DE965597C - Method for bonding materials, in particular metals - Google Patents

Description

Method for bonding materials, in particular metals It is known to use polymerized vinyl compounds such as polystyrene, etc. in solvents to dissolve and thus to carry out gluing as usual by removing the solvent evaporates. It is also known to do the same with linear copolymers to proceed as they are in particular in the case of linear copolymers. Styrene and Maleic anhydride are available. All of these products are linear polymers, so Soluble in solvents and also thermoplastic, d. H. at higher temperatures there are no special adhesive values.

Furthermore, the interpolymerization of unsaturated polyesters, the can be produced by thermal condensation of unsaturated acids and glycols, known with vinyl compounds. However, such products have carboxyl groups as well as carboxyl groups a larger number of free hydroxyl groups, which considerably reduce the adhesive effect.

In patent 910 raq. unsaturated carboxyl-containing polyesters are treated, which arise from the fact that on saturated polyesters with terminal hydroxyl groups Unsaturated Carbonsättreanhydrides are added. Such 4 higher molecular ones unsaturated polyesters containing carboxyl groups can be mixed with monomeric vinyl compounds, such as styrene, are copolymerized in the presence of peroxides and as casting resins Find use.

It has now surprisingly been found that you can use materials from all Kind, especially metals, can bond very well, if one Mixtures these polymerizable compounds, one component of which consists of a carboxyl-containing Z # n, unsaturated condensation or essentially consisting of ester groups Polymerization product and its other component made of copolymerizable, There is unsaturated vinyl compounds at the point of adhesion for Mischpolymeri.sation brings. This method is particularly suitable for bonding metals, casting resins, Glass etc., with perfect bonding up to temperatures of 100 °, without the glued surfaces becoming detached.

Of course, linear unsaturated polyesters that carry free carboxyl groups at the ends. Such linear unsaturated, Carboxyl-containing polyesters can be prepared by known methods by condensation of excess amounts of dicarboxylic acids, maleic acids with glycols by thermal Esterification can be easily made.

The addition of unsaturated carboxylic acid anhydrides is limited also does not apply to branched polyesters containing hydroxyl groups. Of course they can also be linked to other high molecular weight hydroxyl group-bearing compounds, such as partially or completely saponified polymers or copolymers of vinyl acetate etc., attach and use mixed with vinyl compounds as adhesives.

If one builds into the mentioned unsaturated polyesters containing carboxyl groups, as suggested in patents 919,431 and 916,121, tertiary or secondary Amines, bonds can be made at room or slightly elevated temperatures make.

In general, when gluing, the procedure is that in the finished mixture of unsaturated, carboxyl-containing, higher molecular weight condensation or polymerization products and monomeric vinyl compounds peroxides dissolved and then the roughened with this ready-to-polymerize mixture connecting parts thinly coated with light pressure in the case of the peroxide decomposition turn cured at corresponding temperatures.

Casting resins, which are composed of higher molecular weight unsaturated, hydroxyl-containing polymerization or condensation products, as they are, for. B. are also proposed in the patent gio 124, etc., are not suitable as an adhesive. EXAMPLE 100 parts of a branched polyester which is produced from 2 mol of adipic acid, 0.5 mol of phthalic anhydride and 4 times a triol (e.g. hexanetriol) by thermal esterification and has an OH number of 230 and an acid number of 2.1 , it is heated to 120 ° C. and 38 parts of maleic anhydride are added. It is kept at from 120 to 125 ° C. for an hour and then 0.1 part of hydroquinone is added. When the temperature has fallen to 100 ° C., 59 parts of styrene are run in and the mixture is cooled to room temperature.

1% benzoyl peroxide is stirred into the solution capable of copolymerization. This ready-made solution can be used to bond metals, plastics, etc. ioo ° C can be done by removing the slightly roughened surfaces with a thin Covered film provided, immediately placed on top of one another and heated to 100 ° C for 10 minutes will.

The solution capable of copolymerization has an acid number of about SZ = iio to. 115. Aluminum overlap calculated kg / cma cm2 on i cm ' Tear values at 2o ° C 1. 282 1.2 236 2,333 1.4 238 3.283 1.2 236 4. 27 0 1.16 233 5- 3 0 5 1.25 244 at 6o ° 1. 26o 1.38 189 2. 123 o, 65 19 0 3,264 1.5 176 4. 222 1.1 202 5. 212 1.3 163 at 8o ° 1. 162 1.18 137 2. 2 0 3 1.35 15 0 3. 167 1.1 152 4. 125 o, 85 147 5. 19o 1.2 159 at ioo ° 1. 143 1.4 102 2.16 1.1 97 3. 120 1.2 zoo 4.140 1.2 117 5. 135 1.25 1o8 Example e The thermal esterification of 365 parts of adipic acid, 74 parts of phthalic anhydride, 48o parts of hexanetriol and 5 parts of p- (N-diphenyl) diethanolamine produces a branched polyester with an acid number of 1.8 and an OH number of 23o. After cooling to 12.51 ° C., 35 parts of maleic anhydride are added to 100 parts of this polyester and the mixture is stirred well at 25 ° C. for one hour. After the addition, 0.1 part of hydroquinone is added, the mixture is cooled to 100 ° C. and 59 parts of styrene are run in.

After adding i d / o benzoyl peroxide, they are somewhat roughened Thinly brushed metal parts, pressed together and heated to 50 ° C for 20 minutes. the Tear values correspond to the samples from example i. The peroxide-polyester solution lasts at room temperature for about 2 hours.

Claims (3)

PATENT CLAIMS: i. Method for bonding materials, in particular of metals, through copolymerization of unsaturated ones containing carboxyl groups Polyesters made from polyhydric alcohols, dibasic organic acids and maleic anhydride with unsaturated vinyl compounds at the adhesive point, characterized in that those preferably branched polyesters are used, which are composed of a carboxyl-containing, unsaturated condensation product containing essentially ester groups, those containing by reacting hydroxyl end groups, preferably branched Polyesters are obtained with maleic anhydride, the hydroxyl end groups containing Polyester by condensation of dibasic organic acids and polyvalent ones Alcohols are produced in a separate stage. 2. The method according to claim i, characterized in that the mixture of these components prior to gluing Peroxides, such as, in particular, benzoyl peroxide, cumene peroxide, etc., are added. 3. The method according to claim i, characterized in that such unsaturated carboxyl-containing'-condensation or Pc> polymerization products are used in which compounds with a tertiary or secondary nitrogen atom are incorporated. Considered publications: German patent application E 32g IV c / 39 c; British Patent No. 308,659; french Patent No. 859: 21: 2; U.S. Patent Nos. 1,975,246, 2,453,666; Delmonk, "The Technology of Adhesives", 1947, pp. 92 and 155.