DE4040290A1 - Acryloyl functional polyester prepn., used as film formers - by esterifying carboxylic acid, alcohol and acrylic acid, then neutralising catalyst used, etc. - Google Patents

Abstract

Prepn. of polyesters (polyester acrylates) from polycarboxylic acids, opt. hydroxycarboxylic acids, polyhydroxy cpds., and acrylic acids comprises (a) azeotropically esterifying in a mixt. of one or more di- or higher functional carboxylic acids, partially or totally in anhydride form, one or more di- or higher functional hydroxy cpds. and acrylic acid, in a ratio of COOH(total):OH:acrylic acid or 1:0.9-1.5:0.2-0.7 with the addn. of solvent (mixt.) as drug aid, a crosslinking catalyst and a polymerisation inhibitor or a combination of several polymerisation inhibitors under an air inlet at 60-150 deg.C to a constant acid number; and (b reacting the prod. to an acid number of less than 10, pref. less than 5, after adding a carboxy-epoxy catalyst and a mono- or higher functional epoxy cpd. (mixt.) at 50-150 deg.C and the solvent (mixt.) is distilled off. USE/ADVANTAGE - The prepn. is simpler, the time taken is reduced, the prod. has high acryloyl content or high functionality at relatively low viscosity. UV irradiation gives hard adhesion-free and highly crosslinked films. The polyester acrylates are useful as film-formers for UV and electron hardenable coating materials.yl

Description

The use of acryloyl-functional polyesters (poly ester acrylates) as a film former for radiation-curable Be coating materials has long been state of the art; comp. z. For example, FR-OS 20 16 568, DE-OS 22 61 612, DE-OS 28 38 691.

The basic difficulty in esterification with Acrylic acid is that because of the prevention of a vorzei polymerization necessary for mild esterification a residue of unreacted acrylic acid in the reaction pro remains detrimental to the processing and film properties of the coating material.

The classic methods for removing the unreacted Acrylic acid are firstly aqueous washing processes - described z. B. in DE-AS 20 03 579 and Technical Information, Brochure No. 0034, R8 of the company PERSTORP AB (Sweden) - and second, distilling off the acrylic acid in vacuo (e.g., in U.S. Patent No. 4,130,518).

The disadvantages of the washing processes are above all the Ent stand by much unusable washing solution, separation problems due to emulsion formation and the onset of highly charged Industrial wastewater.

The distilling out of acrylic acid succeeds - even at several hours of evacuation and high temperature - only very un Completed.

In European Patent Application 00 54 105 and in DE-OS 33 16 593 and 38 36 370 is the third way to Be Side of the remaining, free acrylic acid implementation of the acidic crude product with epoxy compounds.

However, the cited documents describe exclusively Three-step syntheses, wherein in the first stage a hydroxyl Group-containing polyester (polyester polyol) as a precursor  prepared in the second stage of this polyester acrylated and in the third stage with the epoxy compound is reacted.

The disadvantage of this procedure is due to the Three-stage given high synthesis effort, thereby is reinforced that the as alcohol component to Vereste tion with acrylic polyester high molecular weight polyols xylgehalte must have, which is correspondingly high visco sities and / or inadequate solubility of these precursors in non-polar entrainers (hydrocarbons) brings.

The object of this invention is

• 1. the production process for polyester acrylates wesent simplify it;
• 2. to shorten the production time;
• 3. the necessary operational monitoring effort of the Reduce the process;
• 4. the environmental impact of manufacturing decrease;
• 5. in a simple way high acryloyl contents or high radio at relatively low viscosities To achieve polyester acrylates.

The above objects are achieved by the invention.

The invention relates to a process for the preparation of acryloyl-functional polyesters (polyester acrylates) from polycarboxylic acids, optionally hydroxycarboxylic acids, Polyhydroxy compounds and acrylic acid, characterized gekennzeich net, that in a one-pot process

• a) a mixture of
  one or more difunctional or higher-functional carboxylic acid (s), which may or may also be partly or completely present in anhydride form,
  one or more di- or higher-functional hydroxy compound (s) and
  Acrylic acid in molar ratio COOH (total): OH: acrylic acid = 1: 0.9-1.5: 0.2-0.7 after addition of a solvent or solvent mixture serving as entrainer (azeotrope former), an esterification catalyst and a polymerization initiator or a combination of several polymerization inhibitors under gentle introduction of air at 60 to 150 ° C until the constancy of the acid number azeotropically esterified,
• b) the esterification product solution obtained after addition of a Carboxy-epoxy catalyst with one or higher radio tional epoxy compound or a mixture of epoxy compounds between 50 and 150 ° C up to an acid number of less than 10, preferably less than 5, and dissolving medium or solvent mixture before, during or after the Reaction, optionally in vacuo, distilled off.

