DE1209744B - Process for the production of mixed polyesters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

C 08 g

German children: 39 c -16

Number: 1 209 744

File number: C 25144IV d / 39 c

Filing date: September 28, 1961

Opening day: January 27, 1966

It is known that moldings and coatings can be produced by connecting linear or branched ones polymerized unsaturated polyesters of monomeric polymerizable vinyl or allyl compounds. Linear or branched unsaturated polyesters are obtained by adding unsaturated dicarboxylic acids or their anhydrides, e.g. B. fumaric acid, maleic anhydride, itaconic acid, citraconic acid alone or together with saturated dicarboxylic acids or their anhydrides, e.g. B. isophthalic acid, terephthalic acid, Phthalic anhydride, tetrachlorophthalic anhydride, adipic acid, succinic acid, with polyhydric alcohols thermally polycondensed. The polyhydric alcohols mainly used are ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol or their mixtures are used. You can also use small amounts of trivalent or tetravalent alcohols, z. B. glycerol, trimethylolpropane, pentaerythritol, also use.

US Pat. No. 2,822,350 discloses saturated monomers instead of polyhydric alcohols Alkylene oxides, e.g. B. ethylene oxide, propylene oxide, butylene oxide, with saturated and / or unsaturated Convert dicarboxylic anhydrides in the presence of alkaline catalysts to polyesters. It is further known from German Patent 1034 854, by means of saturated alkylene or arylene oxides Reduce acid number of high molecular weight linear unsaturated polyester.

The unsaturated polyesters obtained in this way can be used in polymerizable monomeric vinyl and / or allyl compounds, e.g. B. styrene, vinyl toluene, divinylbenzene, diallyl phthalate, triallyl cyanurate, dissolved and with organic peroxides and accelerators to three-dimensionally crosslinked insoluble ones and infusible moldings and coatings are fully polymerized.

However, these known resin compositions have the disadvantage that the resin-air interfaces are not tack-free Harden. For this reason, such products are not suitable as paint raw materials.

Numerous methods are known to overcome this disadvantage. If, in addition to saturated dihydric alcohols, those which have a double bond in the ß, y position to an ether oxygen atom are used, e.g. B. glycerol monoallyl ether, pentaerythritol diallyl ether, according to the method of German Auslegeschrift 1 024 654, the oxygen in the air in the presence of heavy metal compounds participates in the crosslinking reactions of the unsaturated polyester resin, even at room temperature, and non-tacky surfaces are obtained.

Process for the production of mixed polyesters

Applicant:

Chemical works in Witten
Company with limited liability,
Witten, Arthur-Imhausen-Str. 92 a

Named as inventor:

Dipl.-Chem. Edith Behnke, née Dembski,

Hamburg cracks;

Dr. rer. nat. Helmut Wulff, Witten-Annen

However, owing to the easy cleavage of the β, γ-unsaturated ether bonds, such polyesters can only be produced by azeotropic esterification.

According to the invention is now a process for the production of mixed polyesters by reacting an acidic unsaturated polyester free of unsaturated ether residues with allyl ethers in the heat, which is characterized in that the polyester, which has an acid number between 80 and 200, at temperatures up to 150 ⁰ C in the presence of basic catalysts with optionally substituted allyl glycidyl ethers on the allyl group.

The German Auslegeschrift 1 024 654 refers to the increased risk of gelation in the production of unsaturated polyesters from dicarboxylic acids and, for example, glycerol monoallyl ether and the addition of monohydric alcohols is recommended.

The Belgian patent 560 981 describes the implementation of acidic unsaturated polyesters with Allyl ether alcohols that still have a free hydroxyl group. These monofunctional ether alcohols thus act as a chain terminator. The glycidic ethers used by us according to the invention however, due to the presence of the epoxy group, they are bifunctional. The reactivity of the epoxy group according to the invention allows a particularly gentle implementation.

It is true that unsaturated polyesters have been prepared from allyl glycidyl ether and phthalic anhydride described in the presence of tertiary amines (Polyesters from Epoxides and Anhydrids, Industrial and Engineering Chemistry, Vol. 52, No. 4, p. 321 ff., April 1960), but refers here to the fact that the the same reaction with maleic anhydride leads to very dark colored products which easily gel.

