EP2027171A1 - Résines aldéhyde-cétone à carbonyle et coeur hydrogéné sans formaldéhyde à base d'alkylarylcétones et de formaldéhyde avec une fonctionnalité oh faible et son procédé de fabrication - Google Patents

Résines aldéhyde-cétone à carbonyle et coeur hydrogéné sans formaldéhyde à base d'alkylarylcétones et de formaldéhyde avec une fonctionnalité oh faible et son procédé de fabrication

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Publication number
EP2027171A1
EP2027171A1 EP07729095A EP07729095A EP2027171A1 EP 2027171 A1 EP2027171 A1 EP 2027171A1 EP 07729095 A EP07729095 A EP 07729095A EP 07729095 A EP07729095 A EP 07729095A EP 2027171 A1 EP2027171 A1 EP 2027171A1
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EP
European Patent Office
Prior art keywords
ketone
formaldehyde
carbonyl
ring
ketones
Prior art date
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Application number
EP07729095A
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German (de)
English (en)
Inventor
Patrick GLÖCKNER
Christian Lettmann
Michael Ewald
Andreas Wenning
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Evonik Operations GmbH
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Degussa GmbH
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Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP2027171A1 publication Critical patent/EP2027171A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G6/00—Condensation polymers of aldehydes or ketones only
    • C08G6/02—Condensation polymers of aldehydes or ketones only of aldehydes with ketones

Definitions

  • 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.
  • ketones or mixtures of ketones and aldehydes can be converted to resinous products in the presence of basic catalysts or acids.
  • 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.
  • 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.
  • 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 arrangementsbücher, Stuttgart, 1995].
  • the hydrogenated products described therein have a relatively high content of free formaldehyde in common.
  • 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.
  • IARC International Agency for Research on Cancer
  • WHO World Health Organization
  • 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.
  • 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.
  • the proportion of crystallizable compounds should be as low as possible.
  • 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.
  • 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- ⁇ -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
  • 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
  • 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
  • R aromatic with 6 to 14 carbon atoms, cycloaliphatic with 6 to 14
  • 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
  • the properties of the carbonyl- and ring-hydrogenated ketone-aldehyde resins according to the invention all possible variations within o. G. Accept values.
  • 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
  • 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.
  • 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
  • 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.
  • nonpolar solvents As polyethylene, polypropylene, natural resins, copolymers of ⁇ -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.
  • polyethylene, polypropylene, copolymers of ⁇ -olefins, paraffins, waxes, modified waxes such.
  • the proportion of aromatic structural elements is less than 10, preferably less than 5 mg of alkylaryl ketone / g of resin.
  • 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.
  • 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).
  • k in formula II is preferably as high as possible without adversely affecting the desired solubility profile.
  • 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 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.
  • 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 ⁇ -methyl ketones such.
  • acetophenone derivatives of acetophenone such.
  • 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.
  • 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.
  • the ketone component such as.
  • 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.
  • aldehyde 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.
  • 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.
  • 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.
  • 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.
  • at least one phase transfer catalyst can additionally be used, whereby z. B. is possible to reduce the amount of alkali compound.
  • 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.
  • suitable basic catalysts such as alkali compounds.
  • the reaction for producing the base resins of ketone and aldehyde can be carried out by using an auxiliary solvent.
  • 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.
  • the basic catalyst used 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.
  • phase transfer catalysts may optionally be additionally used.
  • phase transfer catalyst 0.01 to 15% by weight, based on the ketone, of a phase transfer catalyst of the general formula (A)
  • 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.
  • 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.
  • anions such strong (on) organic acids such. , Cl “, Br” J ", and also hydroxides, methoxide or acetates.
  • quaternary ammonium salts are cetyldimethylbenzylammonium, methylbenzylammoniumchlorid tributylbenzyl, tri-, Trimethylbenzylammoniumjodid, Triethylbenzyl- ammonium chloride or Triethylbenzylammoniumjodid, tetramethylammonium chloride, tetraethylammonium, tetrabutylammonium.
  • benzyltributylammonium, Cetyldimethylbenzylammoniumchlorid and / or triethylbenzylammonium chloride used.
  • Ri -4 alkyl radicals having 1 to 22 carbon atoms and / or phenyl radicals and / or benzyl radicals.
  • anions such strong (on) organic acids such. B. Cl “ , Br “ , J " but also hydroxides, methoxides or acetates in question.
  • 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.
  • the carbonyl group- and aromatics-containing base resin A) is first prepared.
  • 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.
  • 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.
  • 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.
  • 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.
  • the choice of the hydrogenation conditions simultaneously converts the aromatic structural elements into cycloaliphatic units as completely as possible.
  • 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.
  • 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.
  • 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.
  • those with which the acid-base properties of the catalysts can be influenced such.
  • 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.
  • 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.
  • known in the art preparation steps are necessary, such.
  • other auxiliaries such.
  • 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.
  • 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.
  • concentration of the resin in the solvent can be varied between 1 and 99% by weight, preferably between 10 and 50% by weight.
  • 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.
  • the hydrogenation of the produced carbonyl-containing, aromatic resin A) is preferably carried out with catalysts based on nickel, palladium and / or ruthenium.
  • catalysts based on nickel, palladium and / or ruthenium are particularly suitable for the preparation of the resins of the invention.
  • 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.
  • hydrogen and the resin to be hydrogenated, optionally dissolved in a solvent are added to the catalyst bed at the top of the reactor.
  • 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.
  • the removal of the heat of reaction is preferably realized via an external coolant circuit.
  • 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.
  • 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.
  • 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 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.
  • the catalyst 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.
  • 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.
  • the formaldehyde content is determined after post column derivatization after the lutidine
  • the determination is carried out by FT-IR spectroscopy after calibration with 2-ethylhexanone in THF in a NaCI cuvette.
  • the determination is carried out by FT-IR spectroscopy relative to the respectively used alkylaryl ketone (eg acetophenone) in THF in a NaCI cuvette.
  • alkylaryl ketone eg acetophenone
  • 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-%]
  • 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.
  • the color number after thermal stress is determined in this way.
  • 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.
  • 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).
  • 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).
  • the determination is carried out using a capillary melting point measuring device (Büchi B-545) in accordance with DIN 53181.
  • the resins and an amorphous poly- ⁇ -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.
  • the molecular weight (Mn) is 1000 g / mol
  • the OH number is 150 mg KOH / g
  • the carbonyl number is 10 mg KOH / g.
  • Example A Adjustment of Example 2 of DE 892 975
  • Example B Adjustment of Example 3 of DE 33 34 631 A1
  • Example A 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.
  • Example I 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.
  • Example I 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.
  • Example I 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 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.
  • 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.
  • 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).
  • the compatibility of the resins of Comparative Examples B and C is limited to amorphous poly- ⁇ -olefins, while the resins of Examples 1 to 3 according to the invention are compatible therewith.

