CS218997B1 - Process for producing modified aminoamides - Google Patents

Abstract

The invention relates to a method for producing aminoamides modified with low molecular weight acrylic polymers. Its essence lies in the fact that aminoamides based on reaction products of polyamides with aliphatic carboxylic acids and/or epoxy compounds and optionally with phenolaminoaldehyde condensates - or their starting components or intermediates - are subjected to a reaction at a temperature of 50 to 250 °C with 5 to 60% by weight of acrylic polymers and/or copolymers with a molecular weight of 500 to 30,000, while simultaneously distilling off volatile by-products. Modified aminoamides are used for curing epoxy resins.

Description

The invention relates to a process for the manufacture of aimtaoimides modified with low molecular weight acrylic polymers. Modified ammonium amides react cold with epoxy resins, with which they provide three-dimensional mucretmiolecular substances of excellent mechanical properties.

The synthesis of aminoamides consists in the reaction of polyamines with imionomeric or polymeric amino acids. fatty acids (U.S. Pat

279,413, 2,459,940, austral, U.S. Pat. No. 4,146,719, French. No. 1,421,153) and / or epoxy compounds (Australian Patent No. 219,177, German Patent No. 1420,465, U.S. Pat. No. 92,573, 101,588, 106,010, CS, AO No. 187,162, 218 987). The products obtained have free reactive amino groups which react at room temperature with epoxy resins or even with water-dilutable, i.e., eptoxidive, aqueous dispersions or with water-soluble products. Improvements in water permeability of amino amides, stability of their aqueous solutions, and improved properties of cured epoxy resins are achieved by various modifications. This includes, for example, the addition of 4-unsaturated carboxylic acids and their esters (U.S. Pat

816 366) or by reaction with phenolaminoaldehyde condensates (AO No. 193 190).

A substantial improvement in the physico-mechanical properties of the cured epoxy resins is achieved by the use of the curing agents prepared according to the present invention for the production of modified aminoamides based on the reaction products of polyamines containing 2 to 9 nitrogen atoms and 2 to 19 carbon atoms with aliphatic monomeric or polymeric polyamines. carboxylic acids having 2 to 3 carbon atoms and / or epoxide; compounds having a molecular weight of 40 to 1ΌΌΟ and optionally with phiolithaminoaldehyde condensates in a molar ratio of amine, carboxy and epoxide groups of 1: 0.05 to 0.5:

According to the invention, the reaction products having an amine number of 200 to 600 and / or their starting components or intermediates are subjected to a temperature of 50 to 2/50 ° C and optionally in the presence of up to 45 wt. . % organic solvents and / or up to 5 wt.% catalysts reacting with 5 to 60 roles. % of acrylic polymers and / or copolymers having a molecular weight of 500 to 30,000, while distilling off the volatile by-products. Preferably, said reaction products are modified by reaction with thermoplastic or thermo-reactive polymers and / or copolymers of acrylic and mercacrylic acid, their esters, nitriles or amides.

The amidamides modified according to the invention have some advantages over the known amino amides. In particular, by suitably selecting the types and amounts of aminoamide starting materials, modifying acrylic polymers and copolymers, and manufacturing technologies, products having low viscosity and well soluble in water are obtained. They are excellent hardeners of epoxy resins of non-aqueous and especially of water-soluble or water-dilutable (dispersible) types. In this case, 1 are very reactive in the presence of water, so that curing occurs at room temperature. Hardened epoxy resins have good physico-mechanical properties and good adhesion to substrates even in aqueous environments.

The preparation of the modified aminoamides according to the invention is based on the ammonium amides, the synthesis of which is well known. Advantageous production technologies are described, for example, in MS. AO Nos. 187 162, 193 190 and 218 987. The main starting materials here are the amines having 2 to 9 nitrogen atoms and 2 to 19 carbon atoms. These include, in particular, aliphatic alkylene- and polyalkylene polyamines containing primary and secondary amino groups (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, di-1,2- and -1,3-propanediamine, tri-1,3-propahtetramine, ini, hexamethylenediamine). , bis (/ hexamethylene / triamine, etc.), and also primary cyclic di-amines (e.g., cyclohexanediamines, diamammomentanes, diaminodicyclohexylalkalines, diaimiiniodienyl alkanes, xylenediamines, phenylenediamines, and naphthylenediamines).

Other reactive components are aliphatic carboxylic acids having 2 to 36 carbon atoms. They include, in particular, saturated and unsaturated monocarboxylic acids (acetic, propipniic, butyric, 2-ethylhexanoic, dttoic, argonic, lauric, myristoric, palmitic, stearic, oleic, linolenic, linoleic, riciuoleic, and palmltoolearic). eg unsaturated fatty acid dimers, adipoic acid, azelsl, new, maleic and fumaric acids). They are used singly or more often in mixtures such as fatty acids isolated from non-drying oils (rtoinic, tannic, coconut), semi-dry and desiccating (soybean, tallow, linseed, wood, rapeseed, safflower, citric, perillus, bahutic, ricinen, sezaima, olive, poppy, sunflower and fish oils). Synthetic fatty acids are also suitable in place of these natural fatty acids.

