WO2006021478A1

WO2006021478A1 - Products resulting from polymer-analogous reactions

Info

Publication number: WO2006021478A1
Application number: PCT/EP2005/053677
Authority: WO
Inventors: Patrick GLÖCKNER; Friedrich Georg Schmidt
Original assignee: Degussa Ag
Priority date: 2004-08-26
Filing date: 2005-07-28
Publication date: 2006-03-02
Also published as: BRPI0514277A2; KR20070047312A; TNSN07072A1; CN1878803A; DE102004041196A1; EP1786846A1; MA29985B1; CA2577773A1; AU2005276517A1

Abstract

The invention relates to products resulting from polymer-analogous reactions of products comprised of aldehydes and ketones and of radically polymerizable monomers, to a method for the production thereof and to their use.

Description

Products from polymer-analogous reactions

The invention relates to products of polymer-analogous reactions, a process for their preparation and their use.

Radiation-sensitive compounds which may optionally contain acetophenone as a sub-grouping or polymeric secondary products with acetophenone groups are described in EP 0 346 788, EP 0 377 199 and DE 102 06 987.

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. DE 102 06 987 describes vinyl ether derivatives.

None of these documents mentions the polymer-analogous reaction of ketone-aldehyde resins containing acetophenone by means of radical polymerization.

Ketone aldehyde resins are used in coating materials, for. B. used as additive resins to improve certain properties such as gloss, hardness or scratch resistance.

Usually, ketone-aldehyde resins have hydroxy groups and can therefore only with z. As polyisocyanates or amine resins are crosslinked. These crosslinking reactions are usually initiated or accelerated thermally. Other functional groups, e.g. Amino and / or carboxy groups can be introduced only by specific monomers that are either difficult or impossible to obtain on an industrial scale.

The polymer-analogous reaction of cyclohexanone-formaldehyde resins with azo compounds is described in "Die Angewandte Makromolekulare Chemie, 168 (1989), pp. 129 et seq." The process is costly for the industrial scale and, since azo compounds are used, production is very demanding In addition, azo compounds are thermally labile, which makes storage expensive. Cyclohexanone and acetophenone-formaldehyde resins, which become photoactive through the attachment of 10 mol% benzoin or benzoin butyl ethers, are described in "Journal of Applied Polymer Science, Vol. 72 (1999), page 927 ff." The synthesis is complicated Since it is conducted over two stages lasting over 16 hours, complete conversion is not guaranteed so that volatile constituents can be contained, and low molecular weight components reduce the performance profile of high-grade coatings in terms of mechanical properties, and only polymer-analogous reaction products with styrene It is known that the weathering properties of polymers containing styrene are inadequate.

The object of the present invention was the preparation of products of ketone-aldehyde resins and unsaturated monomers which, in addition to carbonyl and hydroxyl groups, possess further functional groups and are distinguished by altered solubility properties relative to the starting resins.

In addition, it was an object to develop a process for their preparation, with the aid of which the properties described above can be widely varied in a simple manner.

The products should be suitable for use in paints, adhesives, inks and inks, gel coats, polishes, glazes, pigment pastes, fillers, cosmetics and / or sealants and sealants.

Surprisingly, this object could be achieved according to the claims, by polymer-analogous reaction of ketone-aldehyde resins containing acetophenone and / or derivatives of acetophenone, with unsaturated monomers, by irradiation by means of UV light.

Suitable ketone-aldehyde resins are polymeric reaction products of aldehydes of the general formula I and ketones of the general formula II, if appropriate using further ketones.

with R =H, unbranched or branched alkyl radical having 1 to 12 carbon atoms, aryl radical,

where R ₁ = unbranched alkyl radical having 1 to 12 carbon atoms

R ₂ =

with R ₃ to R ₇ = H, alkyl, OCH ₃ , OC ₂ H ₅ , Cl, F, COO (C ₁ -C ₃ -alkyl). In addition, R ₄ to R ₆ may be OH, SH.

Suitable unsaturated monomers are all unsaturated monomers which can be free-radically polymerized.

