CS256744B1 - Amides of polyphenols' nitrogen derivatives - Google Patents

Description

(54) Nitrogen derivatives of polyphenols

2

The present invention describes nitrogen amides of polyphenol derivatives of the general formula wherein R 1, R 2 alkyl or alkenyl C 6 -C 22, R 5, R d alkylene C 2 -C 10 or the radical (R 5 -NH), _n- R 5, R 5 alkylene C2 or C3; diane-based resins, m is 1 to 3, n 0 to 5, and salts thereof with water-soluble acids. In particular, the use of these compounds is for the surface treatment of glass and mineral fibers.

OH OH

RlCONH NHCH2CHCH2-R 3 - M CH2CHCH2NH-d-HNCOR2

The invention relates to amides of nitrogen derivatives of polyphenols and their salts with water-soluble acids, suitable as an additive to compositions for treating and processing glass and mineral fibers.

Adducts and polyaducts based on epoxy resins and amines, especially dianes based resins, have found important industrial applications. A number of addition compounds are known whose properties are adapted to the nature of their application. In the case of the application of adducts for the treatment of natural polymeric fatty acids and polyamines with epoxy resins (U.S. Pat. No. 168,515) solubilized by adjusting the pH using water-dissolved acids. Adducts suitable as paints, adhesives or impregnating materials can be prepared by reacting epoxy resins with amino amides based on aromatic acids and amines (U.S. Pat. Nos. 98,358, 98,359). Hardeners for epoxy resins can be prepared by reacting polymeric fatty acids, polyamines, with an epoxy resin (U.S. Patent No. 170,697) or by reacting a copolyaminoamide resin with an epoxy (U.S. Patent No. 170,696). The preparation of these products is generally carried out in such a way that they contain free primary amino groups. The presence of these reactive groups presents considerable problems in the application of different adducts to glass and mineral fiber compositions, in particular because of the stability and coloring of the fibers when they are dried. We have found that these problems can be effectively solved by using the adducts of the invention, the synthesis of which is carried out without the free primary amino groups.

The present invention provides amides of nitrogen derivatives of polyphenols of the general formula

OH OH

R1CONH — R3 — NHCH2CHCH2 — M — CH2CHCH2NH — R4 — HNCOR2 wherein represents

R 1, R 2 is an alkyl or alkenyl radical of 6 to 22 carbon atoms,

R 3, R 1 of a C 2 -C 10 alkylene radical or a radical of structure (R 5 -NH), _n R 5

R 5 is an alkylene radical having 2 or 3 carbon atoms,

M residue of structure

m is 1 to 3 and n is 0 to 5, and salts thereof with water-soluble acids.

Aminoamides based on monomeric fatty acids and aliphatic polyamines are used to prepare the compounds. Fatty acids are used either individually, but more often in mixtures, as fatty acids isolated from various oils and fats, which are amidated with polyamines such as ethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenethylenetrient, triethylenethylamine. Also, polyamines are used not only in pure form, but also in the form of technical products of aminolysis of chlorinated hydrocarbons. In the preparation, it is preferred to add a diane-based epoxy resin to the melt of the amino amides heated to 60-150 ° C, and the reaction is terminated after the epoxide groups have reacted.

If desired, the synthesis can also be carried out in an organic diluent environment, with alcohols and ether alcohols such as ethyl alcohol, ethylene glycol monoethyl ether being the most important. The preparation of salts of water-soluble acids, whether mineral or organic, can be accomplished by simply mixing the resin with the acid either immediately after completion of the synthesis or prior to their application, to form emulsions or solutions in water.

The invention is further illustrated by way of examples.

Example 1

To a flask equipped with a stirrer and a thermometer was added 100 g of amino amides ky256744 selins oil and diethylenetriamine with an amine of 302 mg KOH / g and heated to 130 ° C. While stirring, a diane-based epoxy resin of various average molecular weights was gradually added and the batch was maintained at this temperature for 1.5 hours. The amounts of epoxy resins with different average molecular weights and adduct properties are shown in Table 1.

