EP2027172A1

EP2027172A1 - Formaldehyde-free, oh-functional, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkyl aryl ketones and formaldehyde and a process for preparing them

Info

Publication number: EP2027172A1
Application number: EP07729142A
Authority: EP
Inventors: Patrick GLÖCKNER; Christian Lettmann; Michael Ewald; Andreas Wenning
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2006-06-09
Filing date: 2007-05-15
Publication date: 2009-02-25
Also published as: CN101085823A; DE102006026760A1; JP2009540028A; WO2007141119A1; US20090099332A1

Abstract

The invention relates to formaldehyde-free, OH-functional, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkyl aryl ketones and formaldehyde which have a low proportion of compounds capable of crystallization, a low viscosity, a very low colour number, a wide solubility and a very high heat and light stability and also a process for preparing them.

Description

Formaldehyde-free, OH-functional, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde and a process for their preparation

The invention relates to formaldehyde-free, OH-functional, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde with a low content of crystallizable compounds, low viscosity, very low color number, broad solubility and very high heat and light resistance and a process for their preparation ,

It is known that ketones or mixtures of ketones and aldehydes can be converted to resinous products in the presence of basic catalysts or acids. Thus, it is possible to prepare resins from mixtures of cyclohexanone and methylcyclohexanone (Ullmann, Vol. 12, p. 551). The reaction of ketones and aldehydes usually leads to hard resins, which are often used in the paint industry.

Technically important ketone-aldehyde resins are nowadays mostly produced using formaldehyde.

Ketone-formaldehyde resins have been known for a long time. Process for the preparation are for. As described in DE 33 24 287, US 2,540,885, US 2,540,886, DE 11 55 909, DD 12 433, DE 13 00 256 and DE 12 56 898.

For preparation, ketones and formaldehyde are normally reacted with each other in the presence of bases.

Ketone-aldehyde resins are used in coating materials z. B. as a film-forming

Additional components used to improve certain properties such as drying speed, gloss, hardness or scratch resistance. Because of their relatively low molecular weight, conventional ketone-aldehyde resins have a low content Melting and solution viscosity and therefore serve in coating materials, inter alia, as film-forming functional fillers.

The carbonyl groups of the ketone-aldehyde resins are subject to z. B. irradiation with z. B. sunlight classic degradation reactions such. From the Norrish type I or Il [Laue, Piagens, name and keyword responses, Teubner Studienbücher, Stuttgart, 1995].

The use of unmodified ketone-aldehyde or ketone resins is therefore for high-quality applications such. B. in the outdoor area, in the high

Resistance properties, in particular to weathering and heat are required, not possible. These disadvantages may be due to hydrogenation of the

Carbonyl groups can be improved. The conversion of the carbonyl groups into secondary alcohols by hydrogenation of ketone-aldehyde resins has been practiced for a long time (DE 826 974, DE 870 022, JP 11012338, US 6,222,009).

The preparation of carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones is not described.

Technically important ketone-aldehyde resins are obtained on the basis of formaldehyde and acetophenone (Stoye, Freitag, Lackharze, Chemie, Eigenschaften und Anwendungen, Hanser Fachbuch (July 1996)).

In addition to the presence of the carbonyl groups, the aromatic structural elements limit high heat and light resistance. Therefore, such products, despite their very good general property profile z. B. not suitable for use in weathering stable coatings.

The preparation of carbonyl- and ring-hydrogenated ketone-aldehyde resins based on ketones which contain such aromatic groups is described in DE 33 34 631. The processes listed there lead to products that compared to the starting materials improved properties in terms of color, heat and Have light resistance. In addition, the solubility profile of the starting resins is changed. From today's point of view, the performance of these products, despite their improvement is no longer sufficient.

As comprehensive own findings continue to prove, the hydrogenated products described therein have a relatively high content of free formaldehyde in common. Although the proportion of free formaldehyde over the non-hydrogenated ketone-formaldehyde resins is reduced by the hydrogenation processes described by the prior art, significant amounts of free formaldehyde remain in the hydrogenation products. Longer hydrogenation times can lead to a further reduced formaldehyde content, but this can be disadvantageous to other resin properties such. As color, melting ranges, OH numbers, etc. impact and is for reasons of reduced productivity is not a viable option. Furthermore, own findings show that the content of crystallizable compounds and the color numbers are high.

Formaldehyde can cause health problems. However, an exact classification is not yet made. The International Agency for Research on Cancer (IARC), an institution of the World Health Organization (WHO), recently determined on the basis of a study that formaldehyde causes spontaneously very rare nasopharyngeal cancer in humans.

Although the lARC assessment is purely scientific and does not yet produce any direct legal consequences, the provision of formaldehyde-free products is indispensable in the sense of "sustainable development" and "responsible handling of chemical substances". In addition, it can be assumed that in the medium term only formaldehyde-free products will exist on the market.

A method for lowering the formaldehyde content of non-hydrogenated acetone-formaldehyde resins without reducing the carbonyl groups is disclosed in US 5,247,066 described. Here, a content of free formaldehyde is below 0.4 wt .-% achieved, which is significantly too high by today's standards. In addition, aromatic structural elements and carbonyl groups remain unhydrogenated in this way.

Ketone-aldehyde resins have always been used to increase the content of non-volatile constituents in coating materials. Under the pressure of new guidelines such. For example, Council Directive 1999/13 / EC on the limitation of emissions of volatile organic compounds, these characteristics need to be further improved.

During the synthesis of ketone-formaldehyde resins, crystallizable compounds may be formed, which are mainly cyclic oligomers. Hydrogenation of the carbonyl groups of these secondary components leads to products which tend to crystallize in solution (formula I), which can lead to processing disadvantages in coating materials.

It was therefore an object of the present invention to find carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkyl aryl ketones and formaldehyde, which are free of free formaldehyde and by the presence of OH groups of a crosslinking with z. As polyisocyanates or melamine-formaldehyde resins are available. The proportion of crystallizable compounds should be as low as possible. In addition, the properties of the resins should be considered in terms of solution viscosity high melting range and color further improved and there should be a very high heat and light resistance.

Moreover, it was an object of the present invention to develop a process for the preparation of such products.

Surprisingly, this object could be achieved according to the claims by specially prepared ketone-aldehyde resins based on alkylaryl ketones and formaldehyde in the presence of catalysts which catalyze the one hand, the selective hydrogenation of the carbonyl groups and the aromatic structural elements of the resins, on the other hand, the content of free Reduce formaldehyde, react with hydrogen.

The carbonyl- and ring-hydrogenated ketone-aldehyde resins according to the invention have outstanding light and heat resistance and a very low color. The

Products have a low content of carbonyl groups and aromatic ones

Structural elements and crystallizable compounds and are virtually free of formaldehyde. The hydroxyl number can be adjusted. In spite of the high melting range, the solution viscosity is low in contrast to the prior art and can be realized by the use of tailor-made starting resins for the hydrogenation, which have a particularly narrow molecular weight distribution.