Further embodiments of the invention are in the claims. 2 given to 9.

In the group of polycarboxylic acids include two or higher functional carboxylic acids, which may also be in Form of their anhydrides can be present. examples are Phthalic acid, isophthalic acid, terephthalic acid, tetra- or Hexahydrophthalic acid, succinic acid, glutaric acid, adipin acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Maleic acid, fumaric acid, itaconic acid, citraconic acid, mesa Acid, Trimellitic Acid, Citric Acid, Tartaric Acid.

As two- or higher-functional hydroxy compounds for example: ethylene glycol, di- and triethy glycol, 1,2- and 1,3-propanediol (propylene glycols), di- and tripropylene glycol, 1,2-, 1,3- and 1,4-butanediol, 1,2- and 1,3-pentanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol,  2-ethyl-1,4-butanediol, neopentyl glycol, dimethylolcyclo hexane, trimethylolethane, trimethylolpropane, trimethylol butane, glycerol, pentaerythritol, di- (trimethylolpropane), Di- (pentaerythritol), sorbitol.

Other usable polyfunctional hydroxy compounds are the low molecular weight adducts of ethylene or propyne lenoxid to the abovementioned polyhydric alcohols.

In addition to the polyfunctional carboxylic acids and Hy Hydroxy compounds are also hydroxy as polyester raw materials carboxylic acids, which may also be present as lactone can, be used. Examples are ε-caprolactone and dime thylolpropionsäure.

As an entraining agent for selectively circling the reaction Water is rich in hydrocarbons and coal hydrogen mixtures both aromatic and aliphatic shear and cycloaliphatic nature suitable. examples are Toluene, xylene (s), n-hexane, n-heptane, cyclohexane, commer usual hydrocarbon mixtures such. For example, petroleum ether, Petroleum benzine, ligroin and so-called special benzine (Siede limits 70 to 140 ° C).

Toluene is for the production of polyester acrylates by far the most common entrainers and also for this be described method particularly suitable.

The amount of entraining agent to be added is in the range from 5 to 100%, in the case of toluene preferably between 30 and 50% the weight of the polyester raw materials (starting materials).

Examples of esterification catalysts are strong Säu such as sulfuric acid, methanesulfonic acid, p-toluenesulfone acid or naphthalenesulfonic acid. The amount to be added is between 0.1 and 3% of the raw material weight; for p-toluene Of olsulfonic proved 0.5 to 1.5% as optimal.

The acidic esterification catalyst may, after completion of the azeotropic esterification (step a) are neutralized. Suitable neutralizing agents are, for. B. alkali hydroxides or carbonates and tertiary amines, preferably one or a plurality of hydroxyl group (s) containing tertiary amines such as z. B. N, N-dimethyl-aminoethanol.  

In the case of neutralization of the catalyst acid with a tertiary amine such as. B. N, N-dimethyl-aminoethanol this catalyzes the carboxy-epoxy reaction of stage b.

The premature polymerization of acrylic acid and their Reaction products in the reaction mixture is predominantly through prevents the addition of inhibitors. In addition to hydroquinone Compounds of the hydroquinone mono type are also suitable alkyl ethers, 2,6-di-tert-butylphenol, N-nitrosamines, the phenothiazines and the phosphorous acid ester, which al lein or can be used in combinations, for inhibition. Depending on the effectiveness is the zuzusetzende Inhibitor amount between 0.001 and 2% of the raw material weighed.

In addition to the inhibition by the above Inhibitors, it is useful, by or through the Reacti Onsgemisch a weak stream of air, oxygen or an air / nitrogen mixture to the Polymeri tion of free acrylic acid, especially in the vapor system prevent.

