DE1420585C - Process for the production of high molecular condensation products - Google Patents

Description

This invention relates to a process for the preparation of higher molecular weight condensation products by reacting substituted aminotriazines with formaldehyde at elevated temperature and optionally subsequent hardening by heating, optionally in the presence of catalysts.

It is known that aminotriazines of the general formula

NH ₂

R-C

C-NH-

in which R is an alkylamino, arylamino, alkoxy or aryloxy radical, with formaldehyde to form Polymethylol derivatives can be converted into heat-curing, crosslinked products 'let condense. These products are of particular interest because of the appropriate choice of the substituent R can be achieved relatively easily different properties. When R represents a long-chain alkylamino or alkoxy group, a deviation from the harder, more fragile properties of an unmodified triaminotriazine-formaldehyde condensation product is achieved and flexible resins are formed. By suitable modification of the N-alkyl substituent des Triaminotriazines it was also already possible to use an im Increased compared to the formaldehyde condensate of the corresponding unsubstituted compound To achieve level of water repellency.

The invention relates to a process for the production of higher molecular weight condensation products by reacting substituted aminotriazines with formaldehyde at elevated temperature and is characterized in that the aminotriazines are perfluoroalkyl-substituted aminotriazines of the general formula

N N

I,

C-Y

Rf-Z -C

R denotes hydrogen or a lower alkyl radical and, if appropriate, the resulting products through Heating, optionally in the presence of catalysts, hardens.

For the method according to the invention, for. B. the following connections can be used: 2,4-diamino-6-perfluorododecanoylhydrazido

sym.-triazine,
2,4-diamino-6- (l, l-dihydroperfluorododecycloxy) -

sym.-triazine,
2,4-diamino-6- (N-methyl-perfluorododecane-

sulfonamido) -sym.-triazine, 2,4-diamino-6- (l, l-dihydroperfluorododecyl-

amino) -sym.-triazine,
2,4-diamino-6- (3-oxa-l, l, 2,2-tetrahydroperfluoro-

hexyloxy) -sym.-triazine,
2,4-diamino-6- (w-perfluoroctylundecyIoxy) -

sym.-triazine,
2-Amino-4-hydrazino-6- (N-propyl-perfluoro-

hexanesulfonamido) -sym.-triazine, 2,4-dihydrazino-6- (N-ethyl-perfluorododecan-

sulfonamido) -sym.-triazine, 2,4-dihydrazino-6- (perfluorobutanoylhydrazido) -sym.-triazine.

The substances produced by condensation with formaldehyde are thermosetting resins, which have oil and water repellent properties. They can be in the form of thin sheets or films be cast that have these properties.

example 1

2 g of 2,4-diamino-6- (N-methylperfluorooctanesulfonamido) -sym.-triazine are heated for about 1.5 hours with 10 g 37% ^'s g aqueous formaldehyde at reflux. The reaction mixture is evaporated to dryness, whereupon the remaining resin is dissolved in about 50 ecm of dioxane. Films cast from this solution can be cured at 165 ° C in 30 minutes to produce a hard, insoluble, oleophobic, heat-resistant product. The curing time can be shortened by adding a catalyst such as maleic anhydride or oxalic acid.

B e i s ρ i e 1 2

2,4-diamino-6- (perfluorooctanoylhydrazido) -sym.-tri-

azine (FP 259 and 260 of ⁰ C.) is used for the manufacture of a formaldehyde condensate resin according to the procedure described in Example 1, wherein a hard, insoluble and oleophobic resin is obtained.

used, in which X and Y are amino or hydrazine radicals, Rf is a perfluorinated alkyl radical with 4 to 12 is carbon atoms and Z is divalent Group of formula

- SO ₂ - NH (CH ₂ J _n NH-,

- SO ₂ N (R) -,

- CO - NH (CH ₂ ) _m NH -,

- CONH-,

- (CH ₂ ) "—O— or

- (CH ₂ ), - NH-

is where η is an integer from 1 to 12, m is an integer from 0 to 12, q is an integer from 1 to 13 and

Example 3

A mixture of 6.2 g of 2,4-diamino-6- (N-methylperfluorooctanesulfonamido) -sym.-triazine, 3.2 g of 37% aqueous formaldehyde and 12 g of 1-butanol Boiled under reflux for 4 hours under a Barrett's receiver to remove what was initially present and the water formed during the reaction. The resulting solution of the resin is with diluted about 90 ecm of dioxane, whereupon about 0.05 g of maleic anhydride are added as a catalyst. Films cast from this solution and carefully cured at 165 ° C are hard and brittle and show average, progressive contact angles of 109 and 54 ° for water and Hexadecane and average receding contact angles of 92 and 48 °, respectively. These results clearly show the hydrophobic and oleophobic

a

Properties of this resin, as wetting through
Angle of 0 ° is displayed.

