CS256745B1 - Amides of nitrogen derivatives of polyphenols - Google Patents

Abstract

The solution describes new amides of nitrogenous derivatives of polyphenols of the general formula, where R1 represents alkyl or alkenyl C6 to C22, R2 is —CH2CH (OH) CH2MCH2CH (OH) CH2R5 M residue of a diane-based epoxy resin, R3 a hydrogen atom or R2, R4 alkylene C2 to C12, optionally interrupted by up to 3 nitrogen atoms to which hydrogen is bonded, or R2, R5 a residue of diethanolamine, diisopropanolamine, morpholine, piperidine, pyrrolidine or imidazole, n is 0 to 5, and their salts with water-soluble acids. The compounds are particularly suitable for treating glass fibers.

Description

The invention relates to amides of nitrogenous derivatives of polyphenols and their salts with water-soluble acids.

Epoxy resins in the form of adducts with amines have found significant application in the surface treatment of glass fibers. For the preparation of adducts, mainly secondary amines such as diethanolamine, morpholine, imidazole, piperidine and pyrrolidine are used (US Pat. No. 3,449,281, French Pat. Nos. 1,371,900, 1,371,901, British Pat. No. 1,103,325, Czech Patent No. 178,838, and No. 224,025).

The improvement of the application properties of simple adducts is achieved by the synthesis of mixed adducts based on secondary alkanolamines, aliphatic polyamines and epoxy resins (Cs. aut. osv. No. 211163). Because these adducts are solids, they are plasticized in the case of their application as film-forming substances in lubricating compositions for the treatment of glass fibers, usually using polyethylene glycols. Because of the different affinity of the adducts and plasticizers to the anionic surface of glass fibers, the fiber coating is unevenly plasticized. The elimination of these problems can be effectively solved by internal plasticization of the adducts according to the invention.

The invention describes amides of nitrogenous derivatives of polyphenols of the general formula

R2 /

RlCONH—R4—N \

R3 where represents

R1 is an alkyl or alkenyl radical with 6 to 22 carbon atoms,

R2 remainder about structure

OH OH —CH2CHCH2—M—CH2CHCH2—Rs

M rest about the structure

CH

R3 is a hydrogen atom or R2,

Ri alkylene radical with 2 to 10 carbon atoms or a radical of the structure —R6—NR7—R6, —R6—NR8—-R6·—NR9—Re or —R6—NR10—R6-—NR11—R6—NR12—Re, Rs radical of the structure

-Ní R^CHC^OH^,-

or /-=N

R6 is an alkylene radical with 2 or 3 atoms; R7, R6, R9, R10, R11, R12 is a hydrogen or carbon atom; R2,

R13 is a hydrogen atom or methyl and n is 0 to 5, and their salts with water-soluble acids.

The preparation of adducts can be carried out by the following procedure. The corresponding monoepoxide is prepared by reacting an epoxy resin based on diane with a secondary amine such as diethanolamine, diisopropanolamine, morpholine, pyrrolidine, piperidine and imidazole. The ratio of reactants is governed by the stoichiometry of the reaction and the addition is preferably carried out in a water-soluble organic solvent. It is preferable to use aliphatic alcohols such as ethyl alcohol, ether alcohols such as ethylene glycol monoethyl ether, dioxa, or glycerol or polyethers (Czech aut. osv. No. 210 307). The monoepoxides prepared in this way are subjected to a reaction with aminoamides based on monomeric fatty acids and aliphatic polyamines such as ethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine.

Fatty acids are used either individually, but more often in mixtures as fatty acids isolated from various oils and fats. Similarly, polyamines are used not only in pure form, but also in the form of technical products of aminolysis of chlorinated hydrocarbons. By neutralizing the adducts with water-soluble acids, whether organic or inorganic, they can be converted into the corresponding hydrophilic salts, which facilitates their application in aqueous compositions!. The preparation of salts can be carried out by simply mixing the resin with the acid either immediately after the synthesis is completed, or before their application.

The invention is further illustrated by way of examples in which the composition is given in weight concentration.

Example

In a glass flask equipped with a stirrer, reflux condenser, contact thermometer and separatory funnel, 100 g of diane-based epoxy resin with an average molecular weight of 380, 27.7 g of diethanolamine and 127.7 g of ethyl alcohol were introduced. The batch was kept at reflux temperature for 1.5 h. After this time, a 50% solution of oleic acid aminoamide and diethylenetriamine with an amine number of 302 mg KOH/g in ethyl alcohol was added and the batch was kept at reflux temperature for 2 h. The weights of the aminoamide solution and the properties of the adducts are given in Table 1.

Table 1 aminoamide (g) viscosity color (mPa.s) (mg J2) amine number (mg KOH/g)

193.5

96.7

64.4

60.8 6 101.2

126.7 6 84.1

98.1 5 75.8

Viscosity was determined according to ČSN 67 3014 at a temperature of 20 °C and color was determined according to ČSN 767 3011.

Example 2

100 g of dianane-based epoxy resin with an average molecular weight of 380 and 100 g of ethyl alcohol were placed in the flask. A 50% solution of amine in ethyl alcohol was added to the batch and the temperature was maintained at a slight reflux for 1.5 h. After this time, a 50% aminoamide solution was added as in the example and the batch was kept at reflux temperature

h. The weights of the amine solutions, aminoamide and the properties of the adducts are given in the table

2.

