment o the process according to the invention, a copolymer is prepared from a) 10 to 60 weight % ofadicarboxylic acid ester, preferably based on maleic anhydride, trimethylolpropane and a glycidyl ester of a branched fatty acid with 8 to 16, preferably 10 to 12 carbon atoms, b) 5 to 50 weight% of an ester of acrylic and/or methacrylic acid with a monohydric alcohol with 1 to 6, preferably 1 to 4 carbon atoms, c) 5 to 70 weight ~ of styrene, and d) 0 to 20 weight~ of an ester of acrylic and/or methacrylic acid with a dihydric alcohol with 2 to 6, preferably 2 to 4 carbon atoms.
The polyhydric alcohols which may be used as components of the acrylic or methacrylic acid esters are the same ones which may be used for the preparation of the half esters, namely, for example, diols such as ethyleneglycol, propanediol-1,2, propanediol-1,3, the various butane-, pentane- and hexanediols, such as butanediol-1~4, hexanediol-1,6, neopentylglycol, diethyleneglycol and dipropyleneglycol. It is also possible to use reaction products of polyols, such as, ~or example, glycerol, trimethylolethane and -propane, pentaerythritol, dipentaerythritol with isocyanate compounds or carboxylic acids, e.g. pentaery-thritol diesters with monocarboxylic acids, provided - that they contain two free OH groups per molecule.
The acid number of the copolymers may be from 2 to 20, for example, and the OH number may be, for example, from 50 to 200.
The scope of the invention also extends to the curing of the copolymer, for which various curing agents may be used, namely, for example, masked or free polyisocyanates, polycarboxylic acids, preferably in the form of anhydrides, amine resins and phenolic resins. Examples of polyisocyanates include di-to tetravalent isocyanates, such as toluylene diisocyanate, 7 = ~
9~
isophorone diisocyanate, hexamethylene diisocyanate, 2,4,6-triisocyanatotoluene, 4,4',4"-triisocyanato-triphenylmethane, 2,4,~'-triisocyanato-diphenylmethane, 2,2',5,5'-tetraisocyana~o-diphenylmethane and also trivalent isocyanates, which may be obtained, for example, by the addition of trimethylol propane to toluylene diisocyanate, a triisocyanate which may be prepared by reacting hexamethylene diisocyanate and water, or isocyanates with up to 4 free isocyanate qroups, such as may be obtained, for example, by reactinq toluylene diisocyanate and hexamethylene diisocyanate, or the masked products thereof with acetoacetic acid esters, for example, such as those of methanol, ethanol, propanols or butanols, or with E-caprolactam.
Examples of polycarboxylic acid hardeners which may be used include maleic acid, succinic acid, adipic acid, phthalic acid, trimellitic acid, pyromellitic acid or anhydrides of these acids, as well as low molecular oligomeric esters or polyesters with free COOH groups ~ If desired, a catalyst may also be added, preferred catalysts being organic metal compounds, such as dibutyl-tin dilaurate, dibutyl-tin oxide, cobalt naphthenate or octoate; or amines such as ethylene diamine and the homologues thereof, such as diethylene triamine, tetraethylene pentamine, terti~ary amines, such as triethylamine, tributylamine, dimethylaniline; but~ particularly alkanolamines, such as diethylethanolamine.
Instead of individual components, mixtures may also be used in all these cases.
- The hardening, particularly with polyisocyanates, may be carried out at ambient temperature. At elevated temperatures, it is predominantly the other above-mentioned hardeners, including masked isocyanates, which are used, whilst the amine and phenolic resins may also act as hardeners, for example, in the presence ~f acids, such as toluenesulphonic acid. The thermal
the co-use of solvents. It may be effected thermally.
Preferably, however, copolymerisation is carried out in the presence of catalysts, especially radical initiators, more particularly peroxides, e.g. di-S tert.-butylperoxide, dibenzoylperoxide, cumyl hydro-peroxide and azo compounds such as azo-bis-isobutyro-nitrile or the like. It is appropriate to use solvents or diluents, which may be put in first. Examples of solvents which may be used include high-boiling aliphatic and/or aromatic solvents having a boiling point of from 140 to 185C, such as mineral oils having a boiling point of 160 to 180~C, xylenes, butyl acetate, ethyleneglycol acetate monoethyl ether or the like. If desired, the copolymerisation may also be effected in the presence of chain stoppers such as, for example, alkanethiols such as n-dodecyl-mercaptan, in order to control the molecular weight.
