DE1745464C3 - New, curable, unsaturated polyester amine resin compounds - Google Patents

Description

US Pat. No. 28 06 822 discloses polyester-polyamide copolymers based on condensation products of alkanolamides with saturated dicarboxylic acids having 6 to 13 carbon atoms, wherein the ratio of carboxyl groups to the alkanolamines is 1: 1.02 to 1: 1.2, reaction of this Product with ethylenically unsaturated dicarboxylic acids and the subsequent copolymerization with aromatic comonomers whose side chains are ethylenically unsaturated, known.

where the equivalent ratio of the sum of hydroxyl groups and amino groups to the Carboxyl groups of the polymeric fatty acids can be between 1.2: 1 and 2: 1, and from

C) terminally arranged maleic acid

have been manufactured.

The further development of the subject of the

The main patent is characterized in that, instead of the polymeric fatty acids, higher molecular weight

branched carboxistearic acids of the general formula

C ₁₇ H ₃₄ (COOH) ₂

or their esters can be used.

The unsaturated polyesteramide resins of the present invention show - regardless of the particular special structure - in the various solvents and in particular also purely aromatic solvents up to very high concentrations

good solubilities. The term "soluble" is intended to here liquid at room temperature and not just gel-like Solutions include. Even from an unsaturated polyesteramine resin according to the invention, which contains about 12% maleic acid and in which the equivalence ratio of the amide bonds to the ester bonds is about 2: 1, it is possible to use 70 or even 80%, liquid solutions in toluene or what is of particular interest to manufacture in styrene. However, in order to have such extreme solubility to achieve that certain measures explained below are complied with; on the other hand is enough It is made for many areas of application, especially for impregnation coating when the solubility is up 20 ° u or less is limited.

In addition to the carboxistearic acids contained in the polyesteramide resins according to the invention, also small amounts of short-chain, saturated ones linear or branched aliphatic cycloaliphatic and aromatic dicarboxylic acids, e.g. B. adipic, azelaic, sebacic, dimethyladipic, trimethyladipic acid, Hexahydrophthalic acids, tetrahydrophthalic acids, ortho-phthalic acid, iso-phthalic acid and Terephthalic acid is condensed into the polyesteramide resins, but deteriorates in many cases with increasing amounts of these acids the solubility.

The unsaturated polyesteramide resin compositions of the present invention can be used as co-monomers vinyl monomers, such as styrene and chlorostyrene, acrylic monomers, such as methacrylates and acrylates, allyl esters and other olefinically unsaturated compounds or mixtures the same, commonly used as cocomponent in the field of unsaturated polyester resins are included. These resin compositions can be added at room temperature or at an elevated temperature of radical formers, in particular organic peroxides, and optionally accelerators for Curing are brought. These resin masses are used for charging surfaces as well as laminates, casting resins, fillers, adhesives.

Suitable alkanolamines which contain primary or secondary amino groups are e.g. B. monoethanolamine, Propanolamine, isopropanolamine and N-monoalkylalkanolamine, such as N-methylethanolamine and mixtures thereof. Because of economical reasons monoethanolamine is preferred. Two hydroxyl groups containing monoamines, such as diethanolamine, can also be used in small amounts.

The alkanolamines mentioned can be used alone as containing hydroxyl groups and amino groups Connections are used. According to the invention, however, they can also be used with aliphatic diamines and / or combine dihydric alcohols or else entirely by mixing: of primary or replace secondary aliphatic diamines and dihydric alcohols.

Suitable dihydric alcohols are in principle all those which are also suitable for the preparation of the known unsaturated polyester resins can be used, so z. B. alkylene glycols, such as ethylene, Propylene glycol, butanediols, hexanediols, neopentyl glycol and higher linear or branched dialcohols, so z. B. dimeric fatty alcohols (diol from dimeric fatty acid).

Dihydric alcohols are also suitable, the alkylene chain of which is formed by ether bridges, as in the case of polyglycols, z. B. diethylene glycol, dipropylene glycol, dibutylene glycol, or cycloaliphatic rings, such as with 1,4-dimethylolcyclohexane, or by aromatic Rings, as in bis- (hydroxy-ethoxyphenyl) -propane or 1,4-di- (hydroxyethoxy) -benzene, are interrupted.

Suitable diamines with primary or secondary amino groups are, for. B. ethylenediamine, 1,2- and 1,3-propylenediamine, 1,4-diaminobutane, 1,3-diaminobutane, diaminohexane, 2,4,4- and 2,2,4-trimethylhexamethylenediamine, 2-phenyl-l, 5-diaminopentane, 9- or 10-aminostearylamine, diamine from the dimeric fatty acid, alkyl-substituted on one or both nitrogen atoms Diamines, such as N-ethylethylenediamine, N-methylpropanediamine, N-butylpropanediamine, N, N'-dimethylpropanediamine or cyclic secondary diamines, such as dipiperidylpropane, cycloaliphatic diamines, like S-aminomethyl-S.S.S-trimethylcyclohexylamine, Bis (aminomethyl-cyclohexyl) methane.

