EP2027171A1

EP2027171A1 - Formaldehyde-free, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkyl aryl ketones and formaldehyde which have a low oh functionality and a process for preparing them

Info

Publication number: EP2027171A1
Application number: EP07729095A
Authority: EP
Inventors: Patrick GLÖCKNER; Christian Lettmann; Michael Ewald; Andreas Wenning
Original assignee: Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2006-06-09
Filing date: 2007-05-14
Publication date: 2009-02-25
Also published as: DE102006026758A1; WO2007141114A1; JP2009540027A; CN101085824A; US20090198024A1

Abstract

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

Description

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

The invention relates to formaldehyde-free, carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde with low OH functionality, low proportion of crystallizable compounds, low viscosity, very low color number 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. used as film-forming additional components to improve certain properties such as drying rate, gloss, hardness or scratch resistance. Because of their relatively low molecular weight, conventional ketone-aldehyde resins have a low melt and solution viscosity and are therefore used 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. outdoors, in which high resistance properties, in particular to weathering and heat are required, not possible. These disadvantages can be improved by hydrogenation of the carbonyl groups. 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 which have improved properties relative to the starting materials in terms of color, heat and light resistance. From today's point of view, the performance of these products, despite their improvement is no longer sufficient. According to the method described in DE 33 34 631, the solubility profile of the starting resins changed. As our own investigations showed, however, a compatibility with non-polar polymers such. As amorphous poly-α-olefins or paraffins not given. Furthermore, own findings show that the content of crystallizable compounds and the color numbers are high.

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.

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 of lowering the formaldehyde content of non-hydrogenated acetone-formaldehyde resins without reducing the carbonyl groups is described in US 5,247,066. Here a content of free formaldehyde below 0.4 wt .-% is achieved which, however, 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 non-polar polymers such. As amorphous poly-α-olefins or paraffins are compatible.

The proportion of crystallizable compounds should be as low as possible. In addition, the properties of the resins in terms of solution viscosity, melting range and color should be further improved and very high heat and light resistance should be present. 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 structural elements as well as crystallizable compounds and are virtually free of formaldehyde. A very good compatibility with non-polar polymers such. As amorphous poly-α-olefins or paraffins is given and is set by the carbonyl and hydroxyl number and the aromatic portion. The solution viscosity is low in contrast to the prior art and can be realized by the use of tailor-made hydrogenation starting resins which have a particularly narrow molecular weight distribution.

The invention relates to carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde having a hydroxyl number of 0 to 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

With

R = aromatic with 6-14 carbon atoms, cycloaliphatic with 6 to 14 carbon atoms, wherein the proportion of the aromatic structural elements below 10, preferably below 5 mg alkylaryl ketone / g resin (based on the particular used

Alkylaryl ketone),

R '= H, CH ₂ OH, k = 0 to 6, preferably 0 to 4, particularly preferably 0 to 3, m = 2 to 18, preferably 2 to 15, particularly preferably 2 to 12,

I = 0 to 0.35, preferably 0 to 0.30, the sum of k + I + m being between 2 and 24, preferably between 2 and 19, particularly preferably 2 to 15, the ratio of m / k> 5, preferably> 7.5 and the three structural elements can be distributed alternately or randomly and wherein the structural elements are linearly linked via CH ₂ groups and / or branching via CH groups.

The invention relates to carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde having a hydroxyl number of 0 to 75 mg KOH /, with a content of free formaldehyde of less than 3 ppm, which substantially contain the structural elements according to formula II

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 below 5 mg alkylaryl ketone / g resin (based on the particular used

Alkylaryl ketone),

R '= H, CH ₂ OH, k = 0 to 6, preferably 0 to 4, particularly preferably 0 to 3, m = 2 to 18, preferably 2 to 15, particularly preferably 2 to 12, I = O to 0.35 , preferably 0 to 0.30, wherein the sum of k + I + m is between 2 and 24, preferably between 2 and 19, more preferably 2 to 15, the ratio of m / k> 5, preferably> 7.5 is and the three structural elements can be distributed alternately or randomly and wherein the structural elements via CH ₂ groups are linearly and / or linked 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, 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 50 and 250 bar, preferably between 75 and

225 bar, more preferably between 75 and 200 bar and temperatures between 150 and 250 ⁰ C, preferably between 150 and 225 ⁰ C, particularly preferably 175 and 220 ⁰ C.