Examples of copolymerisable monomers which may be employed include aromatic vinyl compounds, such as styrene, a-methylstyrene, the various vinyl-toluenes and divinylbenzenes (although the latter are generally only used in minor amounts); alkyl acrylates or methacrylates with 1 to 6, preferably 1 to 4 carbon atoms in the alkyl group, such as methyl, ethyl, n- or iso-propyl, n-, sec-, iso- or tert.butyl, the various pentyl and hexyl acrylates or methacrylates;
and hydroxy esters with 2 to 6 carbon atoms, such - as hydroxyethyl or hydroxypropyl acrylate and methacrylate, again either individually or in admixture. If polymer-isation is effected with a monomer mixture, thismixture appropriately contains at least 10 mol-%
and preferably not more than 70 mol-% of aromatic vinyl compounds, preferably styrene and/or not more than 20, preferably not more than 10 weight ~ o~ hydroxy-alkyl ester, based on the total monomer mixture.
Copolymerisation is appropriately continueduntil there is a conversion of at least 9~, preferably at least 98%.
In a preferred embodiment o the process according to the invention, a copolymer is prepared from a) 10 to 60 weight % ofadicarboxylic acid ester, preferably based on maleic anhydride, trimethylolpropane and a glycidyl ester of a branched fatty acid with 8 to 16, preferably 10 to 12 carbon atoms, b) 5 to 50 weight% of an ester of acrylic and/or methacrylic acid with a monohydric alcohol with 1 to 6, preferably 1 to 4 carbon atoms, c) 5 to 70 weight ~ of styrene, and d) 0 to 20 weight~ of an ester of acrylic and/or methacrylic acid with a dihydric alcohol with 2 to 6, preferably 2 to 4 carbon atoms.
The polyhydric alcohols which may be used as components of the acrylic or methacrylic acid esters are the same ones which may be used for the preparation of the half esters, namely, for example, diols such as ethyleneglycol, propanediol-1,2, propanediol-1,3, the various butane-, pentane- and hexanediols, such as butanediol-1~4, hexanediol-1,6, neopentylglycol, diethyleneglycol and dipropyleneglycol. It is also possible to use reaction products of polyols, such as, ~or example, glycerol, trimethylolethane and -propane, pentaerythritol, dipentaerythritol with isocyanate compounds or carboxylic acids, e.g. pentaery-thritol diesters with monocarboxylic acids, provided - that they contain two free OH groups per molecule.
The acid number of the copolymers may be from 2 to 20, for example, and the OH number may be, for example, from 50 to 200.
The scope of the invention also extends to the curing of the copolymer, for which various curing agents may be used, namely, for example, masked or free polyisocyanates, polycarboxylic acids, preferably in the form of anhydrides, amine resins and phenolic resins. Examples of polyisocyanates include di-to tetravalent isocyanates, such as toluylene diisocyanate, 7 = ~
9~
isophorone diisocyanate, hexamethylene diisocyanate, 2,4,6-triisocyanatotoluene, 4,4',4"-triisocyanato-triphenylmethane, 2,4,~'-triisocyanato-diphenylmethane, 2,2',5,5'-tetraisocyana~o-diphenylmethane and also trivalent isocyanates, which may be obtained, for example, by the addition of trimethylol propane to toluylene diisocyanate, a triisocyanate which may be prepared by reacting hexamethylene diisocyanate and water, or isocyanates with up to 4 free isocyanate qroups, such as may be obtained, for example, by reactinq toluylene diisocyanate and hexamethylene diisocyanate, or the masked products thereof with acetoacetic acid esters, for example, such as those of methanol, ethanol, propanols or butanols, or with E-caprolactam.
Examples of polycarboxylic acid hardeners which may be used include maleic acid, succinic acid, adipic acid, phthalic acid, trimellitic acid, pyromellitic acid or anhydrides of these acids, as well as low molecular oligomeric esters or polyesters with free COOH groups ~ If desired, a catalyst may also be added, preferred catalysts being organic metal compounds, such as dibutyl-tin dilaurate, dibutyl-tin oxide, cobalt naphthenate or octoate; or amines such as ethylene diamine and the homologues thereof, such as diethylene triamine, tetraethylene pentamine, terti~ary amines, such as triethylamine, tributylamine, dimethylaniline; but~ particularly alkanolamines, such as diethylethanolamine.
Instead of individual components, mixtures may also be used in all these cases.