The invention therefore relates to polymeric reaction products, essentially comprising the reaction product

A) aldehydes of the general formula I.

with R = H, unbranched or branched alkyl radical having 1 to 12 carbon atoms, aryl radical

and B) at least one ketone of the general formula II

where R ₁ = unbranched alkyl radical having 1 to 12 carbon atoms

where 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 additionally OH, SH

and

C) optionally a further CH-acidic ketone as well

D) at least one unsaturated monomer which can radically polymerize,

for use as the main component, base component or additive component in coating materials, adhesives, printing inks and inks, gelcoats, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealants and insulating materials. As aldehyde component A) according to formula I are in principle unsubstituted or branched aldehydes, such as. As formaldehyde, benzaldehyde, acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, valeric aldehyde and dodecanal. In general, all the aldehydes mentioned in the literature as suitable for ketone-aldehyde resin syntheses can be used. However, preferably formaldehyde and benzaldehyde are used alone or in mixtures.

The required formaldehyde is usually used as about 20 to 40 wt .-% aqueous or alcoholic (eg, methanol or butanol) solution. Other uses of formaldehyde such. As well as the use of para-formaldehyde or trioxane are also possible.

Examples of ketones B) according to formula II are acetophenone, ring-substituted acetophenone derivatives, such as hydroxy, methyl, ethyl, tert-butyl, cyclohexyl-acetophenone.

In addition, in addition to component B) further ketones C) may be included in a mixture, e.g. Acetone, 4-tert-butyl methyl ketone, methyl naphthyl ketone, hydroxynaphthyl ketone, methyl ethyl ketone, heptanone-2, pentanone-3, methyl isobutyl ketone, propiophenone, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone and Cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals having a total of 1 to 8 hydrocarbon atoms, individually or in mixture. As examples of alkyl-substituted cyclohexanones, mention may be made of 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.

Benzoin or alkyl ethers such as methyl, ethyl, propyl, iso-butyl ethers of benzoin can be used as component C) in the subordinate degree to max. 9.9 mol% based on the ketone component can be used. In general, however, all in the literature for ketone and ketone Aldehydharzsynthese called suitable ketones, usually all CH-acidic ketones, as additional ketone C) can be used.

Preference is given to reaction products of formaldehyde and / or benzaldehyde with acetophenone, hydroxy, methyl, tert-butyl and / or cyclohexyl acetophenone and optionally 4-tert-butyl methyl ketone, cyclohexanone, 4-tert-butylcyclohexanone, 3, 3,5-trimethylcyclohexanone and / or heptanone.

The synthesis of the polymers from the components A), B) and optionally C) takes place in a condensation reaction in a manner known from the literature in basic medium (Dieter Stoye, Werner Freitag, Lackharze, chemistry, properties and applications, Carl Hanser Verlag, Munich, Vienna, 1996, pp. 164 et seq., U.S. Patent No. 2,540,885, U.S. Patent No. 2,540,886, German Patent No. 11,555,909, German Laid-Open Patent No. 12,433, German Patent Publication No. 1300256, and German Patent No. 12 56 898; DE 33 24 287, DE 103 38 580.0, EP 0 007 106, DE 12 65 415).

Reaction conditions: Solvents:

The reaction can be carried out using an auxiliary solvent. As suitable, alcohols such. As methanol or ethanol proved. It is also possible as auxiliary solvent water-soluble ketones such. As methyl ethyl ketone or acetone, which then react in the resin with.

bases:

For the preparation of the products according to the invention from A), B) and optionally C) 0.05 to 10 mol% (based on the ketone used) of at least one base are used. Preference is given to (metal) hydroxides, for example hydroxides of the cations NH ₄ , Li, Na, K. It is particularly preferable to use potassium hydroxide and / or sodium hydroxide. Ratio of ketone to Aldchydcomponent:

The ratio between the ketone component (sum B) + C)) and the aldehyde component

A) can vary between 1 to 0.9 to 1 to 4. However, a ketone / aldehyde ratio of 1 to 1 to 1 to 2.5 is preferred. The ketone component and the aldehyde component can be added in pure form or in solvents as mentioned above or aqueous. It is particularly preferred that an aqueous or alcoholic formaldehyde solution, trioxane and / or paraformaldehyde and / or benzaldehyde is used.

Ratio ketone B) to component C):

Based on the total amount of ketones B) and C) used, the ketone component

B) in the range from 10 to 100 mol%, preferably between 20 to 100 mol%, particularly preferably between 25 and 100 mol%. The ketone component C) can be used in the range of 0 to 90 mol%, preferably 0 to 80 mol%, particularly preferably 0 to 75 mol%.

