SE123724C1 - - Google Patents

Description

Inventors: D. Atherton and W. Charlton.

Priority requested from 2 October 1946 (UK).

The present invention relates to a process for the production of new resinous condensation products and is particularly relevant to the production of resinous condensation products which are soluble in oils and especially in drying oils, as well as of varnishes made from said condensation products.

It has already been proposed to react a phenol with the condensation product of an aminotriazine, a compound containing at least one alcohol group and an aldehyde or a substance which releases aldehyde.

It has been found according to the invention that the effect of certain condensation products of the kind mentioned above, namely certain etherified melamine-formaldehyde condensation products with certain phenols, gives new resinous condensation products which are soluble in oils especially in drying oils to form varnishes of excellent breathability.

According to the present invention there is provided a process for the preparation of novel oil-soluble resinous condensation products, which process consists in heating an etherified melamine-formaldehyde condensation product together with at least half of the chemically equivalent amount of a phenol in which one or two of the layers o, phenol group Or or aro unsubstituted.

The chemical duty was no longer used on a chemically equivalent amount of the phenol. Excellent results have been obtained if a mixture of the etherified melamine formaldehyde condensation product is used and approximately two thirds of the chemically equivalent amount of phenol.

The etherified melamia-formaldehyde condensation product is suitably obtained by etherification of a methylol-melamine, containing several to three methylol groups per molecule. The etherification is usually carried out in the presence of a relatively large amount of an acidic catalyst, since this has the tendency of the reaction product to avoid self-condensation. Suitable condensation products Concerned ether hexamethylol melamine and the etherified derivatives of products of lesser composition, which can be obtained by a reaction between less On 6 but more than 3 molecular amounts of formaldehyde and melamine. The substances are suitably etherified with the aid of monohydric alcohols, e.g. lower aliphatic alcohols such as methyl, ethyl, propyl, butyl, amyl and beta-ethoxyethyl alcohol. The phenols which are intended to be used in the process site of the present invention are, as stated above, those in which one or two of the layers o, o and p in the phenol group Or or Oro are unsubstituted. Bet viii in other words, that the phenol may contain in addition to the phenol hydroxyl group a substituent in one or hada o-layers, in the p-layer or in an o-layer and in the p-layer and in each case the joke phenol may or may contain substituents in m-lagena. Lampliga specific phenols Oro exemeplyis 3-methyl- 4: 6-di-tertiar-butylphenol, o-cresol, p-cresol, p-ethylphenol, p-tertiar-butylphenol, p-octylphenol, p-cyclohexylphenol, p-phenylphenol and a mixture of phenols, obtained by alkylation of technical cresols with diisobutylene.

The phenol used should suitably be one in which the p-layer Or is substituted, since the varnishes formed from the condensation products produced therefrom according to the present method have better drying properties and color On similar varnishes made of phenols which lack a substituent in the p-layer.

The chemically elivival amounts of the constituents intended for use in the form of the present invention are determined by reference to the phenol hydroxyl group, in which phenol was used, and by reference to the etherified methylol groups, if etherified melamine formaldehyde condensation products are used.

The conditions under which the process according to the present invention is carried out can be varied according to the nature of the product which it is desired to obtain. The procedure is usually carried out by heating the reagents together in a suitable inert solvent, e.g. in a carbon monoxide solvent, for example toluene or xylene. However, if desired, the welding agent can be omitted. If said Onskas, one can ayen use a condensing agent. Thus an acidic condensing agent may be added to the reaction mixture, e.g. an organic or an inorganic acid or a compound which falls under prehistoric reaction conditions, said that it is Midas acids. Particularly suitable, sum a condensing aro Los-for- and oxalic acid.

Alternatively, other condensing agents may also be used, e.g. sodium, potassium or ammonium carbonate. If desired, a condensing agent does not need anyandas.

The reaction is usually carried out by mixing the constituents with a solvent and then heating to such a temperature that the solvent is distilled, which distillation, if desired, can be accelerated by applying a reduced pressure or by allowing a stream to inert. gas e.g. carbon dioxide or kvaye, pass through the reaction mixture. The application of a reduced pressure during the distillation is advantageous, since the products formed thereby obtain a better color. The temperature is then suitably kept in order to complete the reaction. Suitable temperatures for the final heating am e.g. such, which are between 10 and 160 ° C. The condensation products obtained according to the present procedure dissolve when boiled in drying oils, e.g. heavy oil or linseed oil or mixtures ay these. The formed solutions are varnishes with good color and good resistance to yatten, acids and alkalis, even with drying ability, often with excellent drying ability.