To achieve the desired low acid number of the end product is the acidic polyester acrylate crude, wel Depending on the raw materials used, their Quantity ratios and the reaction conditions with a Acid number between 10 and 50 (based on the residue after Concentration in vacuo) is obtained with an epoxy compound or a mixture of several epoxy compounds at a higher temperature temperature, preferably at 100 to 130 ° C, reacted until the desired acid value is reached. In general, this is a conversion time between 1 to 10 hours required; decisive, however, is the achievement of the required acid number. Examples of suitable epoxy compounds are epoxi dited olefins, glycidyl esters of saturated or unsatd carboxylic acids and glycidyl aliphatic, cyclo aliphatic or aromatic polyols. Particularly suitable are epoxy resins of the bisphenol A-epichlorohydrin type as well as Glycidyl ethers of polyfunctional alcohols, eg. As the butane diols, glycerine and pentaerythritol. examples for Bisphenol A-epichlorohydrin commercial products are the  Epikote® types 812, 828 and 162 from Shell and the comparable products from other manufacturers. The amount of To be added epoxy compound should the acidity of the Crude product preferably be equivalent, but can also be lower or - z. B. to increase the liability verb increasing residual epoxide content in the end product - higher become.

The reaction between the carboxy and the epoxy groups is relatively slow. It is therefore the reaction mixture catalytically active substances in quantities up to 2% of the total mass to. Examples of such carboxy-epoxy catalyst which can be used individually or in combinations NEN, are triphenylphosphine, quaternary ammonium salts, tertiary amines, thioethers such as. Thiodiglycol, dimethyl sulfide, diethyl sulfide and certain metal compounds such as z. B. chromium (III) octoate. Is a tertiary amine already for Neutralization of the acid esterification catalyst after Stage a has been added, then the addition of another Carboxy-epoxy catalyst not required.

Of great importance with regard to the application properties of the radiation-curable coating material is the viscosity of the poly used as a film former esteracrylates. On the one hand, it should be low, ande on the other hand, be so high that the films after Bestrah sufficiently hard, tack-free and resistant. The viscosity of the polyester acrylates is of several factors such as the mean molar mass, the degree of branching, the hydroxyl value u. a. m. dependent. The degree of branching becomes mainly by the ratio of two to higher radio normal source materials (raw materials). For the optimal equivalent ratio of two- to three-functional Starting materials, d. H. without consideration of acrylic acid and the epoxy compound (s) to be added later became Range from 4: 1 to 1.5: 1 found.

The polyester produced in the manner described Acrylates turn yellowish to brown, usually clear  Compositions with viscosities between 5 and 50 Pa · s at 23 ° C They harden under the action of electron beams or - after addition of suitable photoinitiators such as benzophe non-amine combinations, acyldiphenylphosphine oxides or preferably α-cleavable carbonyl compounds such as. B. Acetophenone derivatives - rapidly due to UV irradiation hard, tack-free and highly networked films.

Processing into radiation-curable coating compositions or paints according to the known methods.

For precise adjustment of the viscosity as well as the film Properties can give the polyester acrylate the expert well-known reactive diluents, mainly from the acrylate Type, to be added. Examples are 1,4-butanediol di-alcohol lat, 1,6-hexanediol diacrylate, di-, tri- and tetraethylene glycols cold-acrylate, di- and tripropylene glycol diacrylate, neophen tylglycoldiacrylate, trimethylolpropane triacrylate, pentaery thyretriacrylate and tetraacrylate, acrylic esters of propoxy trimethylolpropane triacrylate, acrylic acid or Methacrylates of monohydric aliphatic or cycloaliphatic alcohols such. B. 2-ethylhexyl (meth) acrylate or cyclohexyl (meth) acrylate and N-vinylpyrrolidone. Also, the addition of small amounts of non-reactive solvents such as z. As methyl isobutyl ketone or butyl acetate is possible.

Furthermore, the coating materials in addition to the poly ester acrylate binder also other radiation-curable, che mixed-reactive or physically drying film-forming agents or Crosslinkers, fillers, dyes, pigments and those in the Paint and printing ink chemistry usual auxiliary substances (additives) such as thixotropic, smoothing, matting, leveling agents and Defoamer included.

The application can according to the in the paint and colors technology usual methods such as rolling, spraying, casting u. Ä. Preferred substrates are wood, wood-like Materials such as veneers and chipboard as well as paper and Cardboard.