- The hardening, particularly with polyisocyanates, may be carried out at ambient temperature. At elevated temperatures, it is predominantly the other above-mentioned hardeners, including masked isocyanates, which are used, whilst the amine and phenolic resins may also act as hardeners, for example, in the presence ~f acids, such as toluenesulphonic acid. The thermal
3~3~0 hardeniny is generally effected within 10 to 30 minutes at 120 to 200C. The addition of catalysts, e.~.
metal compounds such as dibutyl-tin dilaurate and/or amines, such as tertiary alkanolamine, e.g. diethylethanol-amine, may be particularly advantageous when isocyanatesare used.
The hardenable binder may also be combined with conventional pigments, fillers and/or additives.
Even if the products obtained according to the invention contain only a minor proportion of hydroxyalkyl esters of unsaturatèd acids, or even none at all, once they are cured with the curing agents, hardened coatings are obtained which are at least e~uivalent to the known coatings based on acrylate resins containing hydroxyalkyl esters, but in general the coatings accordin`g to ~he invention are surprisingly superior in their technical coating properties. Thanks to the greater possibility of variation and choice of reaction partners in the production of the copolymers, this invention makes it possible to select the optimum systems for the purpose intended. Moreover, the solubility of the polymers is improved by the incorporation of the groups of unsaturated dicarboxylic acids, such as maleic acid esters, in the acrylate-containing systems.
As a result, solvent-containing systems can be produced having a higher solids content than was possible - with the acrylate resins used hitherto, and the systems are therefore environmentally more acceptable.
The products obtained according to the invention may be used for paints and/or coatings for external use and for linings, and also, for example, as a corrosion proofing for various objects, particularly those which are exposed to atmospheric influences, such as in building construction, vehicles and vehicle parts, e.g. bodywork, and for domestic appliances and electrical equipment and components thereof.
They have good adhesion properties to substrates consisting of plastics and metals, such as copper, brass, zinc or iron alloys. Moreover, they have good flow qualities when applied as coatings. The hardened coatings are distinguished by a high gloss, good elasticity, very good weathering resistance and colour stability. The products obtained according to the invention which are hardenable at ambient temperature are particularly suitable for coating construction materials, preferably flooring, e.g.
based on cement and concrete. Moreover, the products obtained according to the invention are suitable for use as adhesives, having the advantages of good solubility and consequently a greater solids content.
The following non-limiting Examples serve to lS illustrate the invention. In the examples ~ refers to weight % and T refers .o parts by weight.
1~9990 `
Examples 1) to 3) Maleic anhydride, trimethylolpropane and the glycidyl ester of a fatty acid` with 10 carbon atoms branched in the -position are heated to 100C, with 5 stirring. After a short time, the internal temperature ri~es to 140C, but after about 30 minutes it falls again. The acid number of the reaction mixture is then 20. It is mixed with the desired solvent or mixture of solvents (e.g. xylene, mixtures of aromatics with a boiling point of 165 to 175C, butyl acetate) and heated to the desired polymerisation temperature (e.g. 140C). At this temperature, first of all a mixture of styrene, initiator and, optio~ally chain stopper are added over 3 hours and then a mixture of one or more methacrylic acid esters, styrene, initiator and chain stopp~ are uniformly added over 3 hours.
The mixture is left to polymerise for a further 2 hours at 175C.
The reaction components and the proportions used are shown in thè Table which follows:-Example 1 2 3 Maleic anhydride 5.3 4.6 4.0 Trimethylolpropane - 7.3 6.3 5.4 Glycidyl ester 13.3 11.7 10.0 Xylene 20 20 20 Alkyl-aromatic mineral oil*) 10 10 10 Butyl acetate 10 10 10 Styrene 16.1 16.1 16.1 Di-tert-butylperoxide 0.3 0.3 0.3 Dodecyl mercaptan 0.2 0.2 0.2 Hyd`roxyethyl methacrylate - 2.7 5.4 Methyl methacrylate 12.1 12.7 13.2 Styrene 4.9 4,9 4.9 Di-tert-butylperoxide 0.3 0.3 0.3 Dodecyl mercaptan 0.2 0.2 0.2 Polymerisation temperature (C) 140 140 140 Solids content % (1 hour at 125C) 59.6 60.5 60.5 Quantity of acid (mg KOH/g 20 solid resin) 6 6 6 Hydroxyl number (mg KOH/g solid resin) 150 155 155 Viscosity mPa.s (50% in xylene) 740 ô80 lOôO
Colour number -25 *) Boiling range 160 to 165C.
