CS204408B1 - Copolyaminohydroxyethere bitumens - Google Patents

Description

The invention relates to copolyaminohydroxyether resins and their addition salts with mineral acids or organic water-soluble acids.

Resins are used in the form of solutions and emulsions for treating various organic and inorganic fibers. The widespread and steadily expanding application of these fibrous materials, mainly based on glass fibers, has necessitated modifying and modifying the properties of the resins with respect to their intended use.

CS patent S. 167 893 describes polymeric reaction products prepared by the reaction of alkylene polyamine dihydrohalide, dicyandiamide, formaldehyde and epichlorohydrin. CS patent no. 168,515 prepares polyaddition products from epoxy resins having at least two epoxy groups by reaction with amino amides. It uses mineral and organic acids for neutralization. The aminoamides used are prepared e.g. condensation of linoleic acid with diethylenetriamine. SU patent no. No. 412,691 discloses the preparation of reaction products of epoxy resins with aliphatic amines and saturated dicarboxylic acids. The preparation of a water-soluble resin by reaction of epoxy with aliphatic monocarboxylic acids of 16 to 22 carbon atoms and neutralization with ammonia, or aliphatic or cycloaliphatic amines is described in SU patent no. No. 451 252. SU patent no. 460,632 provides the preparation of water-soluble polymer reaction products of polyamines with epichlorohydrins. DE patent

204 408

No. 204,408, No. 1,694,718 describes a process for preparing epoxy resin emulsions using reaction products prepared from epoxy resins and monoamines. A process for the preparation of polyadducts from epoxy resins e.g. with DE-A-1-amino-3-aminoethyl-3,5,5, -trimethyl-cyclohexane. All cited patents deal with the preparation of resins for use in the treatment of textiles, whether organic or inorganic, suggesting the importance of this problem.

The present invention provides novel copolyaminohydroxyether resins of the general formula

OH

N / R 1 / CH ₂ CHCH ₂ / R ₂ / _ -O-

OH

Y> -OCH ₂ CHCH ₂

NHR * a

where R 1 is -CH 2 CHgOH in which X is H or -CH 2, R ₂ is a radical of structure

CH ₂ CHCH ₂ n is 0 to 2 m is 2 to 100 and their addition salts with mineral acids or organic water-soluble acids.

Resin formation can be accomplished by polyaddition of monoethanolamine or monoisopropanolamine 8 with epian resins based on diane and epichlorochyrine according to the reaction scheme:

n / r _l / ch ₂ chch ₂ or-och ₂ chch ₂

-> H where R 1 is as defined above and R is from mCH ₂ -CHCH ₂ O-R-OCH ₂ CH-CH ₂ 4 · m + 1 NH 4 -r ^ 0 ^ 0 m

< 8 > -8- (4-exyphenyl) -2,2 propane. Although theoretically and practically it is possible to use monoalkanolamines with a large number of carbon atoms, the two alkanolamines are of technical importance in view of the application of glass fiber resins. When dialkanolamines with a secondary amine are used for addition to epoxy resins, although water-soluble adducts are prepared after neutralization, they do not achieve the necessary film-forming properties and serve as a lubricant for the skins. A similar use of adducts of monoalkanolamines with epoxy resins containing free epoxy groups is undesirable, mainly because of the use of lubricants and cationic characters.

204,408 ter, based on mono and disubstituted fatty acid amides or aminosilanes, are cured in situ during the thermal treatment of glass fibers. The resins according to the invention have the necessary film-forming properties, are characterized by minimal migration and, when converted to salts, can be applied in the form of aqueous solutions. The colloidal solutions of these resins also have surface-active properties and although not as pronounced as conventional surfactants, they can be used as emulsifiers, especially for epoxy resins.

The invention is further illustrated by way of examples.