The invention relates to OH-functional, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde having a hydroxyl number of at least 75 mg KOH / g, with a content of free formaldehyde of less than 3 ppm, which essentially corresponds to the structural elements Formula II included

With

R = aromatic with 6 to 14 carbon atoms, cycloaliphatic with 6 to 14

Carbon atoms, wherein the proportion of the aromatic structural elements is less than 10, preferably less than 5 mg alkylaryl ketone / g (based on alkylaryl ketone), R '= H, CH ₂ OH, k = 1 to 10, preferably 1 to 8, particularly preferably 1 to 5 , m = 2 to 12, preferably 2 to 9, particularly preferably 2 to 8

I = 0 to 0.35, preferably 0 to 0.30, the sum of k + I + m being between 3 and 24, preferably between 5 and 14, the ratio of m / k> 1, 0, preferably> 1, 5 and the three structural elements can be distributed alternately or statistically and wherein the structural elements via CH ₂ groups are linearly and / or branched via CH groups.

The invention relates to OH-functional, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde having a hydroxyl value of at least 75 mg KOH / g, with a content of free formaldehyde of less than 3 ppm, which essentially corresponds to the structural elements Formula II included

With

R = aromatic with 6 to 14 carbon atoms, cycloaliphatic with 6 to 14

Carbon atoms, the proportion of the aromatic structural elements being less than 10, preferably less than 5 mg alkylaryl ketone / g (based on alkylaryl ketone),

R '= H, CH ₂ OH, k = 1 to 10, preferably 1 to 8, particularly preferably 1 to 5, m = 2 to 12, preferably 2 to 9, particularly preferably 2 to 8

I = 0 to 0.35, preferably 0 to 0.30, the sum of k + I + m being between 3 and 24, preferably between 5 and 14, the ratio of m / k> 1, 0, preferably> 1, 5 and the three structural elements can be distributed alternately or randomly and wherein the structural elements via CH ₂ groups are linearly and / or branched via CH groups, obtained by A) the preparation of the base resins by condensation of at least one ketone with at least one aldehyde in the presence of at least one basic catalyst and optionally at least one phase transfer catalyst, solvent-free or using a water-miscible organic solvent,

and subsequently

B) continuous, semicontinuous or discontinuous hydrogenation of the carbonyl groups and the aromatic groups of the ketone-aldehyde resins (A) in the melt or in solution of a suitable solvent with hydrogen in the presence of a catalyst at pressures between 150 and 350 bar, preferably between 175 and 300 bar, more preferably between 200 and 300 bar and temperatures between 150 and 250 ⁰ C, preferably between 150 and 225 ⁰ C.

A preferred subject matter of the invention are carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde, these having the following properties:

The content of free formaldehyde is less than 3 ppm, preferably less than 2.5 ppm, more preferably less than 2.0 ppm,

The content of compounds capable of crystallization is below 3% by weight, preferably below 2% by weight, more preferably below 1% by weight, the carbonyl number is between 0 and 20 mg KOH / g, preferably between 0 and 18 mg KOH / g, more preferably between 0 and 15 mg KOH / g,

The hydroxyl number is between 75 and 350 mg KOH / g, preferably between 75 and 200 mg KOH / g, more preferably between 75 and 180 mg KOH / g,

The proportion of aromatic structural elements is less than 10, preferably less than 5 mg alkylaryl ketone / g (based on alkylaryl ketone),

Gardner color number (50% by weight in ethyl acetate) is less than 1.5, preferably less than 1.0, more preferably less than 0.75,

Gardner color number (50% by weight in ethyl acetate) after thermal loading of the resin (24 h, 150 ^° C.) is below 2.0, preferably below 1.5, more preferably below 1.0,

The polydispersity (Mw / Mn) of the resins is between 1, 35 and 1, 7, more preferably between 1, 4 and 1, 6, The solution viscosity, 40% by weight in phenoxyethanol, is between 1000 and 15000 mPa.s, more preferably between 3000 and 10000 mPa.s,

• The melting point / range is between 50 and 150 ⁰ C, preferably between 60 and 140 ⁰ C, more preferably between 75 and 130 ⁰ C, • The content of non-volatile constituents after annealing for 24 h at 150 ⁰ C is above 97 , 0% by weight, preferably over 97.5% by weight and

• the solubility is given in n-hexane, white spirit and ethanol 10 and 50% by weight.

The properties of the carbonyl- and ring-hydrogenated ketone-aldehyde resins according to the invention all possible variations within o. G. Accept values. As an example: A resin with a hydroxyl number of 350 mg KOH / g - upper limit - and a content of free formaldehyde of less than 2 ppm - lower limit - etc.

The invention also provides a process for the preparation of the OH-functional, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde, having a hydroxyl number of at least 75 mg KOH / g, with a content of free formaldehyde of less than 3 ppm which essentially contain the structural elements according to formula II, characterized by

A) the preparation of the base resins by condensation of at least one

Ketone with at least one aldehyde in the presence of at least one basic

Catalyst and optionally at least one phase transfer catalyst, solvent-free or using a water-miscible organic

Solvent,

and subsequently

B) continuous, semi- or discontinuous hydrogenation of the carbonyl groups and the aromatic groups of the ketone-aldehyde resins (A) in the melt or in solution of a suitable solvent with hydrogen in the presence of a Catalyst at pressures between 150 and 350 bar, preferably between 175 and 300 bar, more preferably between 200 and 300 bar and temperatures between 150 and 250 ⁰ C, preferably between 150 and 225 ⁰ C.

The inventive method, the content of harmful formaldehyde can be greatly reduced. Formaldehyde-free means that the carbonyl-hydrogenated ketone-aldehyde resins according to the invention have a content of free formaldehyde below 3 ppm, preferably below 2.5 ppm, particularly preferably below 2.0 ppm.

The inventive method, the formation of crystallizable compounds is largely prevented. The content of compounds capable of crystallization of the products according to the invention is below 3% by weight, preferably below 2% by weight, more preferably below 1% by weight. This makes it possible to always produce clear solutions of the products of the invention. This is particularly important to clog z. B. of spray gun nozzles or ballpoint pen refills.

It has been found that a low color number and high thermal stability is the result of a low carbonyl number (I <0.35 of II-c). The

Carbonyl number of the products of the invention is between 0 and 20 mg KOH / g, preferably between 0 and 18 mg KOH / g, more preferably between 0 and 15 mg KOH / g, so that the Gardner color number (50% by weight in ethyl acetate) of inventive products under 1, 5, preferably less than 1, 0, more preferably below 0.75 and the Gardner color number (50% by weight in ethyl acetate) after thermal loading of the products of the invention (24 h, 150 ⁰ C) below 2, 0, preferably less than 1, 5, more preferably less than 1, 0.

