AU2005276517A1

AU2005276517A1 - Products resulting from polymer-analogous reactions

Info

Publication number: AU2005276517A1
Application number: AU2005276517A
Authority: AU
Inventors: Patrick Glockner; Friedrich Georg Schmidt
Original assignee: Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2004-08-26
Filing date: 2005-07-28
Publication date: 2006-03-02
Also published as: DE102004041196A1; TNSN07072A1; EP1786846A1; BRPI0514277A2; MA29985B1; CA2577773A1; KR20070047312A; WO2006021478A1; CN1878803A

Description

IN THE MATTER OF an Australian Application corresponding to PCT Application PCT/EP2005/053677 RWS Group Ltd, of Europa House, Marsham Way, Gerrards Cross, Buckinghamshire, England, hereby solemnly and sincerely declares that, to the best of its knowledge and belief, the following document, prepared by one of its translators competent in the art and conversant with the English and German languages, is a true and correct translation of the PCT Application filed under No. PCT/EP2005/053677. Date: 14 February 2007 N. T. SIMPKIN Acting Deputy Managing Director For and on behalf of RWS Group Ltd WO 2006/021478 PCT/EP2005/053677 I Products resulting from polymer-analogous reactions The invention relates to products of polymer-analogous reactions, to a process for preparing them, and to their use. 5 Radiation-sensitive compounds possibly containing, if desired, acetophenone as a submoiety, and/or polymeric derivatives with acetophenone moieties, are described in EP 0 346 788, EP 0 377 199, and DE 102 06 987. 10 EP 0 346 788 describes ethylenically unsaturated, copolymerizable, radiation-sensitive, organic compounds which carry at least one (meth)acrylic ester group. EP 0 377 199 describes UV-crosslinkable compositions based on (meth)acrylic ester copolymers. In DE 102 06 987, vinyl ether derivatives are described. 15 None of these documents mentions the polymer-analogous reaction of ketone-aldehyde resins containing acetophenone by means of free-radical polymerization. Ketone-aldehyde resins are used in coating materials for example as additive resins in order to improve certain properties such as gloss, hardness or scratch resistance. 20 Ketone-aldehyde resins normally possess hydroxyl groups and can therefore be crosslinked only with, for example, polyisocyanates or amine resins. These crosslinking reactions are usually initiated or accelerated by means of heat. Further functional groups, such as amino and/or carboxyl groups, for example, can be inserted only through specific monomers, which 25 are difficult to obtain - if indeed they are obtainable at all - on the industrial scale. The polymer-analogous reaction of cyclohexanone-formaldehyde resins with azo compounds is described in Die Angewandte Makromolekulare Chemie, 168 (1989), p. 129 ff. The process is costly and inconvenient for the industrial scale. Since azo compounds are used, the 30 preparation entails substantial safety impositions. Moreover, azo compounds are thermally labile, making storage costly and inconvenient.

2 Journal of Applied Polymer Science, Vol. 72 (1999), p. 927 ff. describes cyclohexanone- and acetophenone-formaldehyde resins which become photoactive by virtue of the attachment of 10 mol% of benzoin or benzoin butyl ethers. The synthesis is costly and inconvenient, being carried out over two stages, which last more than 16 hours. Full conversion is not guaranteed, 5 and so volatile constituents may be present. Furthermore, low molecular mass fractions reduce the performance profile of high-grade coatings in terms of mechanical properties. Additionally, only polymer-analogous reaction products with styrene as monomer are described. The weathering properties of polymers containing styrene are known to be inadequate. 10 It was an object of the present invention to prepare products of ketone-aldehyde resins and unsaturated monomers which besides carbonyl and hydroxyl groups possess further functional groups and are distinguished by different solubility properties as compared with the initial resins. 15 A further object was to develop a process for preparing them that allows properties described above to be varied widely in a simple way. The products ought to be suitable for use in coating materials, adhesives, inks, including 20 printing inks, gelcoats, polishes, glazes, pigment pastes, filling compounds, cosmetic articles, sealants and/or insulants. Surprisingly it has been possible to achieve this object in accordance with the claims by means of polymer-analogous reaction of ketone-aldehyde resins containing acetophenone and/or 25 derivatives of acetophenone with unsaturated monomers by irradiation with UV light. Suitable ketone-aldehyde resins are polymeric reaction products of aldehydes of the general formula I and ketones of the general formula II, with additional ketones being used if desired. O 30 R R H 3 where R = H, unbranched or branched alkyl radical having 1 to 12 carbon atoms, aryl radical 0 O 5 R R2 () where R 1 = unbranched alkyl radical having 1 to 12 carbon atoms R2 =