The epoxide compounds used in the synthesis of the ammoniacantides of the present invention are mainly represented by the epoxidized C12-C22 unsaturated fatty acid esters isolated from the aforementioned drying and semi-drying vegetable and animal oils. Also suitable are polyepoxide compounds and resins, especially polyglycidyl ethers prepared by the alkaline condensation of epichlorohydrin with 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), biis (4-hydroxyphenyl) sulfoin (bisphenols S) or polyalkylene glyicols. polyglycidyl esters, polyglygildylamines, laliphatic and cycloaliphatic polyepoxides obtained by epoxidation of the respective unsaturated compounds with peracids, epoxy-oxidized homopolymers and butaidiein copolymers are of particular importance. These also include monoglycidyl compounds, especially monoglycidyl ethers, such as butyl glycidyl ether, decylglycidyl ether, phenylglycidyl ether and cresylglycides, ether, as well as monoglycidyl esters, monoglycidylamines and other m onoiejpotoildOve compounds.

(The aminoamides according to the invention do not always need to be based on pre-prepared aminoamides. These may arise from the starting components or intermediates of the "lineage" only during the modification itself. % of carboxyl and epoxy groups ranged from 1: 0.05 to 0.5: 0.1 to 1, i.e. always in a molar excess of amino groups.

The conducting components consist of low molecular weight acrylic polymers and copolymers, the preparation of which is known and is not the subject of the present invention. In their synthesis, ee is primarily based on (meth) acrylic monomers containing one double bond, such as acrylic acid, methyl acrylate, ethyl acrylate, butylacrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, acrylonitrile acrylate its derivatives, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, methacrylamide and methacrylamide. In addition to these (meth) acrylic imiotnomers, the photocopolymer component also comprises other mono-olefins, preferably styrene, vinyl acetate and tert-butyl chloride, as well as vinyl toluene, n-methylstyrene, vinyl vinyl chloride, vinylidene chloride, vinyl ether, allyl and other unsaturated polymers. They consist of liquid oligomers or co-oligomers, low-viscosity to high-viscosity homopolymers and copolymers having a molecular weight of 5-00 to 30 OCX). Liquid products are used directly, the higher molecular weight potymers and copolymers then preferably in the form of solutions in non-reactive solvents or not in reactive monomers. They contain ester, carboxyl, nitrile, amide and other groups which, under the selected reaction conditions, are capable of reacting with amino amides or β starting materials or intermediates thereof. They are added in an amount of 5 to 60 wt. %, based on the total weight of the modified amine amide, depending on the type of modifying component used, the modified amino amide and the desired properties of the end product.

Modifications of said atmiinoamides and acrylic polymers and copolymers are present in the starting acrylic olefins up to 45 wt. % solvents. Depending on the molecular weight! Modifying or modified components used are non-reactive organic solvents (aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, esters, ethers, ketones, alcohols or their mixtures) and / or reactive (liquid acrylic and allylic monomers, imiomoepoxide compounds). The solvents are either present in the starting acrylic oligomers and polymers or are added subsequently. Up to 5 wt. % catalysts.

The aminoamides according to the invention can generally be modified as follows. Typically, amine amides having an amine number of 2C10 to 600 are reacted with liquid acrylic oligomers or polymers or their solutions in organic solvents. At the temperature of 100 to 250 ° C, the amidation occurs while distilling off the reaction water, and possibly even does not react with the active organic solvent. Alternatively, the modifying component can be reacted with the starting raw materials or intermediates of the aimino-amides, which are then additionally formed "in situ" during the modification. Depending on the species and quantity of the components used, various addition condensation and other reactions take place successively at a temperature of 50 to 250 ° C under atmospheric or reduced pressure and by-product distillation. This leads to a much deeper chemical modification of the amino amides and thus to a more efficient treatment of their amino acids. The modified amino amides are prepared in a stirred reactor equipped with a jacket for heating or cooling and a desilator with a condenser.

The obtained (modified umino-amides) are liquid products with a viscosity of 600 to 6000 mPa · s / 25 ° C and an amine number of 200 to 600. They are well soluble in organic polar solvents and partly also in water. They are used primarily as hardeners of polyepoxide compounds, especially In the presence of conventional additives (pigments, fillers, dyes, catalysts, solvents, surfactants and other additives), they provide very reactive epoxy casting compositions, sealants, adhesives, impregnating solutions and impregnating solutions. Curing occurs at room temperature or at a slightly elevated temperature (30-50 ^° C) to form three-dimensional imiaicro-molecular substances with explosive physical-mechanical properties.

The subject of the invention is further exemplified by Example 218997 β

however, its scope is not limited in any way. The parts and percentages are by weight. The determination of the target number of viscosity, content, epoxide groups, etc. was carried out according to the methods given in the monograph Rybnikář F., Dit-speed Z., Klácel Z., Ordelt 0 .: Analysis and testing of plastic himots. SNTL, Prague 1965.

Example 1

Starting from the amine of amine, number 350 and viscosity 320 mPa. s / 25 ° C is prepared by reacting 11.58 parts (0.11 mole) of diethylenetriamine, 16.42 parts (0.11 mole) of triethylenetetramine, 5 parts (0.04 mole) of cktoic acid, 1976 parts (0.07 mole) and 5.2: 10 parts (0.15 mol) of butyl esters of epoxidized linseed acids. 80 parts of this amine-amide are mixed in a reactor with 40 parts of a 50% 50% solution of copolymers of 40% methyl methacrylate, 50% butyl acrylate and 10% acrylic acid (molecular weight 5000) in a mixture of xylene and butanol (4: 1 ratio). . The reaction mixture is gradually heated to a maximum of 200 ° C with stirring. At the same time, the volatile secondary reaction polloidines, i.e. water, partly methanol and butanol, are distilled off and finally the organic solvents used. The obtained modified amine amide has an amine number of 270 and a viscosity of 750 mPa · s / 250 ° C _; It is suitable for curing epoxy paint rot applied to wet surfaces of building materials.

Example 2

Into the heated reactor are successively weighed 40 parts of copolymers with a mole. weight 30 (00 composed of 70% styrene, 25% butyl acrylate and 5% acrylonitrile, 30 parts (iq, 19 moles) of diethylenetriamine, 16 parts (0.11 moles) of triethylenetetramine and 12 parts of ethylene glycol monobutyl ether. After cooling to 40 [deg.] C., the mixture further adds, with stirring, 52 parts (0.15 mole) of soybean epoxy acid butyl esters (Q epoxide equivalent, 2.8 / 103 g); parts (0.04 moles) of octoic acid and 20 parts (0.07 moles) of linseed oil were slowly heated to 80 ° C, held at this temperature for 1 h and then raised to 230 ° C. distilled water of reaction, butanol, -a residual solvent. Prepare 'modified amtinoarnid aimiinovém the number 410 and viscosity' 2Í100 mlPa.s / 25 ^Q C. it can be applied especially when curing epoxy resins under water, such . Piastbetonů in preparation for rectifying vu and waterskiing on hold.

Example 3

40 parts (0.21 mol) of tetraethylenepentamine and 49 parts (Q, 14 mol) of epoxybutyl stearate are introduced into the reactor. The mixture is heated at most n: a 100 ° C for 1 hour and held at this temperature until all epoxy groups have reacted. 12 parts (0.08 moles) of octanoic acid were added to the resulting polyadduct and at 50 to 60 ° C 18 parts of a 50% aqueous dispersion of copolymers having a molecular weight · 25 0 (00 containing 35% diethyl methacrylate / 60% ethyl acrylate and 5% acrylic) The reaction mixture is slowly heated to 160 DEG-200 DEG C. for 2 hours and simultaneously the water from the acrylic dispersion, the reaction water and the corresponding alcohols are distilled off.The modified aminoamide has an amine number of 390 and a viscosity of 3500 mPa · s. 25 ° C. It can be used for curing casting and impregnating epoxy resins, as well as varnishes, adhesives and sealants in the absence of water.

Claims (2)

A process for the production of modified amine amides based on the reaction products of polyamines containing 2 to 9 nitrogen atoms and 2 to 19 carbon atoms with aliphatic monomeric or polymeric carboxylic acids having 2 to 36 carbon atoms and / or epoxy compounds having molecular weights of 40 to 1000 and optionally with phenolaminoialdehyde condensates in a molar ratio of amine, carboxyl and epoxide groups of 1: 0.65 to 0.5: 0.1 to 1, characterized in that said reaction products having an amine number of 200 to 600 and / or their starting materials components or intermediates subjected to OF THE INVENTION at a temperature of 50 to 250 ° C and optionally in the presence of up to 45 wt.% Organic solvents and / or up to 5 wt. % of the catalysts are reacted with 5 to 60 wt.% acrylic polymers and / or copolymers having a molecular weight of 500 to 30,000, while at the same time distilling off the volatile by-products. 2. The process according to claim 1, wherein said reaction products are modified by reaction with thermoplastic or thermore active polymers and / or copolymers of acrylic and methacrylic acid, their esters, nitriles or amides.