As universal solubility as possible is desired, since it ensures compatibility with conventional paint binders and thus does not limit the range of application of the products according to the invention in paint and printing ink applications. The products of the invention are 10 and 50 wt .-% ig soluble in conventional organic solvents such. Alcohols (ethanol, n- and iso-butanol), ketones (eg butanone), esters (eg ethyl acetate, butyl acetate), aromatics (eg xylene) and aliphatic solvents (eg. White spirit or n-hexane). In addition, a solubility in monomers used in UV-curable paints and inks, given such. B. mono- and / or higher functional acrylate monomers. This universal solubility profile can be adjusted by the choice of the ratio of k, I and m according to formula II (k = 1 to 10, preferably 1 to 8, more preferably 1 to 5, m = 2 to 12, preferably 2 to 9, particularly preferably 2 to 8 and I = 0 to 0.35, preferably 0 to 0.30, with m / k> 1, 0) and by the smallest possible proportion of aromatic structures in the resin.

Based on the particular alkylaryl ketone (for example acetophenone), the proportion of aromatic structural elements is less than 10, preferably less than 5 mg of alkylaryl ketone / g of resin.

A very low solution viscosity is desirable so that the proportion of organic solvents, which is necessary, inter alia, to z. B. to reduce the solution viscosity of a coating material in the desired processing range, due to the economy and due to environmental considerations is minimized. The solution viscosity of the products according to the invention is 40% by weight in phenoxyethanol, between 1000 and 15000 mPas, more preferably between 3000 and 10000 mPas.

For a given molecular weight (Mn), the more dissimilar the dissolved polymer is, the higher the solution viscosity (high polydispersity). The resins according to the invention have low polydispersities (Mw / Mn) between 1.35 and 1.7, more preferably between 1.4 and 1.6.

The highest possible melting range of the resins of the invention is desirable so that z. B. the drying rate of the coating materials and the hardness of the coatings are as high as possible. A high melting point / range can be obtained on the one hand via a high molecular weight (sum of k + I + m in formula II). However, the higher the molecular weight, the higher the solution viscosity. Therefore, it has been desired to raise the melting point / range without increasing the molecular weight. This could be achieved, in which k in formula II is preferably chosen as high as possible. However, since a high k in formula II adversely affects the solubility properties in nonpolar solvents, the ratio of m / k is chosen to be always greater than 1.0.

The value for k is 1 to 10, preferably 1 to 8, particularly preferably 1 to 5 and for m 2 to 12, preferably 2 to 9, particularly preferably 2 to 8. The resins according to the invention have melting points / ranges between 50 and 150 ⁰ C, preferably between 60 and 140 ⁰ C, more preferably between 75 and 130 ⁰ C.

However, the value for k of formula II must be chosen so high that the solubility of the resins of the invention in polar solvents such. B. alcohols is given. The value of k correlates with the hydroxyl number. The higher the hydroxyl number (high k), the higher the melting point / range, the better the solubility in polar solvents. Ideally, the hydroxyl number is between 75 and 350 mg KOH / g, preferably between 75 and 200 mg KOH / g, more preferably between 75 and 180 mg KOH / g.

The values for k, I and m as well as the sum of the values can be integers, e.g. B. 2, but also intermediate values, such. B. 2.4 assume.

Components for the preparation of the base resins A) ketones and aldehydes

Suitable ketones for the preparation of the carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde are all ketones with alkylaromatic structural elements, in particular all aromatic α-methyl ketones such. As acetophenone, derivatives of acetophenone such. B. Hydroxyacetophenone, alkyl-substituted acetophenone derivatives having 1 to 8 carbon atoms on the phenyl ring, methoxyacetophenone alone or in mixtures. These ketones are contained from 70 to 100 mol% based on the ketone component in the resins of the present invention.

Preference is given to carbonyl- and ring-hydrogenated ketone-aldehyde resins based on acetophenone.

In addition, further CH-acidic ketones in a subordinate scale in admixture with the above-mentioned ketones up to 30 mol%, preferably up to

15 mol% based on the ketone component are used, such as. Acetone,

Methyl ethyl ketone, 3,3-dimethyl butanone, methyl isobutyl ketone, propiophenone,

Heptanone-2, pentanone-3, 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 carbon atoms have, individually or in mixture. When

Examples of alkyl-substituted cyclohexanones can be 4-tert-amylcyclohexanone,

2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone,

2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone. Preferred as further CH-acidic ketones are cyclohexanone, methyl ethyl ketone,

2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone,

3,3-dimethylbutanone and methyl isobutyl ketone.

In addition to formaldehyde are suitable as additional aldehyde components of the carbonyl-hydrogenated ketone-aldehyde resins based on formaldehyde, in principle, unbranched or branched aldehydes, such as. As acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde and dodecanal. In general, all the aldehydes mentioned in the literature as suitable for ketone resin syntheses can be used. Preferably, however, formaldehyde is used alone. The other aldehydes can be used in proportions between 0 and 75 mol%, preferably 0 and

50 mol%, more preferably between 0 and 25 mol% based on the

Aldehyde component can be used. Aromatic aldehydes, such as. B. Benzaldehyde, may also be included in a mixture with formaldehyde up to 10 mol%.

The required formaldehyde is usually used as about 20 to 40 wt .-% aqueous or alcoholic (eg, methanol or butanol) solution. Other forms of formaldehyde are formaldehyde donating compounds such. For example, para-formaldehyde and / or trioxane.

Very particular preference is given as starting compounds for the carbonyl-hydrogenated resins acetophenone, and optionally CH-acidic ketones selected from cyclohexanone, methyl ethyl ketone, 2-tert-butylcyclohexanone,

4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, 3,3-dimethylbutanone, and

Methyl isobutyl ketone used alone or in mixture and formaldehyde. It is also possible to use mixtures of different ketone-aldehyde resins.

The molar ratio between the ketone and the aldehyde component is between 1: 0.25 to 1 to 15, preferably between 1: 0.9 to 1: 5 and more preferably between 1: 0.95 to 1: 4.

Process for the preparation of the carbonyl-containing base resins A)

Essential properties such. B. molecular weight and molecular weight distribution, content of crystallizable compounds or solution viscosities of the carbonyl- and ring-hydrogenated products of the invention are directly related to the targeted synthesis of the carbonyl group-containing base resins A). In addition, it was surprising that also color numbers and the content of free

Formaldehyde of the carbonyl- and ring-hydrogenated products according to the invention significantly over the selected reaction conditions in the preparation of

Base resins A) are influenced. To prepare the carbonyl group-containing base resins A), the particular ketone or a mixture of different ketones is reacted with formaldehyde or a mixture of formaldehyde and additional aldehydes in the presence of at least one basic catalyst. In particular, when using formaldehyde as an aqueous solution and ketones whose water solubility is limited, water-soluble organic solvents can be used advantageously. Because of the better phase mixing associated therewith, the reaction conversion is then faster and more complete. In addition, optionally at least one phase transfer catalyst can additionally be used, whereby z. B. is possible to reduce the amount of alkali compound. After completion of the reaction, the aqueous phase is separated from the resin phase. The crude product is washed with acidic water until a melt sample of the resin appears clear. Then, the resin is dried by distillation.