A preferred subject 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 below 3 ppm, preferably below 2.5 ppm, more preferably below 2, 0 ppm,

The content of crystallisable compounds is less than 3% by weight, preferably less than 2% by weight, more preferably less than 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 0 and 75 mg KOH / g, preferably between 0 and 60 mg KOH / g, more preferably between 0 and 50 mg KOH / g,

The proportion of aromatic structural elements is less than 10, preferably less than 5 mg alkylaryl ketone / g resin (based on alkylaryl ketone), Gardner color number (50% strength by weight in ethyl acetate) is less than 1.5, preferably less than 1.0 , more preferably below 0.75,

Gardner color number (50% strength by weight in ethyl acetate) is, after thermal loading of the resin (24 h, 150 ^° C.) 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% strength by weight in isopar H, is between 1000 and 15000 mPa.s, more preferably between 3000 and 10000 mPa.s,

• The melting point / range is between 25 and 150 ⁰ C, preferably between 30 and 125 ⁰ C, more preferably between 35 and 100 ⁰ C, • The content of non-volatile constituents after annealing is above 24 h at 150 ⁰ C above 97 , 0 wt .-%, preferably about 97.5 wt .-% and

• Solubility is given in n-hexane, white spirit and isopar H at 10 and 50% dilution (w / w).

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 75 mg KOH / g - upper limit - and a content of free formaldehyde below 2 ppm - lower limit - etc.

The invention also provides a process for the preparation of the carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde having a hydroxyl number of 0 to 75 mg KOH / g, with a content of free formaldehyde of less than 3 ppm, which is substantially contain the structural elements according to formula II, characterized by

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 50 and 250 bar, preferably between 75 and 225 bar, more preferably between 75 and 200 bar and temperatures between 150 and 250 ⁰ C, preferably between 150 and 225 ⁰ C, particularly preferably 175 and 220 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 color number according to Gardner (50 wt .-% in ethyl acetate) of the inventive products under 1, 5, preferably less than 1, 0, more preferably below 0.75 and the Gardner color number (50 wt. % by weight in ethyl acetate) after thermal loading of the products according to the invention (24 h, 150 ^° C.) is below 2.0, preferably below 1.5, particularly preferably below 1.0.

The best possible solubility in nonpolar solvents is desirable because thus the compatibility with nonpolar polymers such. As polyethylene, polypropylene, natural resins, copolymers of α-olefins and / or paraffins is guaranteed and thus the range of application of the inventive products in applications in which these products are used, is not limited. The invention Products are 10 and 50% soluble in non-polar organic solvents such. B. aromatics (eg., XyIoI) and aliphatic solvents (eg, white spirit, paraffins or n-hexane). They have a very good compatibility with nonpolar polymers such. As polyethylene, polypropylene, copolymers of α-olefins, paraffins, waxes, modified waxes such. B. functionalized and / or oxidized polyethylene waxes and / or natural resins.

This solubility profile can be adjusted by the choice of the ratio of k, I and m according to formula II (k = 0 to 6, preferably 0 to 4, more preferably 0 to 3, m = 2 to 18, preferably 2 to 15, especially preferably 2 to 12 and I = 0 to 0.35, preferably 0 to 0.30, with m / k> 5, preferably> 7.5) 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.

The lowest possible solution viscosity is desired so that the proportion of organic solvents which is necessary, inter alia, to lower the solution viscosity into the desired processing range is as low as possible due to the economy and due to environmental considerations. The solution viscosity of the products according to the invention is 40% in isopar H, between 1000 and 15000 mPa.s, more preferably between 3000 and 10000 mPa.s.

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). The higher, however Molecular weight, the higher the solution viscosity. Therefore, it was desired to raise the melting point range without increasing the molecular weight. This could be achieved in which k in formula II is preferably as high as possible without adversely affecting the desired solubility profile. 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 5.