R

3 10 R4 R7 R 5 R6 15 where R 3 to R7, = H, alkyl, OCH 3 , OC 2

H

5 , Cl, F, COO(C 1

-C

3 alkyl). Additionally, R 4 to R 6 can be OH, SH. Suitable unsaturated monomers are all unsaturated monomers which can be free-radically 20 polymerized. The invention accordingly provides polymeric reaction products substantially containing the reaction product of A) aldehydes of the general formula I 25 O R ,,,

H

(D R H where R = H, unbranched or branched alkyl radical having 1 to 12 carbon atoms, aryl radical 30 and 4 B) at least one ketone of the general formula II 0 5 R, R2 where R, = unbranched alkyl radical having 1 to 12 carbon atoms and R 2 = R 3 R4 104

R

7 R5 R6 15 in which the radicals R 3 to R 7 are H, alkyl, OCH 3 , OC 2

H

5 , Cl, F, COO(C 1

-C

3 alkyl), R4 to R 6 are additionally OH, SH, and 20 C) if desired, a further, CH-acidic ketone, and 25 D) at least one unsaturated monomer which is free-radically polymerizable, for use as a principal, base or additive component in coating materials, adhesives, inks, including printing inks, gelcoats, polishes, glazes, pigment pastes, filling compounds, cosmetic articles, sealants and/or insulants. 30 5 Suitable aldehyde components A) of formula I include, in principle, unbranched or branched aldehydes, such as formaldehyde, benzaldehyde, acetaldehyde, n-butyraldehyde and/or isobutyraldehyde, valerianaldehyde, and dodecanal, for example. In general it is possible to use all of the aldehydes said in the literature to be suitable for ketone-aldehyde resin 5 syntheses. Preference is given, however, to using formaldehyde and benzaldehyde, alone or in mixtures. The required formaldehyde is normally employed as an aqueous or alcoholic (e.g. methanol or butanol) solution with a strength of approximately 20% to 40% by weight. Other forms of 10 formaldehyde, such as the use of para-formaldehyde or trioxane, for example, are likewise possible. Examples of ketones B) of formula II are acetophenone and ring-substituted acetophenone derivatives, such as hydroxy-, methyl-, ethyl-, tert-butyl-, and cyclohexyl-acetophenone. 15 Furthermore, in addition to component B), it is possible for further ketones, C), to be present in a mixture, such as acetone, 4-tert-butyl methyl ketone, methyl naphthyl ketone, hydroxynaphthyl ketone, methyl ethyl ketone, heptan-2-one, pentan-3-one, methyl isobutyl ketone, propiophenone, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4 20 trimethylcyclopentanone, cycloheptanone, and cyclooctanone, cyclohexanone and all alkyl substituted cyclohexanones having one or more alkyl radicals containing a total of 1 to 8 hydrocarbon atoms, individually or in a mixture. Examples that may be mentioned of alkyl substituted cyclohexanones include 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone, and 3,3,5 25 trimethylcyclohexanone. Benzoin and/or alkyl ethers, such as methyl, ethyl, propyl, and isobutyl ethers of benzoin, can be used as component C) to a minor extent of up to a maximum of 9.9 mol%, based on the ketone component.