. 509 780/434

The polyesters used according to the invention, which have an acid number between 80 and 200, preferably between 100 and 150, are produced in a known manner by reacting unsaturated dicarboxylic acids or their anhydrides with dihydric alcohols in the melt at temperatures between 180 and 210 ^° C.

The unsaturated dicarboxylic acids can partly be replaced by saturated dicarboxylic acids or their anhydrides, z. B. isophthalic acid, terephthalic acid, tetrahydrophthalic acid, phthalic anhydride, adipic acid, Succinic acid.

Likewise, the dihydric alcohols can be partially replaced by trihydric and higher alcohols, e.g. B. Glycerol, trimethylolpropane, pentaerythritol, and possibly equivalent amounts aromatic or aliphatic monohydric alcohols, e.g. B. benzyl alcohol, endomethylenetetrahydrobenzyl alcohol, Ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, n-heptyl alcohol are also used to prevent cross-linking of the resin during condensation.

The acidic unsaturated polyesters are according to the invention at temperatures up to 15O ⁰ C, preferably between 100 and 120 ° C, in the presence of basic catalysts having the acid value of the polyester appropriate amount of an optionally substituted at the allyl group Allylglycidäthers z. B-Allylglycidathe ^ Allyl-zS-methyl-glycidathe ^ Methallylglycidäther, MethaUyl- / S-methyl-glycidäther, Crotylglycidäther reacted, whereby the acid number of the reaction mixture is reduced.

Suitable basic catalysts are amines, e.g. B. ethylenediamine, diethylenetriamine, triethylamine, dimethylcyclohexylamine, Dimethylaminopropylamine, or metal alcoholates, such as. B. sodium methylate and potassium ethylate.

This gives clear, light-colored mixed polyesters which are dissolved in styrene and used with the usual peroxide catalysts and accelerators are added in a manner known per se, also with admission of air to moldings and coatings with tack-free, easily sandable surfaces can be polymerized.

The method according to the invention is explained in more detail by the following examples:

example 1

A mixture consisting of 294 g of maleic anhydride, 444 g of phthalic anhydride, 106 g diethylene glycol and 228 g of 1,2-propylene glycol with stirring and carbon dioxide as inert gas at 205 ⁰ C in a known manner condensed polyester having an acid number of 130 is after stabilization with 0.2 g hydroquinone are added at 13O ⁰ C and 280 g Allylglycidäther and 1 g of dimethylaminopropylamine and from 5 to 6 hours at 95 to 100 ⁰ C to further condensation to an acid number of about 30 microns.

To prove the technical progress, the mixed polyester obtained is dissolved in as much styrene as that the solution contains 35% styrene. 100 g of the above solution of mixed polyester in styrene are in an

ίο in a known way with 2.5 ml of a commercially available 40% solution of methyl ethyl ketone hydroperoxide in plasticizer and then with 0.4 ml of a 1% cobalt-containing solution of cobalt octoate in styrene was added and painted on glass plates.

The spread is dust-dry after 20 to 30 minutes and fully hardened after 24 hours. It can then be perfectly ground and polished. A batch of similar structure without the addition of amine gels after a condensation time of 12 hours at 130 ^° C. with an acid number of 60.

Example 2

A g in a conventional manner from 196 maleic anhydride, 148 g phthalic anhydride, 106 g of diethylene glycol and 76 g of 1,2-propylene glycol up to an acid number of 100 and condensed with 0.1 g of hydroquinone stabilized acidic polyester is at 14O ⁰ C and 140 g Allylglycidäther and 5 ml of a 10% solution of sodium methylate in methanol are added.

The batch is condensed at 135 to 140 ^° C. for 4 to 5 hours to an acid number of 35 to 38.

100 g of the styrene solution can be used as follows

Example 1 described, catalysed and on with maple

veneered plywood can be applied. The coating is dust-dry after 10 to 15 minutes and afterwards Can be sanded and polished for 24 hours.

Claims (1)

Claim: Process for the production of mixed polyesters by reacting an acidic unsaturated polyester free of unsaturated ether residues with allyl ethers in the heat, characterized in that the polyester, which has an acid number between 80 and 200, is used at temperatures up to 150 ^° C. in the presence of basic catalysts with allyl glycidyl ethers optionally substituted on the allyl group. Considered publications:
German Auslegeschriften No. 1034 854, 1024 654; Belgian patent specification No. 560 981. 509 780/434 1.66 © Bundesdruckerei Berlin