The value for k is 0 to 6, preferably 0 to 4, particularly preferably 0 to 3 and for m 2 to 18, preferably 2 to 15, particularly preferably 2 to 12. The resins according to the invention have melting points / ranges between 25 and 150 ⁰ C, preferably between 30 and 125 ^° C., more preferably between 35 and 100 ^° C.

The value of k correlates with the hydroxyl number. The higher the hydroxyl number, the higher the melting point / range, but the worse the solubility in nonpolar solvents. Ideally, the hydroxyl number is between 0 and 75 mg KOH / g, preferably between 0 and 60 mg KOH / g, more preferably between 0 and 50 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. As hydroxyacetophenone, alkyl-substituted acetophenone derivatives having 1 to 8 carbon atoms on the phenyl ring, methoxyacetophenone alone or in mixtures. These ketones are from 70 to 100 mol%, based on the ketone component, contained in the resins of the invention. Preference is given to carbonyl- and ring-hydrogenated ketone-aldehyde resins based on acetophenone.

Furthermore, further CH-acidic ketones can be used on a subordinate scale in mixture with the abovementioned ketones up to 30 mol%, preferably up to 15 mol%, based on the ketone component, such as. For example, 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 and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals having a total of 1 to 8 carbon atoms, individually or in mixture. As examples of alkyl-substituted cyclohexanones there can be mentioned 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone. Cyclohexanone, methyl ethyl ketone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, 3,3-dimethylbutanone and methyl isobutyl ketone are preferred as further CH-acidic ketones.

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 further aldehydes can be used in proportions between 0 and 75 mol%, preferably 0 and 50 mol%, particularly preferably between 0 and 25 mol%, based on the aldehyde component. Aromatic aldehydes, such as. As benzaldehyde, may be included in a mixture with formaldehyde up to 10 mol% also.

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

Very particular preference is given as starting compounds for the carbonyl-hydrogenated resins to acetophenone, and optionally CH-acidic ketones selected from cyclohexanone, methyl ethyl ketone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, 3,3- Dimethyl butanone 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 group-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 according to the invention are directly related to the targeted synthesis of the carbonyl group-containing base resins A). In addition, it was surprising that color numbers and the content of free formaldehyde of the carbonyl- and ring-hydrogenated products according to the invention are significantly influenced by the chosen reaction conditions in the preparation of the base resins A).

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 associated among other things better phase mixing is the Reaction turnover 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. Suitable hydroxides such. As the cations NH ₄ , NReSt ₄ , with the radical = H, alkyl and / or benzyl, Li, Na, preferably hydroxides of the cations NH ₄ , NReSt ₄ , with the radical = H, alkyl and / or benzyl, or 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,

R 1, R 2, R 3, R 4: may be the same or different and is an alkyl radical having 1 to 22 C atoms in the carbon chain and / or a phenyl and / or a benzyl radical 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, methylbenzylammoniumchlorid tributylbenzyl, tri-, Trimethylbenzylammoniumjodid, Triethylbenzyl- ammonium chloride or Triethylbenzylammoniumjodid, tetramethylammonium chloride, tetraethylammonium, tetrabutylammonium. Preferably benzyltributylammonium, Cetyldimethylbenzylammoniumchlorid and / or triethylbenzylammonium chloride 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. Triphenylbenzylphosphoniumchlorid 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% by mass of a phase transfer catalyst and 1 to 5 mol of an aqueous formaldehyde solution and homogenized with stirring. 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 has been used, additional purification steps may be necessary to completely or partially remove minor or less volatile by-products such as methanol and water can. Suitable solvents are those in which both the starting material and the product dissolve in sufficient quantities, and which are inert under the chosen hydrogenation conditions. These are z. As alcohols, preferably n- and i-butanol, cyclic ethers, preferably tetrahydrofuran and dioxane, alkyl ethers, aromatics, such as. B. XyIoI and esters, such as. For example, ethyl and butyl acetate. There are also mixtures of these solvents 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 50 and 250 bar, preferably 75 to 225 bar, more preferably between 75 and 200 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 ^° C., preferably between 150 and 225 ^° C., particularly preferably 175 and 220 ^° 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 operated at sufficiently low resin concentrations completely without additional reactor cooling, wherein the reaction medium completely absorbs the released energy and thereby convective from the reactor leads 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, the recycling of part of the product to the reactor inlet is also suitable (circulation reactor). The reaction product can, as it leaves the reactor, be recycled without further work-up. However, it can also be advantageous to provide an additional work-up step before the recycling, for example the separation of a part of the solvent used. The product can be recycled with the temperature with which It leaves the reactor, but it can also be first cooled to dissipate 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 produced carbonyl-containing, aromatic resin A) can also be carried out batchwise in batch reactors (autoclave). 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, it is preferable 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 will be to remove catalyst residues passed through a filter. The optionally contained solvent can - if desired - then be separated.