6 Generally speaking, however, it is possible to use all of the ketones said in the literature to be suitable for ketone resin syntheses and ketone-aldehyde resin syntheses, more generally all CH-acidic ketones, as additional ketone C). 5 Preference is given to reaction products of formaldehyde and/or benzaldehyde with acetophenone, hydroxy-, methyl-, tert-butyl- and/or cyclohexyl-acetophenone, and, if desired, 4-tert-butyl methyl ketone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclo hexanone and/or heptanone. 10 The synthesis of the polymers from components A), B), and, if desired, C) takes place in a condensation reaction, in a way which is known from the literature, in a basic medium (Dieter Stoye, Werner Freitag, Lackharze, Chemie, Eigenschaften und Anwendungen, Carl Hanser Verlag, Munich, Vienna, 1996, p. 164 ff.; US-B 2 540 885; US-B 2 540 886; DE-C 1155909; DL-PS 12433; DE-C 1300256; DE-C 1256898; DE 33 24 287; DE 15 103 38 580.0; EP 0 007 106; DE 12 65 415). Reaction conditions: Solvent: The reaction can be carried out using an auxiliary solvent. Examples of those which have 20 proven suitable include alcohols, such as methanol or ethanol. It is also possible to use water soluble ketones as auxiliary solvents, such as methyl ethyl ketone or acetone, for example, which are then incorporated to the resin by reaction. Bases: 25 The products of A), B), and, if desired, C) on which the invention is based are prepared using 0.05 to 10 mol% (based on the ketone used) of at least one base. Preference is given to (metal) hydroxides such as, for example, hydroxides of the cations NH4, Li, Na, and K. Particular preference is given to using potassium hydroxide and/or sodium hydroxide. 30 Ratio of ketone to aldehyde component: 7 The ratio between the ketone component (total of B) + C)) and the aldehyde component A) can vary from 1:0.9 to 1:4. Preference, however, is given to a ketone/aldehyde ratio of 1:1 to 1:2.5. The ketone component and the aldehyde component can be added in pure form or in solvents, as stated above, or in aqueous form. Particular preference is given to using an 5 aqueous or alcoholic formaldehyde solution, trioxane and/or para-formaldehyde and/or benzaldehyde. Ratio of ketone B) to component C): Based on the overall total of the ketones B) and C) employed, the ketone component B) may 10 be present in the range from 10 to 100 mol%, preferably from 20 to 100 mol%, more preferably from 25 to 100 mol%. The ketone component C) can be used in the range from 0 to 90 mol%, preferably 0 to 80 mol%, more preferably 0 to 75 mol%. Through the nature and the ratio of the components to one another it is possible to vary, in a 15 simple way, properties, such as solubility properties in solvents of different polarity, compatibilities with other raw materials, softening ranges, glass transition temperatures or further functionalities, such as OH groups. The reaction products of A), B), and, if desired, C) are reacted polymer-analogously with 20 component D) by irradiation with UV light. Suitable components D) are, in general, all unsaturated monomers that can be free-radically polymerized. Preference is given to using maleic acid, fumaric acid, acrylic acid and/or methacrylic acid, 25 Cl-C 40 alkyl esters and/or cycloalkyl esters of methacrylic acid and/or acrylic acid, hydroxyalkyl acrylates and/or hydroxyalkyl methacrylates, glycidyl methacrylate, glycidyl acrylate, 1,2-epoxybutyl acrylate, 1,2-epoxybutyl methacrylate, 2,3-epoxycyclopentyl acrylate, 2,3-epoxycyclopentyl methacrylate, acrylated polyethers, alone or in a mixture, it being possible in addition for styrene and/or its derivatives to be present to a minor degree. It is also 30 possible to use the analogous amides.

8 Further of suitability are (meth)acryloyl chloride, (meth)acryloyl isocyanate, c,ca-dimethyl-3 isopropenylbenzyl isocyanate, (meth)acryloylalkyl isocyanate with alkyl spacers possessing one to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms, such as methacryloylethyl isocyanate or methacryloylbutyl isocyanate, for example. 5 It is also possible to use di-, tri- and/or tetraacrylates as component D), in which case branched products are formed. Examples are dipropylene glycol diacrylate (DPGDA) or tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), and trimethylolpropane triacrylate, the use being possible of all higher polyfunctional acrylates 10 that are said in the literature to be suitable for free-radical reactions. The ratio of the reaction product of A), B), and, if desired, C) to the unsaturated monomers D) may vary from 99%:1% to 1%:99%, preferably 99%:1% to 20%:80%, more preferably 99%:1% to 40%:60% by mass. 15 It is also possible to carry out polymer-analogous reaction of different reaction products of A), B), and, if desired, C) with the unsaturated monomers D). Depending on the nature and ratio of the components to one another, the reaction products of 20 components A), B), and, if desired, C) and also D) that are relevant to the invention possess * melting ranges from 0 to 200 0 C, preferably 30 to 150'C, more preferably 40 to 125 0 C, * average molecular weights from 300 to 100 000, preferably from 400 to 10 000, more preferably from 500 to 5 000 g/mol, * color numbers (Gardner, 50% in ethyl acetate) of less than 7, preferably less than 5, more 25 preferably less than 3, * OH numbers from 0 to 250 mg KOH/g, preferably from 0 to 200 mg KOH/g, and * acid numbers from 0 to 250 mg KOH/g, preferably from 0 to 200 mg KOH/g. The invention also provides a process for preparing a polymeric reaction product substantially 30 containing the reaction product of 9 A) aldehydes of the general formula I O 5 R H where R = H, unbranched or branched alkyl radical having 1 to 12 carbon atoms, aryl radical and 10 B) at least one ketone of the general formula II O (II)

