DE1028328B - Process for the production of aqueous polyamide dispersions - Google Patents

Description

GERMAN

Linear film-forming polyamides are difficult to disperse in water and the dispersions are not durable. They either have very uneven particle sizes, are too coarse, or begin to gelatinize after a short time. Such dispersions also become by drying at No films at normal temperature, but only dry powders that have no adhesiveness whatsoever and therefore also exclude practical application.

It is known to add polyamide solutions in organic solvents or in aqueous dispersants Disperse and, if necessary, to homogenize the dispersions. These dispersions give coherent Films when pouring onto substrates and allowing the organic solvent to evaporate and of the water. But they contain very considerable amounts of organic solvent, which also causes film formation when the dispersions dry out.

It has now been found that low-solvent and even solvent-free aqueous dispersions can be obtained Can produce solutions of polyamides from organic solvents, which also dry out Closed films are left behind when one consists of solutions dispersed in aqueous dispersant solutions of polyamides, which contain dicarboxylic acids condensed in, the side chain of aliphatic hydrocarbon radicals having at least 6 carbon atoms, the organic solvent completely or partially through Distillation removed.

Such polyamides are preferably those which are made from dicarboxylic acids, the in turn by the action of carbon monoxide and water on olefin carboxylic acids or their functional ones Derivatives in the presence of metal carbonyls or carbonyl-forming metals are available.

Suitable dispersants for the known production of the polyamide dispersions used are above especially water-soluble, highly polymeric substances such as copolymers of unsaturated lactams, e.g. B. des Vinyl pyrrolidones and vinyl caprolactams, acrylic and methacrylic acid salts, unsaturated carboxamides, z. B. of methacrylamide and acrylamides. In many cases, however, also, if necessary additionally, other dispersants and emulsifiers can be used, such as salts of higher molecular weight sulfonic acids or Sulfuric acid esters, salts of fatty acids, polyethylene oxides or polyglycol ethers or esters.

The dispersions used are prepared by dispersing, expediently, an alcoholic solution of the polyamide in the aqueous dispersant solution in a manner known per se. According to the invention, the alcohol used as solvent is completely or partially removed by distillation. It can both with method of manufacture
aqueous polyamide dispersions

Applicant:

Aniline & Soda Factory in Baden
ίο Aktiengesellschaft, Ludwigshafen / Rhein

Dr. Karl Dachs, Dr. Hans Fikentscher,
Dr. Hans Wilhelm and Dr. Hans WoIz,

Ludwigshafen / Rhine,
have been named as inventors

Water-miscible as well as immiscible alcohols can be used, e.g. B. methanol, ethanol, propanol, Butanol, amyl and isoamyl alcohol. However, other solvents can also be used for the polyamides be e.g. B. phenols, cresols and chlorinated hydrocarbons such as trichlorethylene.

The dispersions obtained and treated according to the invention dry to form coherent, in most cases Precipitate perfectly clear films of very high mechanical strength. These films are impermeable to water and oil and very weather-resistant. The dispersions are therefore particularly suitable for the production of coatings on wood, metal, Paper and other material, e.g. B. for corrosion-resistant, seamless lining of containers, for production of top coats on coats of other film-forming substances, for covering wires, for Surface treatment of leather, for finishing textiles, e.g. B. as boil-proof finishes, collar stiffeners, as an additive for the hydrophobic treatment of textiles, as an adhesive for gluing a wide variety of products Materials and for the production of intermediate layers, e.g. B. for glass, as a binder in the manufacture of Fiber fleeces, for fixing pigments, as an impregnating agent for solid and flexible materials as well as for manufacturing of foils.

Since the polyamides used according to the invention are compatible with many of the customary paint raw materials, The dispersions used as the starting material can share these polyamides and other coating raw materials contain. For example, other coating raw materials, such as polymers, can also be used in the solutions of these polyamides and copolymers of unsaturated esters

709 960/432

Claims (1)