The process of the invention is characterized by the following examples games clarified, but without limiting this.

example 1 Polyester acrylate 1

In a reaction trap provided with a water separator paratur becomes a mixture of 154 parts (the term "parts" in this document always means Parts by weight) phthalic anhydride drid, 228 parts adipic acid, 268 parts trimethylol propane, 258 parts of 1,4-butanediol, 375 parts of acrylic acid, 520 parts Toluene, 10.4 parts of p-toluenesulfonic acid monohydrate and 5.2 Divide hydroquinone with gentle introduction of air and stirring Held for 8 hours at high reflux (circulation), wherein Separate 156 parts of acrylic acid water and the Acid number of the reaction solution drops to 17. The boiling temp temperature rises to 129 ° C. 1354 parts of the crude ester Solution are then to distill off the toluene under vigorous stirring for 30 minutes at 130 ° C / 33 hPa (water jet vacuum). There remain 1052 parts of residue with acid number 20. 70.2 parts of Epikote® 828 are added (Epoxy resin from Shell, EEW 190) and 3.2 parts of triphe nylphosphine and kept under stirring for 2 hours at 120 ° C.

The final product obtained has the following data:
Non-volatile content 94%, viscosity (23 ° C) 15.2 Pa.s, acid value 3.5 (mg KOH / g), hydroxyl value 66 (mg KOH / g).

Example 2 Polyester acrylate 2a

In a reaction trap provided with a water separator Paratur is a mixture of 193 parts Phthalsäureanhy third, 190 parts adipic acid, 62 parts ethanediol (ethylene glycol) and 37 parts of toluene for one hour at reflux (Circulation), about 175 ° C, with 21 parts of water deposit. It is allowed to cool to about 100 ° C and esterified after addition of 220 parts of 1,6-hexanediol, 268 parts of tri methylolpropane, 375 parts of acrylic acid, 483 parts of toluene, 10.4 parts of p-toluenesulfonic acid monohydrate and 5.2 parts Hydroquinone with gentle introduction of air in the usual  Continue azeotropically for 8 hours, giving 134 parts of acrylic acid distilling off water and the acid number of the reac tion solution drops to 25. The boiling temperature rises 128 ° C. After 30 minutes concentration at 130 ° C / 33 hPa below Strong stirring left 1127 parts of residue with the Acid number 29.

To 500 parts of the residue are added 48.3 parts of Epikote® 828 (Epoxy resin from Shell, EEW 190) and 1.5 parts Tri phenylphosphine and allowed to stir at 120 ° C for 5 hours.

The final product obtained has the following data:
Non-volatile content 96%, viscosity (23 ° C) 21.4 Pa · s, acid number 5.1 (mg KOH / g), hydroxyl value 79 (mg KOH / g).

Example 3 Polyester acrylate 2b

The preparation of the crude product is carried out as in polyester acrylate 2a. Then proceed as follows:
48.3 parts of Epikote® 828 (epoxy resin from Shell, EEW 190) and 2.16 parts of N, N-dimethylaminoethanol (N, N) are added to 500 parts of the residue obtained after concentration with the acid number 29. Dimethyl-ethanolamine) and stirred for 2 hours at 120 ° C stir.

The final product obtained has the following data:
Non-volatile content 96%, viscosity (23 ° C) 30.4 Pa · s, acid value 2.8 (mg KOH / g), hydroxyl value 84 (mg KOH / g).

Example 4 Polyester acrylate 3

In a reaction trap provided with a water separator Paratur is a mixture of 59.2 parts Phthalsäureanhy third, 58.8 parts maleic anhydride, 127 parts diethylene glycol, 93.9 parts trimethylolpropane, 144 parts acrylic acid re, 200 parts of toluene, 4.0 parts of p-toluenesulfonic acid mono hydrate and 2.0 parts hydroquinone for 8 hours under gentle Air introduction and stirring at high reflux (circulation) held, with 52 parts of acrylic acid-containing water and the acid number of the reaction solution drops to 21. The boiling temperature rises to 127 ° C. After 30 minutes on remain at 130 ° C / 33 hPa with vigorous stirring  408 parts residue with the acid number 26. One gives 35.7 Parts Epikote® 828 (epoxy resin from Shell, EEW 190) and 1.22 parts of triphenylphosphine and kept under stirring 2 Hours at 120 ° C.

The final product obtained has the following data:
Nonvolatile content 95%, viscosity (23 ° C) 31.0 Pa · s, acid number 3.2 (mg KOH / g), hydroxyl value 82 (mg KOH / g).