Analytical methods

Determination of the content of free formaldehyde

The formaldehyde content is determined after post column derivatization after the lutidine

Method determined by HPLC.

Determination of the hydroxyl number

The determination is made on the basis of DIN 53240-2 "Determination of

Hydroxyl ".

It should be ensured that an acetylation time of 3 h 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 by FT-IR spectroscopy relative to the respectively used alkylaryl ketone (eg acetophenone) in THF in a NaCI cuvette.

Determination of non-volatile content (nfA) Non-volatile content is expressed as the mean of a duplicate determination. Approx. 2 g of the sample are weighed into a cleaned aluminum dish (Taramasse mi) on an analytical balance (mass rri2 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 (m ₃ ).

The nonvolatile fraction (nfA) is calculated according to the following equation: [Dimensions-%]

Determination of color number according to Gardner

The Gardner color number is determined in 50% strength by weight solution of the resin in ethyl acetate on the basis of 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 ^° C. in an air atmosphere (see also determination of the non-volatile content). The Gardner color number is then determined in 50% strength 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 in isopar H 40% by weight. 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 Isopar H, xylene, white spirit and n-hexane are prepared. For this purpose, the resins 10 and 50% dissolved in the respective solvent with stirring and assessed the clarity of the solution visually.

Determination of compatibility with APAO

The resins and an amorphous poly-α-olefin (Vestoplast 750 (Degussa AG)) are dissolved in a ratio of 1: 1 in 50% strength XyIoI with stirring and the clarity of the solution is visually assessed.

Calculation of the copolymer 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 drove the reactor (trickle down). The pressure is kept constant by the addition of hydrogen.

Example C: Reconstitution 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.

Inventive Examples

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: (Attempt HDK1 12 to 13.12.2005)

The resin of Example I) was dissolved in tetrahydrofuran 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 150 bar and 200 ⁰ C were passed 360 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: (Experiment HDK1 13 to 16.02.2005)

The resin of Example I) was dissolved in tetrahydrofuran 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 150 bar and 210 ⁰ C per hour 240 ml_ of the reaction mixture from top to bottom driven through the reactor (trickle). The pressure is kept constant by the addition of hydrogen.

Inventive Example 3: (Experiment HDK1 16 to 19.02.2005)

The resin of Example I) was dissolved in tetrahydrofuran 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 150 bar and 220 ⁰ C per hour of 70 ml_ of the reaction mixture from top to bottom down through the reactor (downflow). The pressure is kept constant by the addition of hydrogen.

The resin solutions of Examples 1 to 3 and Comparative Examples B and C were freed from the solvent in vacuo. The properties of the resulting resins are listed in Table 1. Table 1: Properties of the hydrogenated resins of Examples 1 to 3 and Comparative Examples B and C.

The resins 1 to 3 according to the invention have, in comparison to the non-inventive resins of Examples B and C, a significantly lower 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 3 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 Examples 1 to 3 according to the invention are 10 and 50% by weight completely soluble in isopar H, white spirit, xylene and n-hexane. In contrast, the resins of Comparative Examples B and C are no longer perfectly soluble in isopar H and n-hexane at concentrations of 10 wt% solids. This may possibly be due to the higher levels of aromatics and the low ratio of m / k (in both cases by 1). In addition, the compatibility of the resins of Comparative Examples B and C is limited to amorphous poly-α-olefins, while the resins of Examples 1 to 3 according to the invention are compatible therewith.

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. carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkyl aryl ketones and formaldehyde having a hydroxyl number of 0 to 75 mg KOH / g, with a content of free formaldehyde of less than 3 ppm, which substantially contain the structural elements according to formula II

With

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

Alkylaryl ketone),

R '= H, CH ₂ OH, k = 0 to 6, m = 2 to 18,

I = 0 to 0.35, where the sum of k + I + m is between 2 and 24, the ratio of m / k> 5 and the three structural elements can be distributed alternately or statistically and wherein the structural elements are linked linearly via Chb groups and / or branching via CH groups.

2. Carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde having a hydroxyl number of 0 to 75 mg KOH /, with a content of free formaldehyde of less than 3 ppm, which substantially contain the structural elements according to formula II

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 below 5 mg alkylaryl ketone / g resin (based on the particular used

Alkylaryl ketone),

R '= H, CH ₂ OH, k = 0 to 6, m = 2 to 18,

I = 0 to 0.35, where the sum of k + I + m is between 2 and 24, the ratio of m / k> 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 linked via CH groups branching, 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 50 and 250 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 alkylaryl ketones and formaldehyde according to at least one of the preceding claims, characterized in that 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.

6. 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 hydroxyl number between 0 and 75 mg KOH / g, preferably between 0 and 60 mg KOH / g, more preferably between 0 and 50 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 resin (based on the particular alkylaryl ketone used) lies.

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 .-% strength in ethyl acetate) under 1, 5, preferably less than 1, 0th , 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 .-% strength 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 is between 1.35 and 1.7, more preferably between 1.4 and 1.6.

11. 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% in isopar H, between 1000 and 15000 mPa-s, more preferably between 3000 and 10,000 mPa-s is located.

12. 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 melting point / range between 25 and 150 ⁰ C, preferably between 30 and 125 ⁰ C, particularly preferably between 35 and 100 ⁰ C is located.

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 tempering for 24 h at 150 ⁰ C over 97.0 wt .-%, preferably over 97.5 wt .-% is.

14. 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 solubility of the resins in n-hexane, white spirit and Isopar H 10 and 50th

Wt .-%, 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

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 carbon 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 starting compound for the preparation of the ketone-aldehyde resins.

20. 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 compound for the preparation of the ketone-aldehyde resins

Formaldehyde and / or para-formaldehyde and / or trioxane are used.

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%, more preferably between 0 and

25 mol% based on the aldehyde component used.

22. 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 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 between 1: 0.25 to 1: 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 carbonyl- and ring-hydrogenated ketone-aldehyde resins based on alkylaryl ketones and formaldehyde having a hydroxyl value of 0 to 75 mg KOH / g, with a content of free formaldehyde of less than 3 ppm, which substantially the structural elements of the formula II contain according to at least one of the preceding claims, characterized by

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 50 and 250 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 in that for the preparation of carbonyl-containing ketone-aldehyde A) as basic catalysts hydroxides of the cations NH ₄ , NReSt ₄ , with radical = H, alkyl and / or benzyl, Li or Na, preferably hydroxides of Cations NH ₄ , NReSt ₄ , with radical = H, alkyl and / or benzyl, or Na are used.

27. The method according to at least one of claims 24 to 26, characterized the preparation of the carbonyl group-containing ketone-aldehyde resins A) is carried out 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) in addition 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. A method according to any one of claims 24 to 30, characterized in that for the purification of the base resin A) is washed 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, contained as main metals.

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

Modifying agents included.

37. The method according to claim 36, characterized in that additional doping metals are contained, 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 in 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 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 45, 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 that hydrogen and the resin to be hydrogenated, optionally dissolved in a solvent, is added to the catalyst bed at the top of the reactor.

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.

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 according to the claims in a 50 to 90 wt .-% methanol solution, 0 to 5 mass% 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, Adding 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,

• Shut down the stirrer after stirring for another 0.5 to 5 h

Reflux temperature, wherein after about one third of the runtime an additional 0.1 to 1 mol (or a multiple) of an aqueous formaldehyde solution can optionally 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.