Due to the nature and the ratio of the components to each other can be in a simple manner properties such. Solubility properties in different polar solvents, compatibilities with other raw materials, softening ranges, glass transition temperatures or other functionalities such as e.g. OH groups vary.

The reaction products of A), B) and optionally C) are polymer-analogously reacted with the component D) by irradiation by means of UV light.

As component D) are generally suitable all unsaturated monomers which can be polymerized free-radically.

Preferably used are maleic acid, fumaric acid, acrylic acid and / or methacrylic acid, C ₁ - C ₄ alkyl ester of o-and / or cycloalkyl esters of methacrylic acid and / or acrylic acid, hydroxyalkyl acrylates and / or hydroxyalkyl methacrylates, glycidyl methacrylate, glycidyl acrylate, 1,2-Epoxybutylacrylat, 1 , 2-epoxybutyl methacrylate, 2,3-

Epoxycyclopentyl acrylate, 2,3-epoxycyclopentyl methacrylate, acrylated polyethers, alone or in Mixture, wherein also styrene and / or its derivatives may be present to a lesser extent. You can also use the analog amides.

Also suitable are (meth) acryloyl chloride, (meth) acryloyl isocyanate, α, α-dimethyl-3-isopropenylbenzyl isocyanate, (meth) acrylic alkyl isocyanate having alkyl spacers which have from 1 to 12, preferably 2 to 8, particularly preferably 2 to 6, carbon atoms, such as For example, methacrylethyl isocyanate, methacrylic butyl isocyanate.

It is also possible to use di-, tri- and / or tetra-acrylates as component D), in which case branched products are formed. Examples are di- (DPGDA) or tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), trimethylolpropane triacrylate, all of which can be used in the literature for free-radical reactions as suitable higher-functional acrylates.

The ratio of the reaction product from A), B) and optionally C) and the unsaturated monomers D) can vary between 99: 1 to 1: 99, preferably 99: 1 to 20:80, particularly preferably 99: 1 to 40 to 60% by mass.

Various reaction products of A), B) and, if appropriate, C) with the unsaturated monomers D) can also be reacted in a polymer-analogous manner.

The reaction-relevant reaction products of the components A), B) and optionally C) and D) have, depending on the nature and ratio of the components to each other

Melting ranges between 0 and 200 ° C, preferably 30 and 150 ° C, particularly preferably 40 and 125 ° C,

Average molecular weights of 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) less than 7, preferably less than 5, more preferably less than 3, • OH numbers between 0 and 250 mg KOH / g, preferably between 0 and 200 mg KOH / g.

• Acid numbers between 0 and 250 mg KOH / g, preferably between 0 and 200 mg KOH / g. The invention also provides a process for the preparation of polymeric reaction products, essentially comprising the reaction product

A) aldehydes of the general formula I.

and B) at least one ketone of the general formula II

with R ₁ = unbranched alkyl radical having 1 to 12 carbon atoms and R ₂ =

and

C) optionally a further CH-acidic ketone

such as

D) at least one unsaturated monomer which can radically polymerize,

wherein the reaction product of A), B) and optionally C) is mixed with the component D) and is subsequently reacted, preferably in an inert gas atmosphere, by means of UV light irradiation.

The preparation of the invention based resins is carried out in the melt or in solution of a suitable organic solvent.

The reaction may optionally be accelerated by the addition of photosensitizers as catalysts, e.g. tertiary amines.

In a preferred embodiment, the solution or melt of the reaction product of A), B) and optionally C) is the component D), optionally in the presence of a suitable catalyst. Then the irradiation with suitable radiation preferably takes place in an inert gas atmosphere.

The optional solvent may, if desired, be separated after completion of the reaction, in which case a powder or a melt of the product according to the invention is then generally obtained. By using polymerizable acids, such as acrylic acid, methacrylic acid, fumaric acid and / or maleic acid, polymers are obtained which, after neutralization with suitable neutralizing agents, are unsaponifiable and water-dilutable. Water dilutability can also be achieved by using, for example, polyether groups, sulfonate group- and / or amino-group-carrying monomers, if appropriate after neutralization with a suitable neutralizing agent.