The invention is claimed but not limited by the following examples, in which parts and percentages are by weight.

Example 1.

A mixture of 60 parts of hexamethoxymethylmelamine, 90 parts of p-tertiar-butylphenol, 60 parts of toluene and 0 parts of phosphoric acid is stirred and gently boiled for one hour in a reaction vessel equipped with a reflux condenser. The reaction vessel is then fitted with a distillation condenser in the stable of the surface condenser and separated by a gas supply tube which extends below the surface of the mixture. The mixture is heated with stirring up to 1 ° C for 45 minutes while a carbon dioxide stream of carbon dioxide is passed through the mixture. Hdrunder distills off most of the ay toluene. The temperature is then raised to 150-155 ° C for one hour. A light yellow oil is obtained, which on cooling gives a light yellow, brittle resin.

Delta resin dissolves Yid boiling in drying oils and gives varnishes with good drying ability. Fihner or foils obtained ax such varnishes haya good color () eh good resistance to yerkan ay yatten, acids and alkalis.

Example 2.

A mixture of 25 parts of hexamethoxymethylmelamine, 75 parts of o-cresol, 22 parts of toluene and 0.05 parts of phosphoric acid is stirred in an atmosphere of carbon dioxide and heated to 140 DEG C. for 30 minutes in a condenser equipped with a condenser containing toluene. can be distilled. The mixture is then maintained at 140 DEG C. for 4 hours and the temperature is then raised to 150 DEG C. and heating is continued for a further 4 minutes. After cooling, a liquid liquid condensation product is obtained, which on cooling dissolves in drying oils and gives varnishes with drying ability.

Example 3.

A mixture of 40 parts of hexamethoxymethylmelamine, 88 parts of 3-methyl-4: 6-di-tertiar-butyllenol, 35 parts of toluene and 0.05 parts of phosphoric acid is heated under stirring for one hour at 100 ° C with any other liquid refrigerant and then under Ire hours Yid 130 ° G in an atmosphere of carbon dioxide under such conditions that toluene can be separated from the reaction mixture. In such a quiet Yid cooling, a viscous liquid is obtained, which dissolves in drying oils and gives varnishes with good drying ability.

Example 4.

A mixture of 40 parts of hexamethoxymethylmelamine, 82.5 parts of p-octylphenol, 35 parts of toluene and 0.0 parts of phosphoric acid is stirred and heated to 1000 g for one hour in a reaction vessel equipped with a reflux condenser. The temperature is then raised to 140 ° C and heating is continued for 1 hour at 140 ° C under such conditions that toluene distills. In this way, a light yellow solid resin is obtained after cooling, which dissolves during drying in drying oils and gives varnishes with good drying ability.

Example 5.

A mixture of 390 parts of hexamethoxymethylmelamine, 900 parts of p-tertiar-butylphenol, 370 parts of toluene and 1.5 parts of phosphoric acid is heated and stirred for one hour at 100 DEG-1049 DEG C. and then at 150 DEG-157 DEG C. during a bath for a quarter of an hour under such conditions that toluene distills off, a light yellow resin is thus obtained on cooling, which on boiling dissolves in drying oils and gives varnishes with good drying ability. Varnishes obtained from delta resin are somewhat similar. These are obtained from the resin described in Part 1 of Example 1 in terms of drying ability and color, but are generally superior to gloss.

Example 6.

Hexamethoxymethylmelamine is redesigned to the butyl ether by heating sued using a 97 part reboiler with 222 parts of butanol and 0.1 part of lyophilic acid for one hour. The excess butanol and methanol are then distilled off by heating the mixture while stirring to 150 ° C. As a residue, 120 parts of a light yellow viscous liquid are obtained.

To this product are added 146 parts of p-tertiary-hutylphenol and 0.5 parts of oxalic acid, and the mixture is heated with stirring to 150 ° C. The temperature is maintained at 150 ° C for 30 minutes. On cooling, a light yellow, viscous, liquid resin is obtained, which on cooling dissolves in drying oils and gives varnishes with good drying form.

Example 7.