1~i9990 Preparation of coatinq compositions Coating compositions having the following composition are prepared from the solutions of the copolymers:
Example 1 2 3 Copolymer solution 70.80 69.52 69.52 Dibutyl tin dilaurate ~1% in xylene) 0.23 0.23 0.23 Diethylethanolamine 0.38 0.38 0.38 Silicone oil (1% in xylene) 1.00 1.00 1.00 10 Reaction product of hexamethylene diisocyanate and water (75% in ethyleneglycol monoethyl ether acetate) 27.59 28.87 28.87 The polymer solutions are adjusted to a viscosity (DIN 53211/20C) of 45s by the addition of a mixture of solvents consisting of xylene, an aromatic mixture of hydrocarbons (boiling range 165 to 175C), butyl acetate and ethyleneglycol monoethyl ether acetate (weight ratio 40:25:20:15), and then the solutions are applied in a wet layer thickness of lOO~um to sheets of glass and sheet steel. The films are dried in the air at ambient temperature.
0`
Technical tests on the coatings Example ` 1 2 3 Dry so that no dust adheres, min. 21 18 20 Tbuch-Dry, min. 120 120 120 Pendulum hardness according to Kanig, DIN 53157 after 24 hours 85 80 77 Er ichsen cupping DIN 53156 `
af ter 10 days 8 . 8 8. 8 8 . 5 Resistance towards gasoline, min.
after 10 days ~30 ~30 ~30 Solids content %
(1 hour at 125C) Sl.3 51.8. 50.5
metal compounds such as dibutyl-tin dilaurate and/or amines, such as tertiary alkanolamine, e.g. diethylethanol-amine, may be particularly advantageous when isocyanatesare used.
The hardenable binder may also be combined with conventional pigments, fillers and/or additives.
Even if the products obtained according to the invention contain only a minor proportion of hydroxyalkyl esters of unsaturatèd acids, or even none at all, once they are cured with the curing agents, hardened coatings are obtained which are at least e~uivalent to the known coatings based on acrylate resins containing hydroxyalkyl esters, but in general the coatings accordin`g to ~he invention are surprisingly superior in their technical coating properties. Thanks to the greater possibility of variation and choice of reaction partners in the production of the copolymers, this invention makes it possible to select the optimum systems for the purpose intended. Moreover, the solubility of the polymers is improved by the incorporation of the groups of unsaturated dicarboxylic acids, such as maleic acid esters, in the acrylate-containing systems.
As a result, solvent-containing systems can be produced having a higher solids content than was possible - with the acrylate resins used hitherto, and the systems are therefore environmentally more acceptable.
The products obtained according to the invention may be used for paints and/or coatings for external use and for linings, and also, for example, as a corrosion proofing for various objects, particularly those which are exposed to atmospheric influences, such as in building construction, vehicles and vehicle parts, e.g. bodywork, and for domestic appliances and electrical equipment and components thereof.
They have good adhesion properties to substrates consisting of plastics and metals, such as copper, brass, zinc or iron alloys. Moreover, they have good flow qualities when applied as coatings. The hardened coatings are distinguished by a high gloss, good elasticity, very good weathering resistance and colour stability. The products obtained according to the invention which are hardenable at ambient temperature are particularly suitable for coating construction materials, preferably flooring, e.g.
based on cement and concrete. Moreover, the products obtained according to the invention are suitable for use as adhesives, having the advantages of good solubility and consequently a greater solids content.
The following non-limiting Examples serve to lS illustrate the invention. In the examples ~ refers to weight % and T refers .o parts by weight.
1~9990 `
Examples 1) to 3) Maleic anhydride, trimethylolpropane and the glycidyl ester of a fatty acid` with 10 carbon atoms branched in the -position are heated to 100C, with 5 stirring. After a short time, the internal temperature ri~es to 140C, but after about 30 minutes it falls again. The acid number of the reaction mixture is then 20. It is mixed with the desired solvent or mixture of solvents (e.g. xylene, mixtures of aromatics with a boiling point of 165 to 175C, butyl acetate) and heated to the desired polymerisation temperature (e.g. 140C). At this temperature, first of all a mixture of styrene, initiator and, optio~ally chain stopper are added over 3 hours and then a mixture of one or more methacrylic acid esters, styrene, initiator and chain stopp~ are uniformly added over 3 hours.
The mixture is left to polymerise for a further 2 hours at 175C.