The diamines can also have one or more ether groups. Examples are di (aminopropyl) ethers, a, o> -diamino-4,7-dioxadecane, H, o> -diamino-4,9-dioxadodecane, 1,4-di- (amino-n-propoxymethyH-cyclohexane, the ether diamine, which is obtained by cyanoethylation and hydrogenation from dimeric fatty alcohols is obtained. In addition to two primary or secondary amino groups, the amines can also additionally have tertiary amino groups, as z. B. the Aminoäthylpiperazin the I all.

If for the polyester amide resin compositions according to the invention linear, diprimary diamines are often used, the equivalence ratio should be used for the starting materials of the total hydroxyl to amino groups are preferably at least 1: 1 to achieve adequate solubility at room temperature. With increasing degree of substitution of the diamines and / or increasing the size of the substituting alkyl radicals can reduce this equivalence ratio will. For the majority of the diamines mentioned above, it can be less than 1: 1. It can in the event the linear, diprimary diamines are also low when gel-like or thixotropic solutions at room temperature be desired.

As far as higher molecular weight diamines, such as the diamine from dimeric fatty acid, or higher molecular weight divalent ones Alcohols, such as the diol from dimeric fatty acid. Are used in combination with low molecular weight dihydric alcohols or low molecular weight diamines are used.

The ratio of the sum of hydroxyl and primary or secondary amino groups to carboxyl groups in the starting materials of the first stage should be between 1.2: 1 and 2: 1. The ratio of amino groups to carboxyl groups should preferably not exceed 1: 1, but can in certain cases be higher.

In the preparation of the unsaturated soluble polyesteramide resins according to the invention, in a first reaction stage the higher molecular weight carboxystearic acids with the difunctional hydroxyl and compounds containing amino groups to form hydroxyl groups and optionally Polyesteramide resins bearing amino groups are condensed and the water of reaction is separated off.

In general, temperatures of up to about 250 ° C. can be used. In some cases, in particular when using Alkanolamine ^ it is

however, the polycondensation temperature, its processing and / or usage properties, is expedient

to about 170 to 180 C in order not to modify.

wanted to avoid side reactions. To the “. . . ,

speeding up and completing implementation P

can be worked under vacuum. 5 In one with a stirrer, descending condenser and pre-

In the second reaction stage, the reaction vessel provided with the intermediate sample is

products, the still reactive hydroxyl and amino atmosphere 200 g of C _J9 dicarboxylic acid, which in

have end groups, maleic anhydride added, known way from oleic acid by caiboxylation with

wherein per equivalent of the reactive endgroup aid of nickel carbonyl was obtained, with 60 g

pen 0.5 to 1 mole of maleic anhydride used io ethanolamine heated to 150 C within 20 min

will. This second stage of the process is held at 180 ° C. for 15 hours and then immediately. After this time

mean in the temperature range from about 50 to 140 C, a vacuum of 60 to 70 Torr is applied for 1 hour. The

accomplished. Reaction product has the following key figures: OHZ -

The speed of addition depends on 138; AZ = 9.6; SZ - 1.6.

the hydroxyl number of the polycondensation product; 15 217 g of this product are mixed with 212 mg of tert.

low hydroxyl numbers require higher addition butyl catechol stabilized and 50 g with stirring

temperatures or longer addition times. To full-maleic anhydride added; subsequently becomes

To ensure constant addition, the mixture is expediently stirred at 90 to 100 ° C. for 1 h. One receives a at

occasionally analytically checked whether there is still free maleic resin, room temperature tough resin with a DBW of

acid anhydride is present in the reaction mixture. The 0.191, which is in benzene, ethanol, isopropanol,

Addition can be readily soluble in the melt or in the presence of ethyl isobutyl ketone, dioxane, styrene and the like.

of inert to the reactants In styrene dissolved to a 70% solution and with

Solvents are carried out. 2% of a 50% solution of tert-butyl perbenzoate

When the addition in the upper part of the cured in dimethyl phthalate for 2 hours at 120 ° C. gives

If temperature ranges are carried out, a resin with a tensile strength of 539 kp / cm ^{2 is formed}

Usually structures that are produced during copolymerization and an elongation at break of 5%.
of the unsaturated polyester amide according to the invention

Resins with olefinically unsaturated compounds, such as. .