The reaction to produce the base resins from ketone and aldehyde is carried out in a basic medium. In general, all in the literature for ketone resin syntheses mentioned as suitable basic catalysts such. As alkali compounds are used. Preference is given to hydroxides such. As the cations NH ₄ , NR ₄ , with R = H, alkyl and / or benzyl, Li, Na.

The reaction for producing the base resins of ketone and aldehyde can be carried out by using an auxiliary solvent. As suitable, alcohols such. As methanol or ethanol proved. It is also possible to use water-soluble ketones as auxiliary solvents, which then react with the resin.

For the purification of the base resins A), the basic catalyst used must be removed from the resin A). This can be done easily by washing with water using acids for neutralization. In general, for neutralization all acids such. B. all organic and / or inorganic acids, but also ion exchangers suitable. However, preferred are organic Acids having 1 to 6 carbon atoms, more preferably organic acids having 1 to 4 carbon atoms.

In the polycondensation mixture for preparing the base resins from ketone and aldehyde, phase transfer catalysts may optionally be additionally used.

When using a phase transfer catalyst, 0.01 to 15% by weight, based on the ketone, of a phase transfer catalyst of the general formula (A)

used, where

X: a nitrogen or phosphorus atom,

Ri, R2, R3, R ₄ may be different or I gIeJCh and an alkyl group having 1 to 22 carbon atoms in the carbon chain and / or a phenyl and / or benzyl and

Y: the anion of an organic acid or a hydroxide ion.

In the case of quaternary ammonium salts, alkyl radicals (Ri _-4 ) having 1 to 22 C atoms, in particular those having 1 to 12 C atoms, in the carbon chain and / or phenyl and / or benzyl radicals and / or mixtures of both are preferred. As anions such strong (on) organic acids such. , Cl ^", ^Br" J ^", and also hydroxides, methoxide or acetates. Examples of quaternary ammonium salts are cetyldimethylbenzylammonium, tributylbenzylammonium ammonium chloride, tri-methylbenzylammonium chloride, trimethylbenzylammonium iodide, triethylbenzylammonium chloride or triethylbenzylammonium iodide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride. Benzyltributylammonium chloride, cetyldimethylbenzylammonium chloride and / or triethylbenzylammonium chloride is preferably used.

For quaternary phosphonium salts are preferred for Ri _-4 alkyl radicals having 1 to 22 carbon atoms and / or phenyl radicals and / or benzyl radicals. As anions such strong (on) organic acids such. B. Cl ^" , Br ^" , J ^" but also hydroxides, methoxides or acetates in question.

As quaternary phosphonium salts come z. B. Triphenylbenzylphosphonium- chloride or Triphenylbenzylphosphoniumjodid in question. However, mixtures can also be used.

The optionally contained phase transfer catalyst is used in amounts of 0.01 to 15, preferably from 0.1 to 10.0, and in particular in amounts of 0.1 to 5.0 wt .-% - based on the ketone used - in the polycondensation - used mixture.

Particularly preferred embodiment

In a particularly preferred embodiment, the carbonyl group- and aromatics-containing base resin A) is first prepared. For this purpose, 10 mol of ketone (a ketone or a mixture of different ketones) in a 50 to 90 wt .-% methanolic solution, 0 to 5 wt .-% of a phase transfer catalyst and 1 to 5 mol of an aqueous formaldehyde solution presented and stirring homogenized. Then, with stirring, the addition of 0.1 to 5 mol of an aqueous sodium hydroxide solution. At 70 to 115 ⁰ C is then added with stirring, the addition of 4 to 10 mol of an aqueous formaldehyde solution for 30 to 120 min. The stirrer is stopped after further 0.5 to 5 h stirring at reflux temperature. Optionally, after about one third of the runtime, another 0.1 to 1 mol of an aqueous formaldehyde solution may be added. The aqueous phase is separated from the resin phase. The crude product is washed with water using an organic acid until a melt sample of the resin appears clear. Then, the resin is dried by distillation.

Process for the preparation of the resins according to the invention according to process step B)

The resins of ketone and aldehyde are hydrogenated in the presence of a catalyst with hydrogen. The carbonyl groups of the ketone-aldehyde resin are converted into a secondary hydroxyl group. Depending on the reaction conditions, a part of the hydroxyl groups can be split off, so that methylene groups result. The reaction conditions are chosen so that the proportion of unreduced carbonyl groups is low. Furthermore, the choice of the hydrogenation conditions simultaneously converts the aromatic structural elements into cycloaliphatic units as completely as possible. For illustrative purposes, the following simplified scheme is used:

As catalysts, in principle all compounds can be used which catalyze the hydrogenation of carbonyl groups and aromatic groups and the hydrogenation of free formaldehyde to methanol with hydrogen. It is possible to use homogeneous or heterogeneous catalysts; heterogeneous catalysts are particularly preferred.

In order to obtain the formaldehyde-free products according to the invention, in particular metal catalysts selected from nickel, copper, copper-chromium, palladium, platinum, ruthenium and rhodium alone or mixed have proven to be suitable, particularly preferred are nickel, palladium and / or ruthenium catalysts.

To increase the activity, selectivity and / or lifetime, the catalysts may additionally contain doping metals or other modifiers. Typical dopants are z. B. Mo, Fe, Ag, Cr, Ni, V, Ga, In, Bi, Ti, Zr and Mn and the rare earths. Typical modifiers are for. For example, those with which the acid-base properties of the catalysts can be influenced, such. As alkali and alkaline earth metals or their compounds and phosphoric acid or sulfuric acid and their compounds. The catalysts may be in the form of powders or moldings, such as. As extrudates or pressed powders are used. Full contacts, Raney type catalysts or supported catalysts can be used. Preference is given to Raney type and supported catalysts. Suitable carrier materials are, for. For example, diatomaceous earth, silica, alumina, aluminosilicates, titanium dioxide, zirconium dioxide, aluminum-silicon mixed oxides, magnesium oxide and activated carbon. The active metal can be applied in a manner known to those skilled in the carrier material, such as. B. by impregnation, spraying or precipitation. Depending on the nature of the catalyst preparation further, known in the art preparation steps are necessary, such. As drying, calcination, shaping and activation. For shaping optionally other auxiliaries such. As graphite or magnesium stearate. The catalytic hydrogenation may be carried out in the melt, in solution of a suitable solvent or the hydrogenation product itself as a "solvent." The optional solvent may, if desired, be separated after completion of the reaction after the solvent used, additional purification steps may be necessary for the complete or partial removal of by-products or by-products, such as, for example, methanol and water Suitable solvents are those in which both the starting material and the product dissolve in sufficient quantity, and which are inert under the selected hydrogenation conditions, for example alcohols, preferably n- and i-butanol, cyclic ethers, preferably tetrahydrofuran and dioxane, alkyl ethers, aromatics, such as, for example, xylene and esters, such as For example, ethyl acetate and butyl acetate, and mixtures of these solvents are also possible The concentration of the resin in the solvent can be varied between 1 and 99% by weight, preferably between 10 and 50% by weight.