3 4 Mono- and dicarboxylic acids, ζ. B. the acrylic acid, meth- normal temperatures obtained films are transparent acrylic acid, maleic acid, vinyl esters, vinyl ethers, and high mechanical strength. Vinyl halides, vinyl aromatics, and also curable ones. Resins, dissolved and these solutions after the addition of tfeispie Dispersants or emulsifiers and water dispersed 5,100 parts of a polyamide from 60 ° / _{0 of} a salt which according to the invention under complete or l-octylnonanedicarboxylic acid 1,9 and 4,4'-diaminodicyclo partial distillation of the solvent in aqueous hexylmethane, 20 % Capryllactam and 20 ⁰ Z ₀ adipic acid dispersions are converted. Such dispersions of hexamethylenediamine are made at 90 to 100 ° C in 500 parts, but can also be prepared by first dissolving butanol. After addition of 230 parts of water solutions of lacquer raw materials, or io and 10 parts of a 20 ° / ₀ solution of a mixed solvent other than the polyamide solutions corresponds polymer of 70% methacrylic acid and 30% hold, for the same. B. Nitrocellulose !! in ethyl acetate or vinylpyrrolidone in water, 490 parts of butanol-etherified urea resins in alcohols are distilled off azeotropically with solutions with stirring. The obtained these polyamides are mixed in alcohols. This water-in-oil emulsion is brought to room temperature. Mixtures are then cooled to form aqueous dispersions. The mixture is then left with vigorous stirring. 170 parts of water, including 15 parts of a 20% solution The new polyamide dispersions can also be added to the copolymer described above with dispersions or emulsions of other film-forming substances, run in slowly. After a short time, a Substances, e.g. on the basis of etherified urea - paste-like and very easy to spread oil-in-water dispersion Resins, polymers and copolymers of 20 obtained, the clear and solid films on drying Leaves acrylic and vinyl compounds or polyesters. Mix. The dispersion is suitable for coating paper, BeisDiel 1 textiles and upholstery open. By mixing with water phenol-formaldehyde resin dispersions in each 180 parts of a polyamide consisting of 25% capryllactam, 25 mixing ratio obtained dispersions for the metal 25 ⁰ _jD caprolactam, surface coating 25% sebacinsaurem hexamethylene. After thermal hardening of diamine and 25% of a salt of the l-nonyloctanedicarbonic acid, excellent protective coatings with very acidic 1,8 and 4,4'-diaminodicyclohexylmethane have a low water absorption capacity, boiling in 700 parts in a known manner. . Dissolved methanol. After adding 600 parts of water, Example 5 and 13.5 parts of a 20 ° / ₀ solution of a mixing 130 parts of a polyamide from adipic acid 20% polymer from 70% methacrylic acid amide and 30% hexamethylenediamine, 20% caprolactam, 20% caprylic vinylpyrrolidone the lactam and 40% of a mixture of equal parts of the Methanol is distilled off. After cooling, a salt of the l-octylnonanedicarboxylic acid-l ^ and the l-nonyl thick liquid Obtained dispersion which gives clear films. 35 octanedicarboxylic acid-1,8 with 4,4'-diaminodicyclohexyl- . . methane in 500 parts of n-butanol at 80 to 90 ° C Example 2 solved. After adding 270 parts of water and 25 parts 100 parts of a polyamide from 60% of a salt of a 20% solution of a copolymer of 65% of the l-octylnonanedicarboxylic acid-1,9 and 4,4'-diamino-methacrylic acid amide, 30% vinylpyrrolidone and 5% dicyclohexylmethane, 20% caprolactam and 20% % adipine- 40 N-vinylimidazole, 490 parts of butanol are azeotropically acidic hexamethylenediamine are distilled off at 90.degree. After cooling to room temperature, 500 parts of butanol are dissolved. After addition of 395 parts of a pasty and well spreadable dispersion erWasser and 25 parts of a 20% solution of a hold, which is stable in both acidic and in the alkaline copolymer of 70% methacrylic acid and p _H range. It has a solids content of 30%, 30% vinylpyrrolidone in water, 493 parts of butanol 45 can be diluted with water and, on azeotrope, distills off with stirring. The obtained dry a solid, transparent polyamide film. The dispersion is cooled to room temperature. You dispersion is particularly suitable for impregnation has a particle size of 1.5 microns on average of fiber materials, such. B. for the production of collars and after drying leaves a stiff insert on shirts, for "petticoat finishing.! From parent film. 50 polyamide fabrics and for paper finishing." Example 3 claim: 100 parts of a polyamide from 50% of a mixture Process for the production of aqueous polyamide the salts of l-octylnonanedicarboxylic acid-l ^ and the dispersions from solutions of polyamides in organic 1-nonyloctanedicarboxylic acid-1,8 with hexamethylenediamine, 55 niche solvents, characterized in that 25% caprolactam and 25% adipic acid hexamethylene that you get from in aqueous dispersant solutions diamine are at 80 to 90 ° C in 500 parts of cyclo-dispersed solutions of polyamides, the dicarbon hexanol dissolved. After the addition of 395 parts of water, condensed acids contain the side chain and from 25 parts of a 20% solution of a mixed aliphatic hydrocarbon radical with at least Polymer of 70% methacrylic acid amide and 30% have 60 6 carbon atoms, the organic solution Vinylpyrrolidone in water, 490 parts of cyclo-agent are completely or partially removed by distillation. hexanol distilled off azeotropically with stirring. After this Cooling down to room temperature gives a stable. dige dispersion, which has a particle size of by- German Patent No. 748840; section has 2 µ. By drying at 65 U.S. Patent No. 2,405,965. © 709 360/432 4.58