Example 5 Polyester acrylate 4

In a reaction trap provided with a water separator a mixture of 51.2 parts of trimellitic acid, 87.7 parts adipic acid, 140 parts 1,4-butanediol, 35.8 parts Trimethylolpropane, 144 parts of acrylic acid, 200 parts Toluene, 4.0 parts of p-toluenesulfonic acid monohydrate and 2.0 Dissolve hydroquinone 10 hours with gentle air induction and stirring at high reflux (circulation), wherein Separate 65 parts of acrylic acid water and the Acid number of the reaction solution falls to 26. The boilers temperature rises to 124 ° C. 541 parts of the obtained crude ester solution are then used to distill off the volatile Proportions stirred vigorously for about 45 minutes at 130 ° C / 33 hPa, after which 353 parts of residue with the acid number 38.5 remain ben. There are 46.0 parts of Epikote® 828 (epoxy resin from. Shell, EEW 190) and 1.06 parts of triphenylphosphine to and Stirred for 2 hours at 120 ° C with stirring.

The final product obtained has the following data:
Nonvolatile content 90%, viscosity (23 ° C) 10.1 Pa · s, acid value 4.9 (mg KOH / g), hydroxyl number 61 (mg KOH / g).

Example 6 Polyester acrylate 5

In a reaction trap provided with a water separator Paratur is a mixture of 74.1 parts Phthalsäureanhy 73.1 parts of adipic acid, 70.6 parts of glycerol and 17 Divide toluene for one hour at reflux (circulation), approx. 175 ° C, with 16.5 parts of water deposited. It is allowed to cool to about 100 ° C and esterified after addition  of 99.1 parts of 1,4-butanediol, 144 parts of acrylic acid, 183 Partition toluene, 4.0 parts p-toluenesulfonic acid monohydrate and 2.0 parts hydroquinone with gentle introduction of air 10 hours in the usual way azeotrope, where 40 Distill off parts of acrylic acid-containing water and the Acid number of the reaction solution falls to 42. The boiling temp temperature rises to 122 ° C. After about 45 minutes of concentration at 130 ° C / 33 hPa with vigorous stirring remain 372 parts Residue with an acid number of 32. 50.5 parts of Epikote® 828 are added (Epoxy resin from Shell, EEW 190) and 1.12 parts Triphenylphosphine and stops under stirring for 8 hours 120 ° C.

The final product obtained has the following data:
Non-volatile content 89%, viscosity (23 ° C) 14.5 Pa · s, acid value 5.5 (mg KOH / g), hydroxyl value 116 (mg KOH / g).

Comparative example for the detection of the invention Polyester acrylate 6 according to not patented, three-stage process

(Hint: An attempt was made here to prepare a product analogous to the composition of the polyester acrylate 1 according to the three-stage synthetic route polyester polyol-poly ester acrylate crude product (acid) -polyester polyester acrylate end product.
The hydroxyl number of the polyester polyol is about 27% below the theoretically expected value, which is why the amount of acrylic acid used for acrylation must be selected to be 27% lower than for polyester acrylate 1.
The conversion of acrylic acid is much less complete than polyester acrylate 1.
The total esterification time is over three times (!) As long as polyester acrylate 1.)

In a reaction apparatus provided with a water separator, a mixture of 59.2 parts of phthalic anhydride, 87.7 parts of adipic acid, 103 parts of trimethylolpropane, 99.1 parts of 1,4-butanediol, 70 parts of toluene and 4.0 parts of p-toluenesulfonic acid Monohydrate under weak nitrogen for 9 hours held at high reflux (circulation), with 35 parts of water deposited and the acid number drops to 14. The resulting solution of polyester polyol has the following data:
Nonvolatile content 82%, viscosity (23 ° C) 1.25 Pa · s, acid value 14.3 (mg KOH / g), hydroxyl value 264 (mg KOH / g).

323 parts of the polyester polyol solution are 86.5 Tei acrylic acid, 130 parts of toluene and 1.2 parts of hydroquinone offset and with gentle air introduction another 18 hours held at high reflux (circulation), 11 Parts of acrylic acid water and the acid precipitate number falls to 60. The boiling point rises to 117 ° C. After 30 minutes concentration at 130 ° C / 27 hPa under kräf stirring, 298 parts of the residue remain with the acid number 20. 20.0 parts Epikote® 828 (epoxy resin of the Shell, EEW 190) and 0.90 parts of triphenylphosphine to and Stir under stirring for 3 hours at 120 ° C.

The final product obtained has the following data:
Non-volatile content 98%, viscosity (23 ° C) <51 Pa · s, acid value 5.3 (mg KOH / g), hydroxyl value 121 (mg KOH / g).