Styrene, the example in the presence of organic peroxides

The speed of gelation and hardening is positive, analogous to the manner described in Example 1

influence. 133 g of C ₁₉ dicarboxylic acid, as in Example 2, with 47 g

The unsaturated polyester according to the invention of an isomer mixture of 2,2,4- and 2,4,4-tri-

amide resins can be used together with those in the field methylhe.xamethylenediamine and 21 g diethylene glycol

the unsaturated polyester usually used is heated to 180 C within 4 h and then 22 h

Co-Mor.omers kept at 230 ° C. with the formation of hard to viscous flexible 35. After a vacuum of one hour

Resins are copolymerized by free radicals. A reaction product is suitably obtained with 60 to 70 Torr

Nete radical-forming catalysts are in particular the following indicators: OHN = 45; AZ - 1.4;

the known organic peroxides, such as. B. Ben-SZ - 5.9.

zoyl peroxide, di-t-butyl peroxide, lauryl peroxide, t-Bu- After stabilizing 166 g of the reaction styl perbenzoate, t-butyl hydroperoxide, cumene hydroper- product with 57 mg of tert-butyl catechol, oxide, cyclohexanone peroxide and methyl ethyl ketone are added with stirring to 14 g of maleic anhydride at 60 to peroxide, or mixtures thereof. The known accelerators can be added to these peroxides at 70 ° C. and then at 90 to 100 ° C. for 1 hour. A tough at room temperature such as tertiary amines, cobalt or vanadium salts orga-resin with a DBW of 0.079, which among andenic acids, optionally in combination with 45 rem in benzene, styrene, ethanol, methylsiobutyl ketone, mercaptans, such as lauryl mercaptan, diketones, such as and the like is readily soluble.
Acetylacetone can be used. In styrene at a 70 /, ^/, solution and treated with

The 2% of a 50% solution of tert-butyl perbenzoate according to the invention, dissolved in co-monomers

Unsaturated polyesteramide resins can also be cured in dimethyl phthalate for 2 hours at 120 ° C

curing with. Fillers or pigments and 5 ° a resin with a tensile strength of 123 kp / cm ²

in particular can be combined with glass fibers to and an elongation at break of 120%.

Claims (2)

Patent claims: 1. Further training of those curable after the addition of customary radical-forming catalysts unsaturated polyesteramide resin compositions based on condensation products from saturated and ethylenically unsaturated dicarboxylic acids and monoalkanolamines and styrene or its Homologues and, if appropriate, further comonomers and, if appropriate, fillers and others Usual additives, whereby they contain such condensation products as unsaturated polyester amide resins, from A) polymeric fatty acids or their esters and B) difunctional, hydroxyl groups and amino groups bearing compounds on the Base of a) Alikanolaminen with optionally branched ones Alkyne radicals with 2 to 10 carbon atoms and with primary or secondary Amino groups, the alkyl substituent of which can have up to 4 carbon atoms, and optionally additionally aliphatic diamines with primary or secondary amino groups and / or divalent ones Alcohols or b) Mixtures of aliphatic diamines with primary or secondary amino groups and dihydric alcohols, where is the equivalent ratio from the sum from hydroxyl groups and amino groups to the carboxyl groups of the polymeric fatty acids can be between 1.2: 1 and 2: 1, and off C) terminally arranged maleic acid have been produced according to patent 16 45440, characterized in that in place of the polymeric fatty acids or their esters, branched carboxystearic acids of higher molecular weight general formula C ₁₇ H ₃₄ (COOH) ₂ or their esters can be used. 2. Use of the unsaturated polyamide resin compositions according to claim 1 for the coating of surfaces and for the production of laminates, Casting resins, fillers, adhesives. In the USA. Patent 21 18 882, reaction products of α, / j-unsaturated dicarboxylic acids or their anhydrides with long-chain unsaturated fatty acids such as. b. Linolenic acid and, where appropriate, its further reaction with alcohols and inorganic bases. From the British patent 5 80 417 the manufacture of rubber-like products is by Condensation of dimeric fatty acids with alkanolamines in stoichiometric amounts and further conversion these polyester amides with sulfur and carbon are known. In the case of all of the above-mentioned products, however, the solubility in those to be used according to the invention is also important unsaturated comonomers not sufficient. From the USA ^ patent 23 79 413, the Canadian Patent specification 7 44 988, the Belgian patent specification 5 88 555 and the German Auslegeschiift 10 50 053 are polyester amides or polyamides from ao equivalent amounts of acids and amines as well Alcohols known. These reaction products are for the further reaction with '!, / ^ - unsaturated acids not suitable. The subject of patent 16 45 440 is after the addition of customary radical-forming catalysts curable unsaturated polyesteramide resin compositions based on condensation products from saturated and ethylenically unsaturated dicarboxylic acids and monoalkanolamines and styrene or its Homologues and, if appropriate, further comonomers and, if appropriate, fillers and other customary ones Additives, where sje as unsaturated Polyesteramidhar / e contain such condensation products that result from A) polymeric fatty acids or their esters and
B) difunctional compounds containing hydroxyl groups and amino groups, based on a) Alkanolamitien with optionally branched alkylene radicals with 2 to 10 carbon atoms and with primary or secondary amino groups, their alkyl substituents up to 4 carbon atoms may have, and optionally additionally aliphatic diamines with primary or secondary amino groups, and / or two valuable alcohols or b) Mixtures of aliphatic diamines with primary or secondary amino groups and dihydric alcohols,