R

1 R2 15 20 where R 1 = unbranched alkyl radical having 1 to 12 carbon atoms and R 2 = R3 R4 25 R7 R5 R6 30 in which the radicals R 3 to R 7 are H, alkyl, OCH 3 , OC 2

H

5 , Cl, F, COO(C 1

-C

3 alkyl), R4 to R 6 are additionally OH, SH, 10 and C) if desired, a further, CH-acidic ketone, 5 and D) at least one unsaturated monomer which is free-radically polymerizable, 10 the reaction product of A), B), and, if desired, C) being mixed with component D) and subsequently brought to reaction by means of irradiation with UV light, preferably in an inert gas atmosphere. The preparation of the resins on which the invention is based takes place in the melt or in 15 solution in a suitable organic solvent. The reaction can be accelerated if desired by the addition of photosensitizer catalysts, such as tertiary amines. 20 In one preferred embodiment component D), in the presence if desired of a suitable catalyst, is added to the solution or melt of the reaction product of A), B), and, if desired, C). This is followed by exposure to appropriate radiation, preferably in an inert gas atmosphere. The solvent, where present, may be separated off if desired after the end of reaction, in which 25 case generally a powder or a melt of the product of the invention is obtained. Through the use of polymnerizable acids, such as acrylic acid, methacrylic acid, fumaric acid and/or maleic acid, polymers are obtained which, following neutralization with appropriate neutralizing agents, are unhydrolyzable and water-dilutable. Water dilutability may likewise 30 be attained by using monomers which carry polyether groups, sulfonate groups and/or amino groups, for example, following neutralization if desired with a suitable neutralizing agent.

11 The invention also provides for the use of the products of the invention as a principal, base or additive component in coating materials, adhesives, inks, including printing inks, gelcoats, polishes, glazes, pigment pastes, filling compounds, cosmetic articles, sealants and/or 5 insulants. It has been found that fractions from 5% to 80% by mass, preferably from 10% to 70% by mass, more preferably from 15% to 60% by mass, based on the overall formulation, are advantageous. 10 In this context it has also emerged that the products of the invention enjoy broad compatibility with different raw materials and are easy to incorporate. The coating materials, adhesives, inks, including printing inks, gelcoats, polishes, glazes, 15 pigment pastes, filling compounds, cosmetic articles, sealants and/or insulants may also contain auxiliaries and adjuvants, such as, for example, inhibitors, water and/or organic solvents, neutralizing agents, surface-active substances, oxygen scavengers and/or free-radical scavengers, catalysts, light stabilizers, color brighteners, thixotropic agents, antiskinning agents, defoamers, antistats, thickeners, thermoplastic additives, dyes, pigments, flame 20 retardants, internal release agents, fillers and/or blowing agents. The products of the invention improve in particular the gloss, leveling, and hardness of coating materials, adhesives, inks, including printing inks, gelcoats, polishes, glazes, pigment pastes, filling compounds, cosmetic articles, sealants and/or insulants. In some cases an 25 improved adhesion is observed as well. The examples that follow are intended to elucidate the invention further, but not to restrict the scope of its application.