UV curing of the polyester acrylates 1 to 6

From the polyester acrylates 1 to 6 clearcoats are fol gender recipe:

polyester 80 parts dipropylene 20 parts Darocur® 1173 (photoinitiator from Merck) 4 parts Byk® 020 (defoamer from Byk-Chemie) 0.2 parts

(To further reduce viscosity one sets - depending on Viscosity of the polyester acrylate - between 10 and 20% Methyl isobutyl ketone too.)

After drawing each of a 120 micron thick film on a milk glass pane and 5 minutes evaporation is with 120 W / cm (H-radiator F300, electrodeless Fusion® system, Fa. Eltosch) and 5 m / min feed under air access once irradiated.

The films are fully cured immediately after irradiation and tack-free.

Film properties: see table  

table

Properties of hardened paint films on glass

The table clearly shows that the patent manufactures polyester acrylates 1 to 5 films with different, However, consistently good use properties result, elect the polyester acrylate 6 not prepared according to the patent leads to a soft, less resistant coating.

Notes on the examples

Examples 1, 4 and 5 describe the polyester acrylate Preparation according to claims 1, 3 and 4. To be emphasized in Example 4, the concomitant use of an olefinic-unge saturated acid anhydride (maleic anhydride), in Example 5 the use of a trifunctional acid component (Tri mellitic).

Examples 2 and 6 are based on claims 1, 3, 4, 7 and 8. Characteristic here is the short-term Vorvereste tion of ethylene glycol or glycerol with little High temperature entrainer without esterification catalyst sator.

Example 3 describes a method according to the claims 1, 2, 4, 5, 6, 7 and 8. The acidic esterification catalyst here with a tertiary amine (N, N-dimethyl-aminoethanol) neutralized, which in step b the carboxy-epoxy Catalyzed reaction.

Claims (9)

1. A process for the preparation of acrylol-functional poly esters (polyester acrylates) from polycarboxylic acids, where appropriate hydroxycarboxylic acids, polyhydroxy compounds and acrylic acid, characterized in that in a one-pot process

• a) a mixture of
  one or more di- or higher-functional carboxylic acid (s), which may or may also be partially or completely present in anhydride form,
  one or more di- or higher-functional hydroxy compound (s) and
  Acrylic acid in molar ratio COOH (total): OH: acrylic acid = 1: 0.9-1.5: 0.2-0.7 after addition of a solvent or solvent mixture serving as entrainer (azeotrope former), an esterification catalyst and a polymerization initiator or a combination of several polymerization inhibitors under gentle introduction of air at 60 to 150 ° C until the constancy of the acid number azeotropically esterified,
• b) reacting the resulting esterification product solution after addition of a carboxy-epoxy catalyst with a mono- or higher-functional epoxy compound or a mixture of epoxy compounds between 50 and 150 ° C to an acid number of less than 10, preferably less than 5, and the solvent or Solvent mixture before, during or after the reaction, optionally in vacuo, abde distilled.

2. The method according to claim 1, characterized in that the acidic esterification catalyst after esterification (Step a) with an inorganic or organic base is neutralized.   3. The method according to claim 1, characterized in that the acidic esterification catalyst in step b through Reaction with the epoxy compound is bound. 4. Process according to claims 1 to 3, characterized marked records that to achieve end product viscosities between 5 and 50 Pa · s at 23 ° C the equivalent ratio from bifunctional to trifunctional precursors of step a, d. H. without consideration of the acrylic acid and the Epoxy compound (s), ranging from 4: 1 to 1.5: 1. 5. The method according to any one of claims 1, 2 or 4, characterized characterized in that the according to claim 2 as Neutralisa tion medium used so selected organic base is that these in the stage b as carboxy-epoxy-cataly sator acts. 6. The method according to claim 5, characterized in that the neutralizing agent at least one tertiary amine is. 7. The method according to any one of claims 1 to 7, characterized ge indicates that one is in use or co-use a polyhydroxy compound containing the entrainer can distill off azeotropically, this Polyhydroxyverbin with the polycarboxylic acid (s) or corresponding anhydride (s) pre-esterified, then the remaining starting materials and additives added and the Mixture azeotropically finished esterified. 8. The method according to claim 7, characterized in that one with the pre-esterification without esterification catalyst a reduced amount of entrainer performs and then the esterification catalyst together with the remaining starting materials and auxiliaries as well as others Adding entrainer for Fertigveresterung.   9. The method according to any one of claims 1 to 8, characterized ge indicates that below the starting point used (raw materials) one or more hydroxycarbons acid (s), optionally in lactone form.