Table 1 Weight (g) Epoxy resin (Molar mass)

380 51,6

480 65.0

500 205.0 melting point (° C) amine value (mg KOH / g) - 51 197 - 56 180 - 71 96

Example 2

The following amine amides were used for the preparation. Aminoamide A composed of oleic acid and ethylenediamine having an amine number of 170 milligrams of KOH / g. Aminoamide B composed of oleic acid and hexamethylenediamine having an amine number of 145 mg KOH / g. Aminoamide C composed of oleic acid and trimethylhexamethylenediamine having an amine number of 130 mg KOH / g. Aminoamide D composed of oleic acid and dipropylenetriamine having an amine number of 280 mg KOH / g. Aminoamide E composed of oleic acid and triethylenetetramine having an amine number of 406 mg KOH / g. Aminoamide F composed of oleic acid and tetraethylenepentamine having an amine number of 490 mg KOH / g. The flask was charged with 100 g of the appropriate amine amide, which was heated to 120 ° C and maintained at 15 ° C after the addition of the diane epoxy resin having an average molecular weight of 380. The epoxy resin amounts and adduct properties are shown in Table 2.

Table 2

aminoamide epoxy resin melting point amine number (gj (° C) (mg KOH / g) A 58 66 - 69 105 B 50 87-90 94 C 45 17 - 21 87 D 48 46 - 49 182 E 46 42 - 45 275 F 42 40-43 340 Example 3 To 100 g of aminoamides with stirring at temperature 100 ° C added epoxy resin for For the preparation of the adducts, a used amino amide dianu base of different average molecular composed of technical mixture of fatty acids weight on which it was held for 2 h. quantities composition line referred to in Table 3 and diet- of epoxy resins and adduct properties of amine triethylamine number 375 mg KOH / are given in Table 4.

/ G ·

Table 3 fatty acid% by weight

lauric 50.8 myristic 13.8 palmitic 11.6 capric 8.1 caprylic 7.8 oil 3.7 stearic 1.2 unidentified 3.0

epoxy resin weight (mol. weight) (g)

380 64

480 80 bulk 4 melting point amine number (° C) (mg KOH / g) - 52 221 - 61 204

Example 4

For the preparation of the adduct, an amine amide composed of a technical mixture of fatty acids of the composition given in Table 5 and triethylenetetramine having an amine number of 406 mg KOH / / g was used.

Table 5 fatty acid% stearic acid 52,4 palmitic 42,3 lauric 1,9 arachic 0,7 caprylic 0,1 pentadecanoic 0,3 heptadecanoic 1,7 capric 0,3 0,3 unidentified 0,3

To 100 g of amino amides was added 46 g of diene based on an average molecular weight of 380 on which it was held for 2 hours at a temperature. The prepared adduct had a melting point of 70-73 ° C and an amine number of 269 mg KOH / g.

Example 5

The adduct of Example 1 consisting of an epoxy resin having a molecular weight of 380 and oleic acid aminoamides and diethylenetriamine was dissolved in ethyl alcohol to a 50% solution with a viscosity of 170 mPa.s at 20 ° C. with. To 20 g of this solution was added acid and the solution was added with stirring to 200 ml of water. The amounts of various acids and the properties of the solutions are shown in the table

6th

Table 6 Acid weight (g) Properties of the solution

formic 0.8 opalescent solution acid 1.0 opalescent solution glycolic 1.5 white emulsion hydrochloric acid (36%) 2.0 white emulsion monochloroacetic 2.0 opalescent solution

Claims (1)

R E d μ ε τ INVENTION Amides of nitrogen derivatives of polyphenols of general formula OH OH R1.CONH — R3 — NHCH2CHCH- -M — CH2CHCH2NH — R4 — HNCOR2 where represents R 1, R 2 is an alkyl or alkenyl radical of 6 to 22 carbon atoms, R3, R4 C2-C10 alkylene or (R5-NH) _m R5 R 5 is an alkylene radical having 2 or 3 carbon atoms, M is a moiety of the structure m is 1 to 3 n is 0 to 5, and salts thereof with water-soluble acids.