CS266519B1 - Amino amide resins - Google Patents

Abstract

The solution concerns the area of hardeners and modifiers based on aminoamide resins. The problem of preparing aminoamide resins with low vapor pressure, improved compatibility and good surface parameters of the film is solved. The essence is based on the polycondensation of carboxylic acids with an average molecular weight of 146 to 650 with a mixture consisting of 20 to 90 wt. % aliphatic polyamines and 10 to 80 wt. % heterocyclic polyamines in a molar ratio of polyamine : COOH = 0.9 to 3:1.

Description

The present invention relates to aminoamide resins with reduced vapor pressure, lower toxicity and improved surfactant properties. They are used as modifying components of paints, hardeners of epoxy resins and polyfunctional acrylate or maleate. resins.

Aminoamide resins are widely used in the production of hot melt adhesives, paint modifiers to reduce flowability, retention aids in papermaking, in the curing of epoxy and other reactive resins. Low molecular weight aminoamide resins often contain some free polyamines to reduce viscosity. The presence of even a small amount of free polyamines used (especially diethylenetriamine and dipropylenetriamine) causes unpleasant and toxic fumes when working with air pollution. People who come into contact with such fumes for a long time suffer from stubborn eczemas, the treatment of which is long-term and demanding. It is therefore desirable to prepare such aminoamide resins which, even with the content of free polyamines, have negligible or zero vapor pressures and generate only harmless amounts of vapors. Many aminoamide resins are difficult to mix with some types of epoxy modified resins, which causes a number of difficulties in industrial applications. It is therefore desirable to modify the structure of aminoamide resins so that the effect of the lipophilic component is directed or minimized. When aminoamide resins are used as hardeners for epoxy or polyfunctional acrylate resins, it is desirable that the structure of the cured mass be modified to the greatest possible symmetry, which makes the masses highly tough and resistant to common exogenous factors. These shortcomings and problems of aminoamide resins are solved more or less successfully in various ways, such as modification of aminoamide resins, precondensation with cured resins, use of levelers and the like. However, the resulting effects are not sufficiently satisfactory and in recent years the application of aminoamide resins as hardeners has been diverted.

We have now found, through extensive experimental work, that these disadvantages can be largely or completely eliminated if aminoamide resins are prepared by polycondensation of the corresponding carboxylic acids with a mixture of aliphatic and heterocyclic polyamines. The aminoamide resins according to the invention are prepared by polycondensation of carboxylic acids with an average molecular weight of 146 to 650, or their C 1-4 esters, with a mixture of polyamines consisting of 20 to 90 wt. % of aliphatic polyamines of structure

H ₂ NCH ₂ CH ₂ - | --NHCH ₂ CH ₂ ^ ---- NH ₂ az

1-4 'to 80 wt. % of heterocyclic polyamines of structure k ₂ n - [- ch ₂ ch ₂ nh] ---- ch ₂ ch ₂ n

0-4 ^CH ₂ ^CH 2 ^X N ch ₂ ch ₂ ^

CH ₂ CH ₂ N ----- H,

0-4 in a molar ratio of polyamine iCOOH or COOR = 0.9 to 3: 1, where R is alkyl of one to four carbon atoms in the molecule.

The prepared aminoamide resins are viscous liquids with excellent miscibility with known types of epoxy resins. The handling of aminoamide resins according to the invention does not lead to the development of exhalations, or only in small amounts, even in large-scale applications such as the production of cast floors, plastic-concrete components, pouring penetrations and the like. Compared to known aminoamide resins, it is possible to observe an improvement in flow properties, pouring and a reduction in the number of film defects, or their disappearance (craters, greasy eyes, etc.).

CS 266 519 Bl

Example 1

146 g (1 mol) of adipic acid are mixed with 2 moles (368 g) of mixed polyamines having the composition: 3.8% diethylenetriamine, 11.9% triethylenetetramine, 27.9% tetraethylenepentamine, 46.3% pentaethylenehexamine and 10.1% N-aminoethylpiperazine. 1 g of finely divided sodium sulfite is added to the mixture, after which the mixture is heated to 150 DEG C. for 1 hour, to 180 DEG C. for 30 hours and to 190 DEG C. for 30 minutes while stirring and distilling off the precipitated water, keeping the acid number below 5 mg KOH / g. The product is an aminoamide resin with an amine number of 357 mg KOH / g, a viscosity of 8,450 mPa.s / 25 ° C, an equivalent weight of 49.1 and an acid number of 3.1 mg KOH / g. The vapor pressure is less than 13 Pa at 30 ° C.

Example 2

613 g (1 mol) of industrial polymeric fatty acids (MK) containing 5% of monomeric MK, 22% of trimeric MK and 73% of dimeric MK, are mixed with 3 moles (713 g) of a mixture of polamines with the composition: 41.3% tetraethylenepentamine, 20 3% pentaethylenehexamine, 12.1% and 26.3% hexaetylénheptaminu heterocyclic polyamines structure CH ₂ = CH ₂ ^H 2 ^{N '^} - ^{CH2 CH2 _-NH-CH2} ---- CH ₂ N? N-CH ₂ CH ₂ NH ₂ .

3.01 CH ₂ CH ₂ '^

With stirring and simultaneous distillation of the liberated water, the mixture is heated to 180-185 ° C over 30 minutes and maintained at this temperature until the acid number drops below 3 mg KOH / g. The aminoamide resin obtained has a viscosity of 15,980 mPa.s / 25 ° C, an amine number of 422 mg KOH / g, an equivalent weight of 82 and a vapor pressure at 25 ° C of less than 0.1 Pa.

Example 3

186 g (1 mol) of isononanoic acid methyl ester are mixed with 0.9 mol (120 g) of a mixture of polyamines consisting of: 35.0% diethylenetriamine, 34.4% triethylenetetramine, 14.2% N-aminoethylpiperazine and 16.4% bis - (Ν, Ν'-aminoethyl) piperazine. 0.5 g of potassium ethylate is added to the mixture, and the mixture is heated to 150 DEG C. for 60 minutes while distilling off the released methanol, then heated to 180 DEG-185 DEG C., where it is maintained until the evolution of methanol has ceased. The product has a viscosity of 1.845 mPa.s / 25 ° C, an amine number of 520 mg KOH / g, an equivalent weight of 94 and a vapor pressure of 1.5 Pa.

Claims (1)

OBJECT OF THE INVENTION An aninoamide resin obtainable by polycondensation of carboxylic acids having an average molecular weight of 146 to 650, or their C ₁ to C ₄ esters, with a mixture of polyamines consisting of 20 to 90 wt. % of aliphatic polyamines of structure: H ₂ NCH ₂ CH ₂ - £ - NHCH ₂ CH ₂ ^ ---- NH ₂ 1-4 and from 10 to 80% of heterocyclic polyamines of structure in a molar ratio of polyamine: COOH or COOR = 0.9 to 3: 1, wherein R is alkyl of one to four carbon atoms in the molecule.