Table 2

amine solution weight (g) aminoamide (g) viscosity (mPa.s) color (mg J2) amine number (mg KOH/g) morpholine 46.0 193.4 42.4 7 100.2 imidazole 36.0 193.4 132.5 6 138.1 diisopropanol- amine 70.0 193.4 63.6 7 93.9 pyrrolidine 37.5 193.4 46.9 7 102.4

Example 3 composed of a technical mixture of fatty acids with the composition given in Table 3,

An aminoamide was used to prepare the adduct,

Table 3

T a b u Ϊ k a 5 fatty acid % by weight fatty acid % by weight stearic 52.4 palmitic 42.3 lauric 1.9 araic 0.7 caprylic 0.1 pentadecanoic 0.3 heptadecanoic 1.7 capric 0.3 unidentified 0.3

The amylation of these acids was carried out using a technical mixture of aliphatic polyamines with the composition given in Table 4 and the aminoamide has an amine number of 267 mg KOH/g.

Table 4 aliphatic polyampha ethylenediamine diethylenetriamine dipropylenetriamine isomeric propylenediamines isomeric butylenediamines unidentified polyamines % by weight

14.2

70.1

3.4

6.6

1.8

3.9

200 g of a 50% solution of a diane-based epoxy resin with an average molecular weight of 1500 in methyl glycol were introduced into the flask. The batch was kept at reflux temperature for 1.5 h. After adding 37 g of a 50% solution of aminoamides in methyl glycol, it was kept at reflux temperature for 2 h. The prepared adduct solution has a viscosity of 2,130 mPa.s, a color of 7 mg J2 and an amine number of 35 mg KOH/g.

To prepare the adduct, an aminoamide from technical fatty acids with the composition given in Table 5 was used.

laurel myristic palmitic capric caprylic oleic stearic unidentifiable

50.8

13.8 11.6

8.1

7.8

3.7

1.2

3.0 and tetraethylenepentamine with an amine number of 570 mg KOH/g. 100 grams of a diane-based epoxy resin with an average molecular weight of 480, 22 g of diethanolamine and 122 g of ethyl alcohol were introduced into the flask. The batch was kept at reflux temperature for 1.5 h. After adding 36 g of 50% aminoamide in ethyl alcohol, it was kept at reflux temperature for 2 h. The prepared adduct solution has a viscosity of 30 mPa. s, a color of 6 mg J2 and an amine number of 140 mg KOH/g.

Example 5

Aminoamides of oleic acid and the following polyamines were used to prepare the adducts. Aminoamides A using ethylenediamine with an amine number of 170 mg KOH/g. Aminoamide B using trimethylhexamethylenediane with an amine number of 130 mg KOH/g. 100 g of a diane-based epoxy resin with an average molecular weight of 380, 27.7 g of diethanolamine and 127.7 g of ethyl alcohol were introduced into the flask. The batch was heated at reflux temperature for 1.5 h. After this time, a 50% solution of the respective aminoamide in ethyl alcohol was added and the batch was maintained at reflux temperature for 2 h. After the temperature dropped below 40 °C, it was neutralized by adding acetic acid. The weight of the aminoamide solutions, the acids and the properties of the adducts are given in Table 6.

aminoamide weight (g)

Table 6 acetic acid (g) viscosity (mPa. s) amine number (mg KOH/g)

171

222

986

Example 6

The aqueous adducts of Example 2 can be prepared by the following procedure. Acid is added to 50 g of the adduct solution and the composition forms opalescent to milky solutions when added to 1000 ml of water. The amounts of acids are given in Table 7.

Table 7 acid [gj acid (g) monochloroacetic acid 4 -------- ---------------:---- — hydrochloric acid (37%) 5 acetic 5 ants 3.5 Compounds that can be produced subjects of the invention are glycolic 7 especially suitable for editing glass fibers.

LET'S GO

Claims (1)

2 5 6 7 4 5 9 18 Table 7 acid (g) acid (g) monochloroacetic acid 4 -------- ---------------: ---- - hydrochloric acid The formulations of the present invention are glycol 7 particularly suitable for treating glass fibers. CHARACTERS OF NITROGEN DERIVATIVES OF POLYPHENOL GENERAL FORMULA R 2 FROM R 1 CONH-R-4-N R 3 where R 1 is an alkyl or alkenyl radical of 6 to 22 carbon atoms, R 2 is an OH OH II -CH 2 CHCH 2 -M-OH 2 CHCH 2 -R 5 M radical. structure R @ 3 is hydrogen or R @ 2, R @ 1 is an alkylene radical having 2 to 10 carbon atoms or a radical having the structure —R6 — NR7 — R6, -R6 — NR6 — R6 — NR9 — R6 or —R6 — NR10 — Re — NR11 — R6 — NR12— R6, R5 residue on structure - N R R fyC HC t - or N R6 is an alkylene radical having 2 or 3 carbon atoms, R7, R8, R9, R10, R11, R12 a hydrogen atom or R2, R13 is hydrogen or methyl an 0 to 5, and salts thereof with water-soluble acids.