In order to achieve high conversions with the lowest possible residence times in the reactor, relatively high pressures are advantageous. The total pressure in the reactor is between 150 and 350 bar, preferably 175 to 300 bar, more preferably between 200 and 300 bar. The hydrogenation temperature is dependent on the hydrogenation catalyst used. Thus, for rhodium catalysts already temperatures of 40 to 75 ⁰ C, preferably from 40 to 60 ⁰ C sufficient, whereas higher temperatures are necessary with palladium, ruthenium or nickel catalysts. The optimum temperatures are between 150 and 250 ⁰ C, preferably between 150 and 225 ⁰ C.

The hydrogenation to the resins according to the invention can be carried out in discontinuous or continuous mode. It is also possible to use a semi-continuous procedure in which resin and / or solvent is fed in continuously in a batch reactor, and / or continuously one or more reaction products and / or solvents are removed. The catalyst loading is 0.05 to 4 t of resin per cubic meter of catalyst per hour, preferably 0.1 to 2 t of resin per cubic meter of catalyst per hour.

Various methods known to the person skilled in the art are suitable for controlling the temperature profile in the reactor and in particular for limiting the maximum temperature. So z. B. are working at sufficiently low resin concentrations completely without additional reactor cooling, wherein the reaction medium completely absorbs the released energy and thereby convectively leads out of the reactor out. Also suitable are, for example, tray reactors with intermediate cooling, the use of hydrogen circuits with gas cooling, the recycling of part of the cooled product (circulation reactor) and the use of external coolant circuits, in particular in tube-bundle reactors.

Preferred embodiment I for the preparation of the carbonyl hydrogenated resins

The hydrogenation of the produced carbonyl-containing, aromatic resin A) is preferably carried out with catalysts based on nickel, palladium and / or ruthenium. Particularly suitable for the preparation of the resins of the invention are continuous fixed bed reactors, such. B. shaft furnaces and tube bundles, which are preferably operated in trickle bed mode. In this case, hydrogen and the resin to be hydrogenated, optionally dissolved in a solvent, are added to the catalyst bed at the top of the reactor. Alternatively, the hydrogen can also be passed in countercurrent from bottom to top. The reaction mixture leaving the reactor is passed through a filter to remove catalyst residues. The optionally contained solvent can - if desired - then be separated.

Various methods are suitable for removing the heat of reaction liberated during the hydrogenation or for reducing the temperature rise. This can be done for example by a gas cycle by a greater amount of hydrogen than stoichiometrically necessary is fed to the reactor. The hydrogen leaving the reactor is cooled and returned to the top of the reactor. In tube bundle reactors, the removal of the heat of reaction is preferably realized via an external coolant circuit.

For temperature control is also the return of a part of the product to

Reactor inlet suitable (circulation reactor). The reaction product can, as it leaves the reactor, be recycled without further work-up. However, it may also be advantageous to provide an additional work-up step before the return, for example the separation of a part of the used

Solvent. The product may be recycled at the temperature at which it leaves the reactor, but it may also be first cooled to remove at least a portion of the heat of reaction.

There are also combinations of the different variants for temperature control possible.

Preferred embodiment II for the preparation of the carbonyl-hydrogenated resins The hydrogenation of the carbonyl-containing, aromatic resin A) produced can also be carried out batchwise in batch reactors (autoclaves). Again, catalysts based on nickel, palladium and / or ruthenium are preferably used. The resin to be hydrogenated, optionally dissolved in a solvent, is added to the reactor. The catalyst is added in the form of a powder and suspended in the reaction medium by suitable methods known to those skilled in the art. Particularly suitable reactor types are, for example, stirred tank reactors, bubble columns, Kvaerner-Buss loop reactors and Biazzi reactors. The total pressure is adjusted by adding the hydrogen. It is also possible to control the progress of the reaction or the product quality over the offered amount of hydrogen. So it may be z. B. especially at the beginning of the reaction be advantageous to limit the amount of hydrogen introduced, to prevent excessive heat generation due to the exotherm of the reaction. It is also possible not to suspend the catalyst as a powder in the reaction medium in batchwise operation, but with the usual for fixed bed reactors moldings such. As extrudates, pellets or tablets to work. In this case For example, it is preferred to pass the resin to be hydrogenated, optionally dissolved in a solvent, over the fixed-bed catalyst until the desired degree of hydrogenation is reached. The fixed bed catalyst may be placed in a separate reaction tube, but may also be located in metal baskets or other suitable containers directly in the reactor.

Regardless of whether powder or fixed bed catalysts are used, the reaction mixture leaving the reactor is passed through a filter to remove catalyst residues. The optionally contained solvent can - if desired - then be separated.

Analytical methods

Determination of the content of free formaldehyde

The formaldehyde content is determined by post-column derivatization according to the lutidine method by HPLC.

Determination of the hydroxyl number

The determination is made in accordance with DIN 53240-2 "Determination of the Hydroxyl Number." It must be ensured that an acetylation time of 3 hours is exactly maintained.

Determination of carbonyl number

The determination is carried out by FT-IR spectroscopy after calibration with 2-ethylhexanone in THF in a NaCI cuvette.

Determination of the content of unhydrogenated aromatic structural elements

The determination is carried out FT-IR spectroscopically relative to the respectively used

Alkyl aryl ketone (eg acetophenone) in THF in a NaCI cuvette. Determination of the content of nonvolatile matter (nfA)

The content of non-volatile components is given as the mean value of a duplicate determination. 2 g of the sample are weighed into a cleaned aluminum dish (Taramasse rrii) on an analytical balance (mass m _{2 of} the substance). Then you give the aluminum dish over 24 h at 150 ⁰ C in a convection oven. The dish is cooled to room temperature and weighed to the nearest 0.1 mg (1ΥI ₃ ). The nonvolatile fraction (nfA) is calculated according to the following equation:

_n fa = ^{mi ~ mi} - 100 [wt%]

Determination of color number according to Gardner

The Gardner color number is determined in 50% strength by weight solution of

Resin in ethyl acetate based on DIN ISO 4630.

Also, the color number after thermal stress is determined in this way.

For this purpose, the resin is first stored for 24 h at 150 ⁰ C in an air atmosphere

(see determination of non-volatile content). Then the determination of the

Color number according to Gardner in 50% by weight solution of the thermally loaded resin in ethyl acetate on the basis of DIN ISO 4630.

Determination of the solution viscosity

To determine the solution viscosity, the resin is dissolved at 40% strength by weight in phenoxyethanol. The viscosity is measured at 20 ⁰ C using a plate / cone viscometer (1 / 4OS).

Determination of polvdispersity

The molecular weight distribution of the resins according to the invention is measured by means of gel permeation chromatography in tetrahydrofuran against polystyrene as standard. The polydispersity (Mw / Mn) is calculated from the ratio of weight average (Mw) to number average (Mn). Determination of the melting range

The determination is carried out using a capillary melting point measuring device (Büchi B-545) in accordance with DIN 53181.

