DE1645636A1 - Process for the preparation of copolymers containing maleic acid monoureide and coating agents containing them - Google Patents

Description

-ING. H.-J. MOOER

t'attntanwalt
8t.-li '^ ⁽ ' ^{llEil 80}
ecii.-.- "" - ^ "- ^^ BiOVA RESIN

⁴⁴³ ^ ESELLSCHAFT P 16 45 636. j

in Vienna (Austria), _u October 1969

Johannesgasse 14

Process for the production of copolymers containing maleic acid monoureide and coating agents containing them.

The invention relates to the production of copolymers from maleic acid monoureide (I) with other copolymerizable compounds and the use of such copolymers . for the production of coating agents.

(I) H-C = C-C

1 I.
HOOC CONH-CO-NH ₂

According to French patents nos. 795.414 and 813.544 it is known to implement copolymers of maleic anhydride with urea. The end products are in terms of their Composition not further characterized. Compared to these processes, the copolymerization with maleic acid monoureide offers the advantage that precisely known amounts of ureide are incorporated and thus the properties of the end products are targeted can be adjusted.

In principle, the incorporation of maleic acid monoureide into polymers of various types, both through the presence of the carboxyl group and the presence of the ureide group, results in crosslinking possibilities, whereby the ureid group, like an amide group, is capable of further reactions through reaction with aldehydes and alcohols, amines or amides.

009843/1778

-Z-

As comonomers for the preparation of the copolymers according to the invention are very generally copolymerizable vinyl and vinylidene compounds, such as (meth) acrylic acid, styrene, Maleic acid, as well as the homologues and derivatives of the compounds mentioned.

The known process of polymerization in is particularly suitable for the production of the products according to the invention Solution. The solvents used are e.g. alcohols, dimethylformamide, Diacetone alcohol, water and glycol monoethers are suitable, the usual peroxides or azo compounds are suitable as accelerators. The use of regulators to reduce the molecular weight is possible.

The ureid groups of the copolymer can optionally with Formaldehyde are converted to methylol groups or in the presence of alcohols to ureide methylene alkyl ethers, whereby the copolymers Obtain self-crosslinking properties.

The amount of formaldehyde is generally about 0.5 2.5 mol. Per 1 mol of maleic acid monoureide, the formaldehyde gaseous or dissolved in water or an organic solvent, preferably butanol, or as paraformaldehyde for Action can be brought.

The alcohols suitable for etherification have preferred

wise 1 - 6 carbon atoms, whereby glycol monoethers, e.g. Ethylene glycol monoethyl ether, come into question. The water of reaction is advantageously removed during the reaction, e.g. by circling.

If sufficient acid groups are provided, which come either only from maleic acid monoureide or partly from copolymerized acid or partly from saponification of ester or amide groups, the polymers are water-soluble as salts. When the polymers according to the invention are used as coating agents, this offers many advantages, since water is cheap, non-flammable and non-flammable

009843/1776

is toxic solvent, and on the other hand the deposition of resins from aqueous solutions. Electrophoresis becomes possible.

On the other hand, interferes with the copolymerization with maleic acid monoureide introduced acid content, the acid groups can be obtained by reacting the polymer with alkoxy groups Compounds, e.g. with ethylene oxide, are wholly or partially converted into oxyester groups.

If the polymers produced according to the invention are condensed in alcoholic solution with formaldehyde or such releasing substances, groups are formed which crosslink through the action of heat (approx. 1 kO - 180 ° C.). This cross-linking has a beneficial effect on the hardness, elasticity and chemical resistance of the coatings.

To the cross-linking at lower temperatures, preferably at 100 - 150 ⁰ C to run, melamine, urea or benzoguanamine are in amounts of 5 - 30 $ based on the Maleinsäuremonoureid copolymer - were added.

The resins according to the invention are suitable for modifying the resins Epoxy, acrylic and alkyd resins.

The following examples illustrate the invention. All data relate to parts by weight.

Example 1:

20 parts of Malexnsauremonoureid (ureid) are dissolved in 9-0 parts of ethylene glycol monomethyl ether in the heat and a Mixture of 30 parts of styrene and 15 parts of butyl acrylate and 35 parts of ethyl acrylate with 1 part of di-tert. Butyl peroxide and 0.7 parts of tert. Dodecyl mercaptan are added, added dropwise over the course of 2 hours, always refluxing must rule. After two and again two hours, 0.5 parts of di-tert-butyl peroxide are added, whereupon the Polymerization has ended. 8 parts of paraformaldehyde are added

009843/1776

and the water of reaction circulates from within two hours. Finally, peel the solution down to $ 70 solid of the solvent concentrated in vacuo and diluted to 50 $ by the addition of diacetone alcohol.