The reaction components and the proportions used are shown in thè Table which follows:-Example 1 2 3 Maleic anhydride 5.3 4.6 4.0 Trimethylolpropane - 7.3 6.3 5.4 Glycidyl ester 13.3 11.7 10.0 Xylene 20 20 20 Alkyl-aromatic mineral oil*) 10 10 10 Butyl acetate 10 10 10 Styrene 16.1 16.1 16.1 Di-tert-butylperoxide 0.3 0.3 0.3 Dodecyl mercaptan 0.2 0.2 0.2 Hyd`roxyethyl methacrylate - 2.7 5.4 Methyl methacrylate 12.1 12.7 13.2 Styrene 4.9 4,9 4.9 Di-tert-butylperoxide 0.3 0.3 0.3 Dodecyl mercaptan 0.2 0.2 0.2 Polymerisation temperature (C) 140 140 140 Solids content % (1 hour at 125C) 59.6 60.5 60.5 Quantity of acid (mg KOH/g 20 solid resin) 6 6 6 Hydroxyl number (mg KOH/g solid resin) 150 155 155 Viscosity mPa.s (50% in xylene) 740 ô80 lOôO
Colour number -25 *) Boiling range 160 to 165C.
1~i9990 Preparation of coatinq compositions Coating compositions having the following composition are prepared from the solutions of the copolymers:
Example 1 2 3 Copolymer solution 70.80 69.52 69.52 Dibutyl tin dilaurate ~1% in xylene) 0.23 0.23 0.23 Diethylethanolamine 0.38 0.38 0.38 Silicone oil (1% in xylene) 1.00 1.00 1.00 10 Reaction product of hexamethylene diisocyanate and water (75% in ethyleneglycol monoethyl ether acetate) 27.59 28.87 28.87 The polymer solutions are adjusted to a viscosity (DIN 53211/20C) of 45s by the addition of a mixture of solvents consisting of xylene, an aromatic mixture of hydrocarbons (boiling range 165 to 175C), butyl acetate and ethyleneglycol monoethyl ether acetate (weight ratio 40:25:20:15), and then the solutions are applied in a wet layer thickness of lOO~um to sheets of glass and sheet steel. The films are dried in the air at ambient temperature.
0`
Technical tests on the coatings Example ` 1 2 3 Dry so that no dust adheres, min. 21 18 20 Tbuch-Dry, min. 120 120 120 Pendulum hardness according to Kanig, DIN 53157 after 24 hours 85 80 77 Er ichsen cupping DIN 53156 `
af ter 10 days 8 . 8 8. 8 8 . 5 Resistance towards gasoline, min.
after 10 days ~30 ~30 ~30 Solids content %
(1 hour at 125C) Sl.3 51.8. 50.5
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the manufacture of hardenable copolymers which comprises reacting in a first single stage an olefinically unsaturated dicarboxylic acid anhydride with a polyhydric alcohol and a monoepoxy compound to form I) an ole-finically unsaturated diester containing OH-groups and having an OH-number in the range from 280 to 450, and copolymerizing the diester in a second stage with II) at least one unsaturated copolymerisable monomer free from CCOH-groups.
2. A process as claimed in claim 1, wherein the reaction product compris-ing the diester having OH-groups is immediately admixed - without isolation of the diester - with an organic solvent being inert under the reaction conditions and the mixture is then heated to the desired polymerisation temperature and the diester is copolymerized in at least one further step with the unsaturated mono-mers alone or in the presence of at least one substance selected from the group consisting of a polymerisation initiator and combinations thereof with a chain stopper.
3. A process as claimed in claim 1, wherein the diester containing OH-groups has been prepared at a temperature between 50 and 200°C.
4. A process as claimed in claim 1 or 2 or 3, wherein the copolymerisation is performed with a mixture of monomers containing at least 10 mol-% of aromatic vinyl compounds.
5. A process as claimed in claim 1 or 2 or 3 wherein the copolymerisation is at least partially performed in the presence of a radical initiator.
6. A process as claimed in claim 1 or 2 or 3 wherein a copolymer consist-ing of a) between 10 and 60% by weight of the dicarboxylic diester, b) between 5 and 50% by weight of an ester of acrylic acid, methacrylic acid or a combinatian of both with a monohydric alcohol having from 1 to 6 C-atoms, c) between 5 and 70% by weight of styrene and d) between 0 and 20 % by weight of an ester of acrylic acid, methacrylic acid or of both with a dihydric alcohol having from 2 to 6 C-atoms is prepared.
7. A process as claimed in claim 1 or 2 or 3 wherein the copolymerisation is performed until a yield of at least 95 % is obtained.