Determination of the content of crystallizable compounds

Solutions of the hydrogenated resins in phenoxyethanol are stored for crystal formation. The crystals are separated diluted with ethanol, isolated through a membrane filter and weighed.

Determination of solubility

Solutions of the resins in ethanol, white spirit and n-hexane are prepared. For this purpose, the resins are dissolved 10 and 50 wt .-% strength in the respective solvent with stirring and assessed the clarity of the solution visually.

Calculation of the Copolver distribution

To calculate the values for k, I and m, proceed as follows. Calculation example (for illustrative purposes, integers are used):

with R = cyclohexyl

assumptions:

The molecular weight (Mn) is 1000 g / mol, the OH number is 150 mg KOH / g, the carbonyl number is 10 mg KOH / g.

From an OH number of 300 mg KOH / g result (150/56110 * 1000) 2.7 OH groups per 1000 g / mol. This means that k = 2.7. From a C = O-ZaM of 10 mg KOH / g result (10/56110 * 1000) 0.2 C = O groups per 1000 g / mol. This means that I = 0.2. Calculation of m: (1000 g / mol - (5.35 mol ^* 139 g / mol) - (0.18 mol ^* 137 g / mol)) / 123 g / mol = 4.9. The sum of k + m + I is thus 7.8.

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

Examples:

Non-inventive comparative examples

The document which best describes the state of the art is DE 33 34 631 A1. The acetophenone / formaldehyde resin used here was obtained according to Example 2 of DE 892 975.

Example A: Adjustment of Example 2 of DE 892 975

After addition of 240 g of 50% strength by weight potassium hydroxide solution and 400 g of methanol, 1200 g of 30% strength by weight formaldehyde solution are added to 1200 g of acetophenone over the course of 2 hours with vigorous stirring. The temperature increases to 90 ^° C. This temperature is maintained for 10 hours. It is acidified with sulfuric acid and the resulting condensation product is washed with hot water, melted and dehydrated in vacuo. There are obtained 1260 g of a yellow resin. The resin is clear and brittle and has a melting point of 67 ^° C. The Gardner color number is 3.8 (50% by weight in ethyl acetate). It is Z. B. in acetates such. Butyl and ethyl acetate, soluble in aromatics such as toluene and xylene. It is insoluble in ethanol. The formaldehyde content is 255 ppm. Example B: Adjustment of Example 3 of DE 33 34 631 A1

The resin of Example A was dissolved in i-butanol with heating at 30% by weight. The hydrogenation was carried out in a continuously operated fixed bed reactor, which was filled with 400 ml_ of a commercial nickel contact (Engelhard Ni 5126T1 / 8). This catalyst is in accordance with the indication of the Engelhard identical to that used in DE 33 34 631 catalyst "Harshaw Ni 5124". At 300 bar and 180 ⁰ C are hourly 250 ml_ of the reaction mixture from top to bottom through the reactor (trickle) The pressure is kept constant by the addition of hydrogen.

Example C: Adjustment of Example 4 of DE 33 34 631 A1

300 g of the resin from Example A were dissolved with heating in 700 g of i-butanol. The hydrogenation was then carried out at 300 bar and 200 ^° C. in an autoclave (Parr Co.) with a catalyst basket filled with 90 g of a commercial Pd catalyst (0.5% by weight of Pd on Al ₂ O ₃ ). After 4 hours, the reaction mixture was drained from the reactor via a filter.

Examples according to the invention

Inventive Example I)

Preparation of a base resin for further hydrogenation based on acetophenone and formaldehyde

1200 g of acetophenone, 220 g of methanol, 0.3 g of benzyltributylammonium chloride and 360 g of a 30 wt .-% aqueous solution of formaldehyde are introduced and homogenized with stirring. Then, with stirring, the addition of 32 g of a 25 wt .-% aqueous sodium hydroxide solution. At 80 to 85 ⁰ C is then added with stirring, the addition of 655 g of a 30 wt .-%, aqueous formaldehyde solution over 90 min. The stirrer is stopped after 5 h stirring at reflux temperature and the aqueous phase separated from the resin phase. The crude product is washed with acetic acid water until a melt sample of the resin appears clear. Then, the resin is dried by distillation. There are 1270 g of a slightly yellowish resin. The resin is clear and brittle and has a melting point of 72 ^° C. The Gardner color number is 0.8 (50% strength by weight in ethyl acetate). It is Z. B. in acetates such. Butyl and ethyl acetate, soluble in aromatics such as toluene and xylene. It is insoluble in ethanol. The formaldehyde content is 35 ppm.

Hydrogenation of the Resin Based on Acetophenone and Formaldehyde from Example I)

Inventive Example 1:

The resin from Example I) was dissolved in i-butanol with heating at 30% by weight. The hydrogenation was carried out in a continuously operated fixed bed reactor which was filled with 400 ml_ of a commercial Raney nickel fixed bed catalyst. At 275 bar and 180 ⁰ C were passed 240 ml of the reaction mixture from top to bottom through the reactor (downflow). The pressure is kept constant by the addition of hydrogen.

Inventive Example 2:

The resin from Example I) was dissolved in i-butanol with heating at 30% by weight. The hydrogenation was carried out in a continuously operated fixed bed reactor which was filled with 400 ml_ of a commercial Raney nickel fixed bed catalyst. At 275 bar and 170 ⁰ C were passed 400 ml of the reaction mixture from top to bottom down through the reactor (downflow). The pressure is kept constant by the addition of hydrogen.

Inventive Example 3:

300 g of the resin from Example I) were dissolved with heating in 700 g of i-butanol. Then the hydrogenation was carried out at 260 bar and 160 ⁰ C in an autoclave (Fa. Parr) with a catalyst basket with 100 ml of a commercially available nickel catalyst was filled (Engelhard Ni 5126T1 / 8). After 5 h, the reaction mixture was drained from the reactor via a filter. Inventive Example 4:

300 g of the resin from Example I) were dissolved with heating in 700 g of i-butanol. Then the hydrogenation was carried out at 260 bar and 180 ⁰ C in an autoclave (Fa. Parr) with a catalyst basket with 100 ml of a commercially available Raney nickel catalyst fixed bed was filled. After 4 hours, the reaction mixture was drained from the reactor via a filter.

The resin solutions of Examples 1 to 4 and Comparative Examples B and C are freed from the solvent in vacuo. The properties of the resulting resins are listed in Table 1.

Table 1: Properties of the hydrogenated resins according to Examples 1 to 4 and Comparative Examples B and C.

All resins obtained are bright, clear and brittle.

The resins 1 to 4 of the invention have a significantly lower compared to the non-inventive resins according to Example B and C.

Content of free formaldehyde and crystallizable compounds.