The invention also relates to the use of the products according to the invention as the main component, base component or additional component in coating materials, adhesives, printing inks and inks, gel coats, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealing and insulating materials.

It has been found that proportions of between 5 and 80% by weight, preferably between 10 and 70% by weight, more preferably between 15 and 60% by weight, based on the overall formulation, are advantageous.

It has also been found that the products of the invention are broadly compatible with different raw materials and can be easily incorporated.

The coating materials, adhesives, printing inks and inks, gelcoats, polishes, glazes, pigment pastes, fillers, cosmetics and / or sealants and insulating materials may also contain auxiliaries and additives such as, for example, inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, Oxygen scavengers and / or radical scavengers, catalysts, light stabilizers, color brighteners, thixotropic agents, skin preventatives, defoamers, antistatics, thickeners, thermoplastic additives, dyes, pigments, fire retardants, internal release agents, fillers and / or blowing agents.

The products according to the invention in particular improve the gloss, the course and the hardness of coating materials, adhesives, printing inks and inks, gelcoats, polishes, Glazes, pigment pastes, fillers, cosmetics and / or sealants and insulating materials. In part, improved adhesion is also observed.

The following examples are intended to further illustrate the invention but not to limit its scope:

Examples

Example 1: Preparation of the reaction products

600 g of acetophenone, 108 ml of methanol, 200 g of Cavasol W 7 M (methylated β-cyclodextrin derivative, Wacker, Burghausen) and 180 g of formalin (30% in water) are introduced and heated to 50 ° C with stirring in a three-necked flask in a nitrogen atmosphere. 16 g of 25% sodium hydroxide solution are added, the reaction mixture being heated to 70.degree. In 90 minutes 33O g of formalin (30% in water) was added, then heated to 95 ° C and the reaction mixture was refluxed for 5 h.

The aqueous phase is separated from the resin phase, the resin is washed neutral with water at 100 ° C and devolatilized to 150 ° C in vacuo.

There is obtained a yellowish, clear and brittle resin which is 50% soluble in methyl ethyl ketone, acetone, ethyl acetate and xylene and has a softening point of 48 ° C. The Gardner color number of a 50% solution in ethyl acetate is 2.2. The OH number is below 10 mg KOH / g.

The produced resin is mixed in a ratio of 1: 4 with hydroxyethyl acrylate and methyl methacrylate in a ratio of 1: 1. By irradiation in an inert gas atmosphere, the average molecular weight increases after separation of the volatile constituents from about 700 g-mol ^"1 to about 2 250 g-mol ^{" 1} . The OH number is 137 mg KOH / g.

Use Example 10 g of the reaction product from Example 1 are dissolved in 10 ml of butyl acetate and 5 g of Vestanat IPDI (Degussa AG) and also 0.1 g of dibutyltin dilaurate are added. The solution is applied with a pulling frame on a glass plate and stored for 60 min at 120 ° C. The previously soluble film is no longer soluble in butyl acetate.

Claims

claims:

1. Products of polymer-analogous reactions, consisting of polymeric reaction products prepared from

A) aldehydes of the general formula I.

and

B) at least one ketone of the general formula II

with R ₁ = unbranched alkyl radical having 1 to 12 carbon atoms and R ₂ =

where 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 additionally for OH, SH and

C) optionally a further CH-acidic ketone

such as

D) at least one unsaturated monomer which can radically polymerize.

2. Products of polymer-analogous reactions according to claim 1, characterized in that as aldehyde component A) formaldehyde, benzaldehyde, acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, valeric aldehyde and dodecanal are used alone or in combination.

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

4. Products of polymer-analogous reactions according to claim 3, characterized in that are used as the ring-substituted acetophenone derivatives hydroxy, methyl, ethyl, tert-butyl or cyclohexyl-acetophenone alone or in combination.

5. Products of polymer-analogous reactions according to claim 1, characterized in that as further CH-acid ketone component under C) acetone, 4-tert-butyl methyl ketone, methyl naphthyl ketone, hydroxynaphthyl ketone, methyl ethyl ketone, heptanone-2, pentanone-3, methyl isobutyl ketone, propiophenone , Cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone, cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals total of 1 to 8 hydrocarbon atoms, may be used alone or in combination.