8. A process for the manufacture of hardenable copolymers which comprises reacting in a first single stage an olefinically unsaturated dicarboxylic acid anhydride with a polyhydric alcohol and a monoepoxy compound to form I) an ole-finically unsaturated diester cantaining OH-groups and having an OH-number in the range of frcm 280 to 450, and copolymerizing the diester in a second stage with II) at least one unsaturated copolymerisable monomer free from COOH-groups, wherein the diester containing OH-groups has been prepared at a temperature be-tween 50 and 200 & and at least partially in the presen oe of a radical initiator until a yield of at least 95 % is obtained and wherein a copolymer consisting of a) between 10 and 60 % by weight of the dicarboxylic diester, b) between 5 and 50 % by weight of an ester of acrylic acid, methacrylic acid or a combination of both with a monohydric alcohol having from 1 to 6 C-atoms, c) between 5 and 70% by weight of styrene and d) between 0 bis 20% by weight of an ester of acrylic acid, methacrylic acid or of both with a dihydric alcohol having from 2 to 6 C-atcms is prepared.
9. A hardenable binder for lacquers or coatings containing at least one copolymer prepared according to the process as claimed in claim 1 or 2 or 8.
10. A hardenable binder for lacquers or coatings containing at least one copolymer prepared according to the process as claimed in claim 1 or 2 or 8 in combination with a polyisocyanate as a hardener.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3020524A DE3020524C2 (en) | 1980-05-30 | 1980-05-30 | Process for the preparation of curable copolymers |
| DEP3020524.4 | 1980-05-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1159990A true CA1159990A (en) | 1984-01-03 |
Family
ID=6103561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000378601A Expired CA1159990A (en) | 1980-05-30 | 1981-05-29 | Process for the manufacture of hardenable copolymers and the use thereof |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0041209A1 (en) |
| JP (1) | JPS5721412A (en) |
| CA (1) | CA1159990A (en) |
| DE (1) | DE3020524C2 (en) |
| ES (1) | ES502472A0 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090894A (en) * | 1998-12-18 | 2000-07-18 | Ppg Industries Ohio, Inc. | Hydroxy-functional copolymer by reacting epoxy with ≧C8 monocarboxylic acid/dicarboxylic ester copolymer |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3504336A1 (en) * | 1985-02-08 | 1986-08-14 | Hoechst Ag, 6230 Frankfurt | POLYMERIZABLE CARBAMOYLOXYALKYLDICARBONIC ACID ESTERS CARRYING HYDROXYL GROUPS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| DE3504337A1 (en) * | 1985-02-08 | 1986-08-14 | Hoechst Ag, 6230 Frankfurt | CURABLE COPOLYMERISATE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| US5612416A (en) * | 1995-10-10 | 1997-03-18 | Ppg Industries, Inc. | Unsaturated hydroxy diester copolymers and their use in coating compositions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6704630A (en) * | 1967-03-31 | 1968-10-01 | ||
| DE2907997C2 (en) * | 1979-03-01 | 1982-04-15 | Hoechst Ag, 6000 Frankfurt | Process for the preparation of curable copolymers |
-
1980
- 1980-05-30 DE DE3020524A patent/DE3020524C2/en not_active Expired
-
1981
- 1981-05-23 EP EP81103984A patent/EP0041209A1/en not_active Withdrawn
- 1981-05-25 ES ES502472A patent/ES502472A0/en active Granted
- 1981-05-28 JP JP8021781A patent/JPS5721412A/en active Granted
- 1981-05-29 CA CA000378601A patent/CA1159990A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090894A (en) * | 1998-12-18 | 2000-07-18 | Ppg Industries Ohio, Inc. | Hydroxy-functional copolymer by reacting epoxy with ≧C8 monocarboxylic acid/dicarboxylic ester copolymer |
| US6284855B1 (en) | 1998-12-18 | 2001-09-04 | Ppg Industries Ohio, Inc. | Copolymer of monocarboxylic acid with at least 8C and unsaturated dicarboxylic ester |
Also Published As
| Publication number | Publication date |
|---|---|
| ES8203924A2 (en) | 1982-04-01 |
| EP0041209A1 (en) | 1981-12-09 |
| DE3020524C2 (en) | 1983-10-27 |
| JPH0134252B2 (en) | 1989-07-18 |
| ES502472A0 (en) | 1982-04-01 |
| JPS5721412A (en) | 1982-02-04 |
| DE3020524A1 (en) | 1981-12-10 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |