CS231697B1 - Polyaminoamides - Google Patents

Abstract

Polyaminoamides based on reaction products of polyamines with monomeric and/or polymeric acyclic carboxylic acids or derivatives of these starting materials contain, from the total amount of amide-bonded carboxylic acids, 2 to 100% by weight of polymeric carboxylic acids with an average molecular weight of 400 to 5,000. They are copolymers and adducts of , , -unsaturated carboxylic acids with unsaturated hydrocarbon monomers or with their unsaturated copolymers. Polyaminoamides optionally also contain up to 98% by weight of monomeric saturated and unsaturated acyclic carboxylic acids with an average molecular weight of not more than 1,000. They are a suitable hardener for epoxy resins and water-dilutable epoxy systems.

Description

The invention relates to polyaminoamides which contain amide-linked polymeric carboxylic acids and optionally also monomeric and / or oligomeric acyclic carboxylic acids.

The synthesis of polyaminoamides is well known and most commonly involves the reaction of polyamines with monomeric or oligomeric saturated and / or unsaturated acyclic carboxylic acids (U.S. Patent Nos. 2,379,413, 2,450,940, Australian Pat. No. 446,719, French Pat. No. 1). 421,153) or with epoxidized unsaturated fatty acids and their esters (Australian Pat. No. 219,177, German Pat. No. 1,420,465). In order to improve the properties, the polyaminoaraids are further modified, for example by reaction with phenol-formaldehyde condensates (No. AO no.

193 190) and carboxyl homopolymers or copolymers of conjugated dienes (No. AO No. 218 996) or (meth) acrylic compounds (No. AO No. 218 997). A common disadvantage of these products is their considerable viscosity due to the relatively high weight of the modifying components.

This drawback is overcome by the present invention, which is based on the reaction products of polyaraines containing 2 to 9 nitrogen atoms and 2 to 19 carbon atoms with ronomeric and / or polymeric acyclic carboxylic acids having 6 to 54 carbon atoms or derivatives of these starting materials. According to the invention, polyaminoaraids contain from 2 to 100% by weight of the total amount of amide-linked carboxylic acids. polymeric carboxylic acids having an average molecular weight of 400 to 5,000. They are copolymers and adducts of .alpha.

231 697 xylic acids containing 3 to 6 carbon atoms with unsaturated hydrocarbon monomers having 4 to 12 carbon atoms or their unsaturated copolymers. The polyaminoamides optionally also contain up to 98 wt. % of saturated and unsaturated acyclic carboxylic acids having 6 to 24 carbon atoms and / or oligomers thereof with an average molecular weight of 1 000 or less.

The polyaminoamides of this invention have some advantages over known types. In particular, by suitable selection of species and amounts of modifying polymeric carboxylic acids and optionally other starting components, low-viscosity and very reactive products are obtained. These are well mixed with other low molecular weight and especially high molecular weight substances and are easy to process.

The polyaminoamides of the present invention are the reaction products of polyamines with carboxylic acid polymers and optionally also with monomeric and / or oligoraeric saturated and unsaturated acyclic carboxylic acids or derivatives of these starting materials.

The amine starting component is polyamines having 2 to 9 nitrogen atoms and 2 to 19 carbon atoms. These include, in particular, acyclic alkylene polyamines and polyalkylene polyamines containing primary and secondary amino groups (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, di-1,2-propanetriamine, di-1,3-propanetriamine, tri-1,3-propanetriamine, pentamethylenediamine, hexamethylenediamine bis (hexamethylene) triamine, decamethylenediamine, ethanolamine and others).

Primary cyclic diamines (cyclohexanediamine, diarainomenthanes, diaminodicyclohexylalkanes, phenylenediamines, naphthylenediamines, xylylenediamines, diaminodiphenylalkanes) also come. The polyamines are always added in a molar excess of the amino group relative to the carboxylic acid groups. Acyclic polyamines provide more reactive polyaminoamides compared to cyclic polyamines.

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The acid component comprises, in particular, polymeric carboxylic acids having an average molecular weight of 400 to 400

According to the invention, only copolymers and / or adducts of .alpha.,. Beta.-unsaturated carboxylic acids having up to 6 carbon atoms (acrylic, methacrylic, maleic, fumaric, citraconic, pyrocinchon, mesaconic, itaconic or their respective anhydrides, in particular maleic anhydride) are exclusively used. unsaturated hydrocarbons having 1 or 2 double bonds (butenes, pentenes, hexenes, heptenes, cyclopentene, cyclohexenes, indene, methyl · indenes, butadiene, isoprene, piperylene, dimethylbutadiene, chloroprene, pentadienes, hexadienes, cyclopentadiene, dicyclopentadiene, cyclohexadiene) or Unsaturated polymers · These include liquid oligomers, co-oligomers or low-molecular-weight copolymers of various mixtures of the above, unsaturated hydrocarbons. The proportion of amide-linked polyaminoamides of these polymeric carboxylic acids is 2 to 100% by weight. This means that in addition to polymeric carboxylic acids, the polyaminoamides may also contain other amide-linked carboxylic acids. This group consists of saturated and unsaturated monomeric and / or oligoraeric acyclic carboxylic acids. Monomeric acids are derived mainly from natural drying oils (linseed, woody, safflower, rapeseed, oiticic, perilla, ricinine, fish), semi-dry (soybean, talium, sunflower, cotton) and non-drying (coconut, castor, olive, podzeranic) a mixture of saturated acids (caproic, carp, lauric, lauric, myristic, palmitic, stearic, peanut, behenic and lignoceric) and unsaturated (oleic, linoleic, linolenic, oC- and / 3-eleostearic, erucic, ricinoleic and 9,11- ricinen).

Synthetic saturated acids (neoacids, Koch acids), 2-ethylhexanoic acid, octoic acid, pelargonic acid and others are also suitable. These monomeric acids containing up to 24 carbon atoms can also be used in the form of their derivatives, such as esters, epoxidized esters or glycidyl esters.

231 697

These unsaturated polymerized acids are of great importance. Mostly technical products usually contain higher oligomers (trimmers) and have a maximum average molecular weight of 1,000. Some of the raonomeric or oligomeric acids can be replaced by acyclic and / or cyclic dicarboxylic acids or their anhydrides such as adipic acid, azelaic acid, fumaric acid and maleic anhydride;

The synthesis of the polyaminoamides according to the present invention includes generally known technological processes. The individual processes depend on the starting materials used. Thus, it is possible first to start from the polymeric carboxylic acids themselves. These are prepared either in advance or even at the start of the synthesis of polyaminoamides in a single reactor, for example by adding an unsaturated carboxylic acid to an unsaturated hydrocarbon polymer. Mixtures of these polymeric carboxylic acids with monomeric or oligomeric acyclic unsaturated carboxylic acids may also be used. The polyaraines which then react with these acid components are predominantly represented by reactive polyalkylene polyaraines. The reaction is carried out in a stirred reactor equipped with a heating jacket and a distillation head with a condenser. The starting components, i.e. the corresponding polyamines, the polymeric carboxylic acids and optionally the raonomer and / or oligomeric carboxylic acids or derivatives thereof are introduced into the reactor. With efficient stirring, the reaction mixture is heated to a temperature of 100 to 250 ° C, during which aaidation and possibly other reactions take place. Similarly, polymeric carboxylic acids are amidated by reacting them with preformed conventional types of polyaminoamides. monograph (F · Rybnikář, Z · Ditrych,

Z. Klácel, 0. Ordelt: Analysis and Testing of Plastics, SNTL, Prague 1965).

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The polyaminoaraids of the present invention are homogeneous and clear liquid or even solid products having an amine number of 100 to 400 and a softening temperature of up to 130 ° C. They are suitable for processing in the field of plastics and paints ·

The invention is further illustrated by the following examples, wherein parts and percentages are by weight. In Examples 1 to 4, the following reaction components are used:

Polymeric carboxylic acid PKK-1 It was obtained by a Priedel-Crafts reaction from a mixture of styrene, butadiene, pentene, hexene, indene, piperylene and maleic anhydride and had the following parameters:

acid number 120 mg KOH / g softening point 100 ° C average mol. weight 2 800

Polymeric carboxylic acid PKK-2 Adduct 15 parts of maleic anhydride to 85 parts of unsaturated hydrocarbon resin based on a mixture of pentene, hexene, cyclopentadiene, dicyclopentadiene, isoprene and styrene with the following parameters: acid number 150 mg KOH / g softening point 130 ° C average mol. weight 600

NP-1 unsaturated polymer

It was prepared by a Priedel-Crafts reaction from a mixture of styrene, butadiene, pentene, hexene, indene, piperylene with * parameters: average mol. weight 500 degree of unsaturation corresponding to four double bonds per 1000 g of resin ^ NP-2 unsaturated polymer

It was prepared by a Priedel-Crafts reaction of a mixture of pentene, hexene, cyclopentadiene, dicyclopentadiene, isoprene and styrene with the parameters:

average mol. weight 4,500 degree of unsaturation corresponding to 2.5 double bonds per 1000 g resin.

Example 1 23i 697

Polyaminoamide based on diethylenetriarain and an adduct of unsaturated polymer NP-1 with maleic anhydride containing 100% polymeric carboxylic acids of the total amount of amide-linked carboxylic acids ·

To prepare a polyaminoaraid, proceed as follows:. 450 parts of unsaturated NP-1 polymer are clogged in the reactor. The solution is heated to melting and then 50 parts of raaleic anhydride and 25 parts of toluene are added with good stirring at 165 ° C. The reaction mixture was heated to 200 ° C over 2 hours and maintained at this temperature for 3 hours. The conversion of maleic anhydride addition after this time is more than 98.5% and the resulting polymeric carboxylic acid has an acid number of 140 mg KOH / g. After cooling to 120 ° C, 140 parts of diethylenetriamine are added with stirring and the reactor contents are heated to 200 ° C and maintained at this temperature for 3 hours. After cooling to 170 ° C, it was dissolved in a mixture of xylene and butanol (3: 1 part) to a 50% solution. The amine number of the polyaminoaraid solution is 112 mg KOH / g. The product is a suitable hardener of solution epoxy systems.

Example 2

Polyaminoamide based on dipropylenetriamine, acyclic monocarboxylic acids obtained by cleavage of linseed oil and adduct of unsaturated polymer NP-2 with citraconic anhydride, containing 60,8% polymeric carboxylic acids and 39,2% acyclic monocarboxylic acids prepared by cleavage of rope oils.

To prepare the polyaminoaraid, 400 parts of acyclic monocarboxylic acids obtained by cleavage of linseed oil and 400 parts of unsaturated NP-2 polymer are introduced into the reactor. The mixture was heated to 150 ° C while stirring the ligatures and 160 parts of maleic anhydride were added

231,697 and 60 parts citric acid anhydiide. Continue heating up to 205 ° C and hold at this temperature for 4 hours. After this time, the conversion of the addition reaction, judged by the presence of free anhydrides, is greater than 90% and the acid value of the prepared intermediate is 305 mg KOH / g. After cooling to 100 ° C, 783 parts of dipropylene triamine are added and the reaction mixture is kept at 210 ° C for 3 hours, then cooled to 100 ° C and diluted to 50% with distilled water. The amine number of this solution is 175 mg KOH / g and the polyamine amide solution obtained is a suitable hardener for water-dilutable epoxy systems.

Example 3

Polyethylenetriamine-based polyaminoamide and a mixture of polymeric carboxylic acid PKK-1 with dimerized carboxylic acids obtained by fission of linseed oil, containing 20% polymeric carboxylic acids and 80% oligomers with an average molecular weight of 560, prepared from acyclic carboxylic acids by total amide-linked carboxylic acids obtained by fission of linseed oil.

To prepare the polyamine amide, 400 parts of diraeric acyclic carboxylic acids of linseed oil were charged to the reactor and 100 parts of polymeric carboxylic PKK-1 were added. The mixture is heated to 130 ° C with an Ng inlet and 180 parts of diethylenetriamine are added with stirring, the temperature of the reaction mixture is gradually raised to 205 ° C and kept at this temperature for 4 hours. A polyaminoamide having an amine number of 270 mg KOH / g is obtained, which can serve as a hardener for epoxy resins.

Example 4

Polyaminoamide based on dipropylenetriamine and a mixture consisting of adducts of acrylic acid with an unsaturated polymer

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IIP-2 and acyclic carboxylic acids obtained by cleavage of soybean oil and polymeric carboxylic acid PKK-2 containing 5.3% polymeric carboxylic acids and 94.7% acyclic monocarboxylic acids out of the total amide-linked carboxylic acid ·

To prepare the polyamino amide, 475 parts of acyclic monocarboxylic acids obtained by soybean oil cleavage are introduced into the reactor. 12.5 parts of unsaturated NP-2 polymer are added and heated to 160 ° C with Ng being introduced. 3 hours 90 parts of methacrylic acid and the reaction mixture is maintained at this temperature for a further 5 hours. Then 16 parts of PKK-2 are added, cooled to 130 ° C and 432 parts of dipropylene triamine are added. Heat to 210 ° C and react for 4 hours. This gave a polyamine amine having an amine number of 332 mg KOH / g.

Claims (1)

SUBJECT OF THE INVENTION 231 697 'Polyaminoamides based on reaction products of polyamines containing 2 to 9 nitrogen atoms and 2 to 19 carbon atoms with monomeric and / or polymeric acyclic carboxylic acids having 6 to 54 carbon atoms or derivatives of these starting materials, characterized in that % of amide-linked carboxylic acids contain 2 to 100 wt. polymeric carboxylic acids having an average molecular weight of 400 to 5,000 from the group of copolymers and adducts of C, β-unsaturated carboxylic acids containing 3 to 6 carbon atoms with unsaturated hydrocarbon monomers having 4 to 12 carbon atoms or their unsaturated copolymers and optionally up to 98% wt. monomeric saturated and unsaturated acyclic carboxylic acids having 6 to 24 carbon atoms and / or their oligomers with an average molecular weight not exceeding 1 000.