Hexamethoxymethylrnelamine is converted to the ethyl ether by heating using a reflux condenser of a mixture of 96 parts and 138 parts of absolute alcohol and 0.1 part of phosphoric acid for two. hours. The excess ethanol and methanol are then distilled off by heating the mixture with stirring to 120 ° C.

To the residue are added 146 parts of p-tertiarbutylphenol and the mixture is heated with stirring to 1 ° C. The temperature is maintained at 140 ° C for 30 minutes. Arid cooling results in a light yellow, viscous liquid, resin which, when boiled, dissolves in drying oils and gives varnishes with good drying ability.

Example 8.

A mixture of 60 parts of p-tertiar-butylphenol, 40 parts of hexamethoxymethylmelansine, 35 parts of toluene and 0.6 parts of soda ash is heated with stirring at 100 ° C for one hour. The temperature is then raised to 170 ° 180 ° G and heating is continued at this temperature for two hours under conditions such that toluene distills off. On cooling, a light yellow, plastic, solid resin is obtained, which, when boiled, dissolves in drying oils and gives varnishes sued good drying ability.

The hexamethoxymethyl melamine used in Examples 1 to 8 is prepared by first reacting melamine with 6.3 molecular amounts of formaldehyde in the presence of alkali, after which the hexamethylol melamine thus obtained is treated with an excess of methanol in the presence of chlorine water. . Man erhaller pa sa. sail an acid, which consists essentially of hexamethoxymethylmelamine but which contains small quantities of products, containing minor On 6 methoxymethyl groups and certain non-etherified methylene groups.

Example 9.

A mixture of 126 parts of melamine, 407 parts of a 37% aqueous formaldehyde solution and 5 parts of acidic disodium phosphate is heated with stirring up to 75 ° C for 10 minutes. The resulting solution is placed in a shallow tray and dried in a sieve at ° C for 48 hours. Beta obtained, dried, solid has a formaldehyde content of 48.7 ¶ (tetramethylol-melamine contains 48, s'; ", formalclehyde).

A mixture of 82 parts of this product and 128 parts of methanol is stirred, while a stream of dry chlorine gas is allowed to bubble through it for 30 minutes. at a temperature of 20-25 ° C. The clear solution formed is cooled in ice and neutralized to bromothymol sheet by adding a methanol solution of sodium methoxide, the inorganic salts which precipitate are filtered off and the filtrate is evaporated off under a pressure of 35 mm Hg a temperature of 25 ° C in order to remove excess methanol. The viscous residue is diluted with 100 parts of toluene and the solution formed is filtered off from a further precipitate of inorganic material. The formed, clear solution has a volatile matter content of 54.2%.

A mixture of 68.5 parts of the solution obtained and 60 parts of p-tertiar-butylfermi is heated with stirring up to 140 ° C for several hours and maintained at this temperature under conditions such that toluene distills off. Man erlraller pa. said salt on cooling a yellow, viscous cheese, liquid resin, which mashes in drying oils and gives varnishes with good drying ability.

Claims (8)

Fatentansprak: A process for the preparation of oil-soluble resinous condensation products, characterized in that an etherified melamine-formaldehyde condensation product is heated together with at least half the chemically equivalent amount of a fermi, in which one or two of the layers o, o and p in the phenol group are or arc unsubstituted. A process according to claim 1, characterized in that no more chemically equivalent amount of phenol is used. 4— - 3. A process according to claim 1, characterized in that a mixture of the etherified melamine-formaldehyde condensation product and about 2/3 of the chemically equivalent amount of phenol was used. A process according to any one of the preceding patent claims, characterized in that the phenol Sr used is one in which the p-layer is substituted. 5. A process according to any one of the preceding claims, characterized in that the etherified melamine-formaldehyde condensation product is obtained by etherifying a methylol-melainin containing more than 3 methylol groups per molecule. Process according to any one of the preceding patent claims, characterized in that an acidic condensing agent is added to the reaction mixture. Oil-soluble, resinous condensation products, prepared according to any one of the preceding claims of an etherified melamine-formaldehyde condensation product and at least half of the chemically equivalent amount of a phenol in which one or two of the layers o, o and p of the phenol group Sr or aro are unsubstituted. Varnishes obtained by boiling products according to patent claim 7 in drying oils. Stockholm 1948. Kong]. Sok tr. P. A. tiorstedt & Niter 480089