Corresponding to the lower carbonyl number, the color numbers and the color numbers after thermal loading are lower. The solution viscosities of the resins 1 to 4 according to the invention are significantly lower in comparison to the non-inventive resins of Examples B and C. This may optionally be explained by the higher polydispersity of the non-inventive resins.

The resins of the inventive examples 1 to 4 are 10 and 50 wt .-% ig perfectly soluble in ethanol, white spirit and n-hexane. In contrast, the resins of Comparative Examples B and C are no longer perfectly soluble in ethanol and n-hexane at concentrations of 10 wt% solids. This may possibly be attributed to the higher levels of aromatics and the low ratio of m / k (in both cases by 1, 0).

Since not all the properties of the resins of the present invention are due to the hydrogenation conditions, obviously, the production process of the starting resin has a significant influence on the properties of the obtained hydrogenated resins.

Claims

claims:

1. OH-functional, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde having a hydroxyl number of at least 75 mg KOH / g, with a content of free formaldehyde of less than 3 ppm, which substantially the structural elements according to formula II contain

With

R = aromatic with 6 to 14 carbon atoms, cycloaliphatic with 6 to 14

R '= H, CH ₂ OH, k = 1 to 10, m = 2 to 12,

I = 0 to 0.35, where the sum of k + I + m is between 3 and 24, the ratio of m / k> 1, 0 and the three structural elements can be distributed alternately or randomly and wherein the structural elements are linked linearly via CH ₂ groups and / or branching via CH groups.

2. OH-functional, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde having a hydroxyl number of at least 75 mg KOH / g, with a content of free formaldehyde of less than 3 ppm, which are essentially the structural elements according to formula II contain

with R = aromatic with 6 to 14 carbon atoms, cycloaliphatic with 6 to 14

Carbon atoms, wherein the proportion of the aromatic structural elements below

10, preferably less than 5 mg alkylaryl ketone / g (based on alkylaryl ketone),

R '= H, CH ₂ OH, k = 1 to 10, m = 2 to 12,

I = 0 to 0.35, where the sum of k + I + m is between 3 and 24, the ratio of m / k> 1, 0

and the three structural elements can be distributed alternately or statistically and wherein the structural elements are linearly and / or via CH ₂ groups via CH ₂ groups.

Groups are branched linked, obtained by

A) the preparation of the base resins by condensation of at least one ketone with at least one aldehyde in the presence of at least one basic catalyst and optionally at least one

Phase transfer catalyst, solvent-free or using a water-miscible organic solvent,

and subsequently

B) continuous, semi- or discontinuous hydrogenation of the carbonyl groups and the aromatic groups of the ketone-aldehyde resins (A) in the melt or in solution of a suitable solvent with hydrogen in the presence of a catalyst at pressures between 150 and 350 bar and temperatures between 150 and 250 ⁰ C.

3. carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the content of free formaldehyde is less than 3 ppm, preferably less than 2.5 ppm, more preferably less than 2.0 ppm ,

4. carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the content of crystallizable compounds below 3 wt .-%, preferably below 2 wt .-%, more preferably below 1 wt .-% lies.

5. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkyl aryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the carbonyl number between 0 and 20 mg KOH / g, preferably between 0 and

18 mg KOH / g, more preferably between 0 and 15 mg KOH / g.

6. carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the hydroxyl number between 75 and 350 mg KOH / g, preferably between 75 and 200 mg KOH / g, more preferably between 75 and 180 mg KOH / g.

7. carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the proportion of aromatic structural elements is less than 10, preferably less than 5 mg alkylaryl ketone / g (based on alkylaryl ketone).

8. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the Gardner color number (50 wt .-% in ethyl acetate) below 1, 5, preferably below 1, 0, more preferably below 0.75.

9. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkyl aryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the Gardner color number (50 wt .-% in ethyl acetate) after thermal loading of the resin (24 h, 150 ⁰ C) is less than 2.0, preferably less than 1.5, more preferably less than 1.0.

10. carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the polydispersity (Mw / Mn) of the resins between 1, 35 and 1, 7, more preferably between 1, 4 and 1, 6 lies.

1 1. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the solution viscosity, 40 wt .-% strength in isopar H, between 1000 and 15000 mPa-s, more preferably between 3000 and 10000 mPa-s is located.

12. carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkyl aryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the melting point / range between 50 and 150 ⁰ C, preferably between 60 and 140 ⁰ C, particularly preferably between 75 and 130 ⁰ C lies.

13. carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the content of non-volatile constituents after annealing for 24 h at

150 ⁰ C over 97.0 wt .-%, preferably above 97.5 wt .-% is.

14. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkyl aryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the solubility in n-hexane, white spirit and ethanol 10 and 50 wt .-% strength, is given.

15. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that aromatic α-methyl ketones are included.

16. carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkyl aryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that acetone phenone, derivatives of acetophenone such as. As hydroxyacetophenone, alkyl-substituted acetophenone derivatives having 1 to 8 carbon atoms on the phenyl ring, methoxyacetophenone alone or in mixtures, are included.

17. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that further CH-acidic ketones in mixture with the alkylaromatic ketones up to 30 mol%, preferably up to 15 mol% %, based on the ketone component, selected from acetone, methyl ethyl ketone, 3,3-dimethylbutanone, methyl isobutyl ketone, propiophenone, heptanone-2, pentanone-3, 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 having a total of 1 to 8 hydrocarbon atoms, individually or in mixture.

18. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that as alkyl-substituted cyclohexanones 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and / or 3, 3, 5-trimethylcyclohexanone are included.

19. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that formaldehyde and / or formaldehyde donating compounds are used as the starting compound for the preparation of the ketone-aldehyde resins.

20. carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that are used as starting compound for the preparation of the ketone-aldehyde resins formaldehyde and / or para-formaldehyde and / or trioxane.

21. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that as starting compounds for the preparation of the ketone-aldehyde resins in addition to formaldehyde and / or formaldehyde-donating compounds aldehydes selected from acetaldehyde, n-butyraldehyde , Iso-butyraldehyde, valeric aldehyde, dodecanal, alone or in mixtures in proportions between 0 and 75 mol%, preferably 0 and 50 mol%, particularly preferably between 0 and 25 mol% based on the aldehyde component used.

22. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkyl aryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that as starting compounds for the preparation of the ketone-aldehyde resins

Acetophenone, and optionally CH-acidic ketones selected from cyclohexanone, methyl ethyl ketone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone and 3,3,5-trimethylcyclohexanone, used alone or in mixtures and formaldehyde.

23. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that the molar ratio between the ketone and the aldehyde component is between 1: 0.25 to 1 to 15, preferably between 1: 0.9 to 1: 5 and more preferably between 1: 0.95 to 1: 4 ,

24. A process for the preparation of the OH-functional, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde, having a hydroxyl value of at least 75 mg KOH / g, with a content of free formaldehyde of less than 3 ppm, the substantially contain the structural elements according to formula II, characterized by

A) the preparation of the base resins by condensation of at least one

Ketone with at least one aldehyde in the presence of at least one basic catalyst and optionally at least one phase transfer catalyst, solvent-free or using a water-miscible organic solvent,

and subsequently

B) continuous, semicontinuous or discontinuous hydrogenation of

Carbonyl groups and the aromatic groups of the ketone-aldehyde resins (A) in the melt or in solution of a suitable solvent with hydrogen in the presence of a catalyst at pressures between 150 and 350 bar and temperatures between 150 and 250 ⁰ C.