12 Examples Example 1: Preparation of reaction products 600 g of acetophenone, 108 ml of methanol, 200 g of Cavasol W 7 M (methylated 13 cyclodextrin derivative, Wacker, Burghausen (DE)) and 180 g of formalin (30% strength in 5 water) are charged to a three-necked flask and heated under nitrogen to 50 0 C with stirring. 16 g of 25% strength sodium hydroxide solution are added, and the reaction mixture heats up to 70 0 C. Over 90 minutes 330 g of formalin (30% strength in water) are added, after which the reaction mixture is heated to 95 0 C and then held at reflux for 5 hours. 10 The aqueous phase is separated from the resin phase, and the resin is washed to neutrality with water at 100 0 C and freed from volatiles under reduced pressure at up to 150 0 C. This gives a yellowish, clear, brittle resin which possesses a solubility of 50% in methyl ethyl ketone, acetone, ethyl acetate, and xylene and a softening point of 48 0 C. The Gardner color 15 number of a 50% strength solution in ethyl acetate is 2.2. The OH number is less than 10 mg KOH/g. The resin prepared is mixed in a ratio of 1:4 with hydroxy ethyl acrylate and methyl methacrylate in a ratio of 1:1. As a result of irradiation under an inert gas atmosphere, and 20 following removal of the volatiles, the average molecular weight rises from approximately 700 g-mol 1 to approximately 2250 g-mol -1 . The OH number is 137 mg KOH/g. Application example 10 g of the reaction product from Example 1 are dissolved in 10 ml of butyl acetate, and 5 g of 25 Vestanat IPDI (Degussa AG) and 0.1 g of dibutyltin dilaurate are added. The solution is applied to a glass plate using a drawing frame, and is stored at 120 0 C for 60 minutes. The film, soluble beforehand, is no longer soluble in butyl acetate.

Claims

1. A product of a polymer-analogous reaction, composed of polymeric reaction products prepared from 5 A) aldehydes of the general formula I O R H 10 where R = H, unbranched or branched alkyl radical having 1 to 12 carbon atoms, aryl radical and 15 B) at least one ketone of the general formula II O (II) R, R2 20 where R 1 = unbranched alkyl radical having 1 to 12 carbon atoms and R

2 R3 R4 25 R7 R 5 R6 30 in which the radicals R 3 to R 7 are H, alkyl, OCH 3 , OC 2 H 5 , Cl, F, COO(CI-C 3 alkyl), R 4 to R6 are additionally OH, SH, 14 and C) if desired, a further, CH-acidic ketone, 5 and D) at least one unsaturated monomer which is free-radically polymerizable. 10 2. A product of a polymer-analogous reaction according to claim 1, characterized in that formaldehyde, benzaldehyde, acetaldehyde, n-butyraldehyde and/or isobutyraldehyde, valerianaldehyde, and dodecanal, alone or in combination, are used as aldehyde component A). 15

3. A product of a polymer-analogous reaction according to claim 1, characterized in that acetophenone and ring-substituted acetophenone derivatives, alone or in combination, are used as ketone component B). 20

4. A product of a polymer-analogous reaction according to claim 3, characterized in that hydroxy-, methyl-, ethyl-, tert-butyl- or cyclohexyl-acetophenone, alone or in combination, are used as ring-substituted acetophenone derivatives. 25

5. A product of a polymer-analogous reaction according to claim 1, characterized in that acetone, 4-tert-butyl methyl ketone, methyl naphthyl ketone, hydroxynaphthyl ketone, methyl ethyl ketone, heptan-2-one, pentan-3-one, methyl isobutyl ketone, propiophenone, 30 cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone, cyclooctanone, cyclohexanone, and all alkyl-substituted cyclohexanones 15 having one or more alkyl radicals containing a total of 1 to 8 hydrocarbon atoms are used, alone or in combination, as further, CH-acidic ketone component under C).

6. A product of a polymer-analogous reaction according to claim 5, 5 characterized in that 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert butylcyclohexanone, 2-methylcyclohexanone, and 3,3,5-trimethylcyclohexanone, alone or in combination, are used as alkyl-substituted cyclohexanones. 10

7. A product of a polymer-analogous reaction according to claims 1, 5, and 6, characterized in that up to a maximum of 9.9 mol% of the CH-acidic ketone component C) may be replaced by benzoin or alkyl ethers of benzoin. 15

8. A product of a polymer-analogous reaction according to any one of the preceding claims, characterized in that unsaturated monomers which are free-radically polymerizable are used as component D).

9. A product of a polymer-analogous reaction according to any one of the preceding claims, 20 characterized in that maleic acid, fumaric acid, acrylic acid and/or methacrylic acid, CI-C 40 alkyl esters and/or cycloalkyl esters of methacrylic acid and/or acrylic acid, hydroxyalkyl acrylates and/or hydroxyalkyl methacrylates, glycidyl methacrylate, glycidyl acrylate, 1,2-epoxybutyl acrylate, 1,2-epoxybutyl methacrylate, 2,3-epoxycyclopentyl acrylate, 2,3-epoxycyclo 25 pentyl methacrylate, acrylated polyethers, alone or in a mixture, are used as component D), use being made also of styrene and/or its derivatives and also the analogous amides.

10. A product of a polymer-analogous reaction according to any one of the preceding claims, characterized in that 30 (meth)acryloyl chloride, (meth)acryloyl isocyanate, ct,ca-dimethyl-3-isopropenylbenzyl isocyanate, (meth)acryloylalkyl isocyanate with alkyl spacers possessing one to 12 carbon 16 atoms, such as methacryloylethyl isocyanate and methacryloylbutyl isocyanate, alone or in a mixture, are used as component D).

11. A product of a polymer-analogous reaction according to any one of the preceding claims, 5 characterized in that di-, tri- and/or tetraacrylates are used as component D).

12. A product of a polymer-analogous reaction according to any one of the preceding claims, characterized in that 10 dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA) or trimethylolpropane triacrylate are used as component D).

13. A product of a polymer-analogous reaction according to any one of the preceding claims, 15 characterized in that the ratio of the reaction product of A), B), and, if desired, C) to the unsaturated monomers D) varies from 99%:1% to 1%:99% by mass.

14. A product of a polymer-analogous reaction according to any one of the preceding claims, 20 characterized in that the polymeric reaction products of components A), B), and, if desired, C) and also D) possess * melting ranges from 0 to 200 0 C, * average molecular weights from 300 to 100 000 g/mol, 25 * color numbers (Gardner, 50% in ethyl acetate) of less than 7, * OH numbers from 0 to 250 mg KOH/g, * acid numbers from 0 to 250 mg KOH/g.

15. A product of a polymer-analogous reaction according to any one of the preceding claims, 30 characterized in that 17 the ratio of ketone components (total of B) and C)) to the aldehyde component is 1:0.9 to 1:4.

16. A product of a polymer-analogous reaction according to any one of the preceding claims, 5 characterized in that the ketone component B), based on the overall total of the ketone components (total of B) and C)) used, amounts to 10 to 100 mol%.

17. A process for preparing a polymeric reaction product 10 substantially containing the reaction product of A) aldehydes of the general formula I O 15 (I) R H where R = H, unbranched or branched alkyl radical having 1 to 12 carbon atoms, aryl radical 20 and B) at least one ketone of the general formula II O 25 (II) 25 R, R2 where R, = unbranched alkyl radical having 1 to 12 carbon atoms and R2 = 18 R3 R4 5 R7 R5 R6 in which the radicals R 3 to R 7 are H, alkyl, OCH 3 , OC 2 H 5 , Cl, F, COO(C 1 -C 3 alkyl), R 4 to R 6 are additionally OH, SH, 10 and C) if desired, a further, CH-acidic ketone, 15 and D) at least one unsaturated monomer which is free-radically polymerizable, the reaction product of A), B), and, if desired, C) being mixed with component D) and 20 subsequently brought to reaction by means of irradiation with UV light, preferably in an inert gas atmosphere, in the presence if desired of a suitable catalyst.

18. A process for preparing a polymeric reaction product according to claim 17, characterized in that 25 the reaction products of A), B), and, if desired, C) are prepared in the presence of a base.

19. A process for preparing a polymeric reaction product according to either of claims 17 and 18, characterized in that 30 the reaction products of A), B), and, if desired, C) are reacted in the melt or in solution in a suitable solvent with component D). 19

20. The use of a polymeric reaction product according to any one of the preceding claims as a principal, base or additive component in a coating material, adhesive, ink, including printing ink, gelcoat, polish, glaze, pigment paste, filling compound, cosmetic article, 5 sealant and/or insulant.

21. The use of a polymeric reaction product according to claim 20, it being possible additionally for auxiliaries and adjuvants, inhibitors, water and/or organic solvents, neutralizing agents, surface-active substances, oxygen scavengers and/or free-radical 10 scavengers, catalysts, light stabilizers, color brighteners, thixotropic agents, antiskinning agents, defoamers, antistats, thickeners, thermoplastic additives, dyes, pigments, flame retardants, internal release agents, fillers and/or blowing agents, alone or in combination, to be present.