The resin is pigmented with X10 “, applied to sheet metal and ^{baked at 170 °} C. for 30 minutes. The film is hard, glossy and elastic (varnish A).

For example, an epoxy resin with an epoxy equivalent is added to the resin between 450 and 525 and a commercially available, Melamine resin partially etherified with butanol in proportion 75 ί 10; 15, applies to sheet metal and burns in for 30 minutes at 140 ° C, which also creates a hard, shiny one and elastic film (varnish B).

A. Gloss ¹ ' 2)
Impact test ' Surfaces-
hardness3) Pendulum
Persoz paint B. 89 15th 3 H 262 " paint 92 15th 3 H 269 "

1) Glossmeter according to Lange

2) 1 kg from 1 m height; 10 best value, 50 worst value

3) pencil hardness

Example 2:

A polymer which is not reacted with formaldehyde is produced analogously to Example 1.

After pigmentation, the resin was mixed with an epoxy resin and a melamine resin and baked at 140 ° C. for 30 minutes. The film was hard and elastic (impact sample 22, pendulum hardness 247 "). ^The gloss was weaker than in Example 1, namely 78.

009843 / 177B

Example 3 '

20 parts of ureid were dissolved in 50 parts of hot ethylene glycol monomethyl ether, cooled and treated with 25 parts of a glycidyl esters of a synthetic tertiary carboxylic acid of the general formula R-C-O- CH "- CH - CH_, in which R is a

Ί. 2 n> s 2

0 0

branched aliphatic hydrocarbon with 8-10 carbon atoms is added. To this mixture, 20 parts of styrene, 2 parts of methacrylic acid, 58 parts of ethyl acrylate, 0.8 parts of tert. Dodecyl mercaptan and 1 part di-tert. Butyl peroxide is added and the total mixture is polymerized until the theoretical solids content is reached. 7 parts of paraformaldehyde were then added, the solution was brought to reflux and the water of reaction was removed from the system. It is diluted with a mixture of butanol-ethylene glycol monoethyl ether to 50 io.

By using the above-mentioned glycidyl ester, the acid number is reduced to 31.

The non-blended resin showed during baking (30 minutes at 170 ⁰ C) results in good elasticity and surface hardness, a pendulum hardness of 23I ". The gloss was 79 ·

The resin mixed with an epoxy and melamine resin (30 Baked in minutes at 140 ° C.) was also elastic and shiny and had a pendulum hardness of 145 ".

Example k:

20 parts of ureid

0 parts of 4-oxy-butyl maleic acid 15 parts of styrene

45 parts of ethyl acrylate

1 part di-tert. Butyl peroxide

are dissolved in 90 parts of ethylene glycol monomethyl ether and the polymerization was initiated by heating to reflux. To complete the polymerization are still

009843/1776

- 6 two times 0.5 part each of di-tert. Butyl peroxide yielded.

After the end of the polymerization, 7 parts of paraformaldehyde are added and the water of reaction is removed from the system at the reflux temperature. The solution is largely concentrated by applying a vacuum, by adding a mixture of butanol-ethylene glycol monoethyl ether-diacetone alcohol the solids content is set to $ 50 and the resin is neutralized with diethanoiamine. It is mixed with a melamine resin in a ratio of 8: 2. Water can be used to dilute to spray viscosity. That Resin is pigmented and applied to sheet metal. After baking at 140 ° C it gives hard, shiny and elastic ones Films with particularly good surface hardness.

009843/1776

Claims (3)

Patent claim before: . Process for the production of copolymers from alpha-beta ethylenically unsaturated monomers, characterized in that malexic acid monoureide is polymerized with other copolymerizable vinyl compounds and, if appropriate, the copolymer is reacted with formaldehyde, if appropriate in the presence of alcohols. 2. The method according to claim 1, characterized in that the polymers with alkylene oxides forming "wn oxyester groups implemented. 3. The method according to claim 1, characterized in that the Copolymers can be converted into water-soluble salts by partial or complete neutralization. H. Use of the copolymers prepared by copolymerization of malexic acid monoureide with other copolymerizable vinyl compounds and optionally modified with formaldehyde and optionally alcohols for the production of coating agents, optionally after mixing with hardening components such as melamine and / or epoxy resins. 009843/1776