Example 1

A 250 ml flask equipped with a stirrer, a contact thermometer, and a reflux condenser was charged with 73 g of monoethanolamine and 115 g of a diane-epichlorohydrin epoxy resin containing 0.51 epoxy / 100 g dissolved in 120 g of chloroform. The batch was heated to reflux temperature for 3 h. After cooling, it was extracted with water until neutral and the solvent was distilled off at atmospheric pressure. The copolyaminohydroxyether resin (Zn = 0.1 and m = 6) prepared in this manner has an amine number of 148.5 mg KOH / g and a melting point of 50-53 ° C. It is preferred to dissolve the resin in a water-soluble solvent e.g. acetone. When such a solution is added to water having a pH of 3 to 5, a clear solution is formed.

A salt can also be prepared by directly mixing the resin with an acid that dissolves freely in water.

Example 2

25 g of monoethanolamine and 180 g of epian resin based on diane and epichlorohydrin containing 0.21 epoxy / 100 g dissolved in 180 g of chloroform were introduced into the apparatus described in Example 1. The reaction mixture was heated at moderate reflux for 4 h. After washing with water until neutral and distilling off the solvent, an amine resin of 71.5 mg KOH / g / n 2 was obtained; m = 3.6 / mp 85-88 ° C. The resin was dissolved in a 50% solution in dioxane which, when added to water of pH = 3.5 using acetic acid, gave clear solutions, slightly opalescent.

Example 3

In the apparatus described in Example 1, 46 g of monisopropanolamine and 114 g of epoxy resin based on diane and epichlorohydrin containing 0.51 epoxy / 100 g dissolved in 114 g of chloroform were charged. The batch was heated at moderate reflux for 3 hours. After washing with water until neutral and distilling off the solvent, an amine resin of 140 mg KOH / g (n = 0.1 µm = 6.5) having a melting point of 83-86 ° C was obtained. The resin was dissolved in acetone to a 50% solution, whose pH = 3.5 using formic acid gave clear solutions.

204 408

Example 4

Into the apparatus described in Example 1, additionally equipped with a separatory funnel, was added monoethanolemine 74 g and 74 g chloroform. 114 g of Dian-epichlorohydrin-based epoxy resin containing 0.51 epoxy / 100 g dissolved in 74 g of chloroform was slowly added from the separatory funnel at 70-71 ° C over 1.5 h. After addition of the resin, the batch was heated for 1.5 hours, washed with water until neutral, and the solvent distilled off under vacuum. The prepared copolyaminohydroxyether resin has an amine number of 179 mg KOH / g / n = 0.1; m = 2.1 / mp 47-49 ° C. The resin was dissolved in dioxane to a 50% solution, which was added under stirring to water of pH 4 using phosphoric acid. The resulting clear solutions were stable and their change was not observed even after 2 months of standing.

Example 5

The preparation was carried out in the apparatus described in Example 4 using the same epoxy resin, except that monoethanolamine was added slowly in the resin. 190 g of resin were dissolved in 200 g of chloroform in a flask. Slowly within 1 hour 30 g of monoethanol amine were added at 70 ° C. The batch was diluted by adding 100 g of chloroform, and then 60 g of monoethanolamine was added over 1 h. After the addition, the batch was heated for 1 h (70 ° C). After cooling, it was washed with water until neutral and the solvent was distilled off. The copolylaminohydroxy ether resin has an amine number of 130 mg KOH (g / n = 0.1} m = 100) and a melting point of 82-85 ° C.

Claims (2)

OBJECT OF THE INVENTION A copolyaminohydroxyether resin of the general formula OH CBj OH N / R / CHgCHCHg / R /. -O-C-OCHgCHCH. CH, NHR. - m wherein R 1 is -CHXCH 2 OH wherein X is -H or -CH 2, R 8 is a residue of structure -0OH I -CHAIR is 0 to 2 m is 2 to 100 and their addition salts with mineral acids or organic water-soluble acids. 2. The copolyaminohydroxyether resins of the general formula (1), in which R1 is -CH2GHgOH and m is 3 to 6;