6. Products of polymer-analogous reactions according to claim 5, characterized in that as alkyl-substituted cyclohexanones 4-tert-amylcyclohexanone, 2-sec-butylcyclo-hexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone may be used alone or in combination.

7. Products of polymer-analogous reactions according to claim 1, 5 and 6, characterized in that up to a maximum of 9.9 mol% of the CH-acid ketone component C) can be replaced by benzoin or alkyl ethers of benzoin.

8. Products of polymer-analogous reactions according to any one of the preceding claims, characterized in that are used as component D) unsaturated monomers which can be polymerized free-radically.

9. Products of polymer-analogous reactions according to one of the preceding claims, characterized in that as component D) maleic, fumaric acid, acrylic acid and / or methacrylic acid, C ₁ - 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-Epoxycyclopentylmethacrylat, acrylated polyethers are used alone or in admixture, wherein styrene and / or its derivatives and the analogous amides are used.

10. Products of polymer-analogous reactions according to one of the preceding claims, characterized in that in that as component D) (meth) acryloyl chloride, (meth) acryloyl isocyanate, α, α-dimethyl-3-isopropenylbenzyl isocyanate, (meth) acrylic alkyl isocyanate having alkyl spacers having from 1 to 12 carbon atoms, such as methacrylethyl isocyanate, methacrylic butyl isocyanate, used alone or in mixture ,

11. Products of polymer-analogous reactions according to one of the preceding claims, characterized in that di-, tri- and / or tetraacrylates are used as component D).

12. Products of polymer-analogous reactions according to any one of the preceding claims, characterized in that are used as component D) di (DPGDA) tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA) or trimethylolpropane triacrylate.

13. Products of polymer-analogous reactions according to any one of the preceding claims, characterized in that the ratio of the reaction product of A), B) and optionally C) and the unsaturated monomers D) varies between 99 to 1 to 1 to 99% by mass ,

14. Products of polymer-analogous reactions according to any one of the preceding claims, characterized in that the polymeric reaction products of the components A), B) and optionally C) and D)

• melting ranges between 0 and 200 ° C,

• average molecular weights from 300 to 100,000 g / mol, • color numbers (according to Gardner, 50% in ethyl acetate) less than 7,

OH numbers between 0 and 250 mg KOH / g,

• have acid numbers between 0 and 250 mg KOH / g.

15. Products of polymer-analogous reactions according to one of the preceding claims, characterized in that in that the ratio of ketone components (sum B) and C)) to aldehyde component 1 is 0.9 to 1: 4.

16. Products of polymer-analogous reactions according to any one of the preceding claims, characterized in that the ketone component B), based on the total sum of the ketone components used (sum B) and C)), 10 to 100 mol%.

17. A process for the preparation of polymeric reaction products, consisting essentially of the reaction product

A) aldehydes of the general formula I.

with R =H, unbranched or branched alkyl radical having 1 to 12 carbon atoms,

aryl

and B) at least one ketone of the general formula II

with R ₁ = unbranched alkyl radical having 1 to 12 carbon atoms and R ₂ =

and

C) optionally a further CH-acidic ketone

such as

D) at least one unsaturated monomer which can radically polymerize,

wherein the reaction product of A), B) and optionally C) is mixed with the component D) and then preferably in an inert gas atmosphere, if appropriate in the presence of a suitable

Catalyst, is reacted by means of UV light irradiation.

18. A process for the preparation of polymeric reaction products according to claim 17, characterized in that the reaction products of A), B) and optionally C) are prepared in the presence of a base.

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

20. Use of the polymeric reaction products according to any one of the preceding claims, as the main component, base component or additive component in coating materials, adhesives, printing inks and inks, gel coats, polishes, glazes, pigment pastes, fillers, cosmetics and / or sealing and insulating materials.

21. Use of the polymeric reaction products according to claim 20, wherein additionally auxiliaries and additives, inhibitors, water and / or organic solvents, neutralizing agents, surface-active substances, oxygen and / or free-radical scavengers, catalysts, light stabilizers, color brighteners, thixotropic agents, skin preventatives, defoamers, Antistatics, thickening agents, thermoplastic additives, dyes, pigments, fire protection equipment, internal release agents, fillers and / or blowing agents may be contained alone or in combination.