25. The method according to claim 24, characterized in that the reaction A) is carried out in a basic medium.

26. The method according to claim 25, characterized hydroxides of the cations NH ₄ , NR ₄ , with R =H, alkyl and / or benzyl, Li or Na, preferably hydroxides of the cations NH ₄ , NR ₄ , with R = for preparing the carbonyl-containing ketone-aldehyde resins A) H, alkyl and / or benzyl, or Na are used.

27. The method according to at least one of claims 24 to 26, characterized in that the preparation of the carbonyl-containing ketone-aldehyde A) takes place using an auxiliary solvent.

28. The method according to claim 27, characterized in that the preparation of the carbonyl-containing ketone-aldehyde A) using an auxiliary solvent selected from water-miscible alcohols and / or ketones occurs.

29. The method according to at least one of claims 24 to 28, characterized in that for the preparation of carbonyl-containing ketone-aldehyde A) optionally additionally a phase transfer catalyst is used, in amounts of

0.01 to 15, preferably from 0.1 to 10.0, and in particular in amounts of 0.1 to 5.0 wt .-% - based on the ketone.

30. The method according to claim 29, characterized in that are used as quaternary ammonium salts, cetyldimethylbenzylammonium chloride, benzyltributylammonium chloride, and / or triethylbenzylammonium chloride and as quaternary phosphonium salts, Triphenylbenzylphosphoniumchlorid and / or Triphenylbenzylphosphoniumjodid.

31. The method according to at least one of claims 24 to 30, characterized for washing the base resin A) with water using acids.

32. The method according to claim 31, characterized in that for the purification of the base resin A) with water using organic acids having 1 to 6, preferably 1 to 4 carbon atoms is washed.

33. The method according to at least one of claims 24 to 32, characterized in that a homogeneous or heterogeneous catalyst for hydrogenating the carbonyl group-containing base resins A) is used.

34. The method according to at least one of claims 24 to 33, characterized in that metal catalysts are used for hydrogenation.

35. The method according to at least one of claims 24 to 34, characterized in that metal catalysts are used for the hydrogenation, the metals nickel, copper, copper-chromium, palladium, platinum, ruthenium and rhodium alone or in mixtures, preferably nickel, Palladium and ruthenium alone or in mixtures, as main metals.

36. The method according to at least one of claims 24 to 35, characterized in that the metal catalysts additionally contain dopants and / or other modifiers.

37. The method according to claim 36, characterized that additional doping metals are selected, selected from Mo, Fe, Ag, Cr, Ni, V, Ga, In, Bi, Ti, Zr and Mn and the rare earths.

38. The method according to at least one of claims 24 to 37, characterized in that modifiers are included, selected from alkali and alkaline earth metals and / or their compounds, and / or phosphoric acid and / or sulfuric acid and their compounds.

39. The method according to at least one of claims 24 to 38, characterized in that the catalysts are used in the form of powders or moldings.

40. The method according to at least one of claims 24 to 39, characterized in that the catalysts are used as solid contacts, Raney type catalysts or supported catalysts.

41. The method according to claim 40, characterized in that are used as carrier material diatomaceous earth, silica, alumina, aluminosilicates, titanium dioxide, zirconium dioxide, aluminum-silicon mixed oxides, magnesium oxide and / or activated carbon.

42. The method according to at least one of claims 24 to 41, characterized in that the catalytic hydrogenation is carried out in the melt, in solution of a suitable solvent or the hydrogenation product itself as a "solvent".

43. The method according to claim 42, characterized that n-butanol, i-butanol, tetrahydrofuran, ethyl and butyl acetate, xylene, dioxane, diethyl ether and / or diethylene glycol are used as solvents.

44. The method according to at least one of claims 42 and 43, characterized in that the optionally contained solvent is separated after completion of the reaction and recycled to the circulation.

45. The method according to at least one of claims 24 to 44, characterized in that compounds according to at least one of claims 1 to 23 are used.

46. The method according to at least one of claims 24 to 43, characterized in that the catalyst loading 0.05 to 4 t of resin per cubic meter of catalyst per hour, preferably 0.1 to 2 t of resin per cubic meter of catalyst and hour.

47. The method according to at least one of claims 24 to 46, characterized in that the hydrogenation is carried out batchwise, continuously or semicontinuously.

48. The method according to at least one of claims 24 to 47, characterized in that the hydrogenation is carried out continuously.

49. The method according to at least one of claims 24 to 48, characterized in that is hydrogenated in a fixed bed reactor.

50. The method according to at least one of claims 24 to 49, characterized in that the hydrogenation takes place in shaft furnaces or tube bundles.

51. The method according to at least one of claims 24 to 50, characterized in that the hydrogenation takes place in trickle bed mode.

52. The method according to at least one of claims 24 to 51, characterized in that hydrogen and the resin to be hydrogenated, optionally dissolved in a solvent, is added to the head of the reactor on the catalyst bed.

53. The method according to at least one of claims 24 to 52, characterized in that the hydrogen is passed in countercurrent from bottom to top.

NEW (taken from EM 060088)

54. The method according to at least one of claims 24 to 53, characterized in that the hydrogenation is discontinuous.

55. The method according to at least one of claims 24 to 54, characterized in that the hydrogenation is carried out in batch reactors (autoclave).

56. The method according to at least one of claims 24 to 55, characterized in that the hydrogenation is carried out in stirred tank reactors, bubble columns, Kvaerner-Buss loop reactors or Biazzi reactors.

57. The method according to at least one of claims 24 to 56, characterized in that first the carbonyl group-containing base resin A) is prepared by

Preparation and homogenization of 10 mol (or a multiple) of a ketone or a mixture of different ketones, as claimed in a 50 to 90 wt .-% methanol solution, 0 to 5 wt .-% of a phase transfer catalyst and 1 to 5 mol (or a multiple) of an aqueous formaldehyde solution with stirring,

Adding with stirring from 0.1 to 5 mol (or a multiple) of an aqueous sodium hydroxide solution,

• Addition of 4 to 10 mol (or a multiple) of an aqueous

Formaldehyde solution at 70 to 115 ⁰ C with stirring over 30 to 120 min,

• Stopping of the stirrer after further 0.5 to 5 h stirring at reflux temperature, optionally after about a third of the runtime further 0.1 to 1 mol (or a multiple) of an aqueous

Formaldehyde solution can be added

Separation of the aqueous phase from the resin phase,

• Wash the crude product with water using an organic

Acid until a melt sample of the resin appears clear

and

• final drying of the resin by distillation.