Example 4

According to the method described in Example 3, 1.5 g of 2,4-diamino-6- (l, l-dihydroperfluorooctoxy) -sym.-triazine condensed with formaldehyde by treating it for about 2 hours with 20 g of a 37% aqueous Formalin solution is refluxed and the water is removed. A product is formed that is in Dioxane is soluble and that in the presence or absence of maleic anhydride forms a hard, brittle, insoluble polymer is hardened in the heat, as an inert protective coating for metal surfaces is valuable. In the film-forming coating of metal, it is in the form of a solution in a suitable solvent such as dioxane, and then baked according to the usual method.

Example 5 ^a °

2,4-Dihydrazino-6- (l, l-dihydroperfluorohexylamino) -sym.-triazine is treated with formaldehyde according to the procedure from Example 3 condensed. This makes it water-insoluble, oleophobic and hardenable by heating Resin made.

Example 6

A mixture of 4.5 g (0.01 mol) of 2,4-diamino-6 - (N - methylperfluorobutanesulfonamido) - sym. - triazine and 3.3 g (0.04 mol) of 37% aqueous formaldehyde in 5 ecm dioxane is refluxed for 2.5 hours. The solution obtained can be used directly for casting films. A film was baked for 2 hours at 120 ⁰ C, is totally clear and transparent, shiny, hard and brittle, showing progressive contact angle from 54 to 96 ° and from 0 ° to 28 ° for water and hexadecane. The measured receding contact angles changed in different parts of the film when they were brought into contact with water, and were 0 ° when they came into contact with hexadecane.

Example 7

A mixture of 7 g of crude 2,4-diamino-6 - (6 - perfluoroctansulfonamidohexylamino) - sym -. Triazine, approximately 5 cc of 37 ° / ^s o'g aqueous formaldehyde and a few drops of a 10 "/ intrinsically sodium hydroxide in 15 cc Dioxane is refluxed for 1 hour, a solution of the corresponding condensation product being obtained.

The formaldehyde condensates of the invention can also be used as hardeners for alkyl urea formaldehyde and melamine-formaldehyde resins can be used. A simultaneous increase in oil and water repellency of the surfaces of resins hardened in this way is achieved due to the fluorocarbon chains that are created by it have been introduced and chemically bound. Even if the condensation of the monomers of the Invention with formaldehyde for the purpose of forming resinous products has been explained, can of course also compounds that can release formaldehyde, such as paraformaldehyde and hexamethylenetetramine, with the same result.

Claims (5)

Patent claims: 1. Process for the production of higher molecular weight condensation products by reaction of substituted aminotriazines with formaldehyde at elevated temperature, thereby characterized in that the aminotriazines are perfluoroalkyl-substituted aminotriazines the general formula Rf -Z-C C-Y used, in which X and Y are amino or hydrazine radicals, Rf is a perfluorinated alkyl radical 4 to 12 carbon atoms and Z is a divalent group of the formula - SO ₂ - NH (CH ₂ ) "NH -,
-SO ₂ N (R) -, - CO - NH (CH ₂ J _1n NH -, - CONH -, - (CH ₂ ) _e - O - or - (CH ₂ ), - NH- is where η is an integer from 1 to 12, m is an integer from 0 to 12, q is an integer from 1 to 13 and R is hydrogen or a lower alkyl radical, and optionally the resulting products by heating, optionally in the presence of Catalysts, hardens. 2. The method according to claim 1, characterized in that in the presence of a low Amount of alkali heated. 3. The method according to claim 1 and 2, characterized in that the initially present and the water formed during the reaction azeotropically with recycling of the solvent distilled off. 4. The method according to claim 1 to 3, characterized in that after removal of the water heated ^{to 110 to 180 0 C for hardening.} 5. The method according to claim 4, characterized in that one is in the presence of maleic anhydride heated as a catalyst.