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  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne des résines aldéhyde-cétone à carbonyle et coer hydrogéné sans formaldéhyde, à base d'alkylarylcétones et de formaldéhyde avec une fonctionnalité OH faible, une part plus faible de composés cristallisables, une viscosité plus faible, un indice de couleur très faible et une résistance très élevée à la chaleur et à la lumière, ainsi que son procédé de fabrication.
EP07729095A 2006-06-09 2007-05-14 Résines aldéhyde-cétone à carbonyle et coeur hydrogéné sans formaldéhyde à base d'alkylarylcétones et de formaldéhyde avec une fonctionnalité oh faible et son procédé de fabrication Withdrawn EP2027171A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006026758A DE102006026758A1 (de) 2006-06-09 2006-06-09 Formaldehydfreie, carbonyl- und kernhydrierte Keton-Aldehydharze auf Basis von Alkylarylketonen und Formaldehyd mit geringer OH-Funktionalität und ein Verfahren zu ihrer Herstellung
PCT/EP2007/054643 WO2007141114A1 (fr) 2006-06-09 2007-05-14 Résines aldéhyde-cétone à carbonyle et cœur hydrogéné sans formaldéhyde à base d'alkylarylcétones et de formaldéhyde avec une fonctionnalité oh faible et son procédé de fabrication

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EP2027171A1 true EP2027171A1 (fr) 2009-02-25

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EP07729095A Withdrawn EP2027171A1 (fr) 2006-06-09 2007-05-14 Résines aldéhyde-cétone à carbonyle et coeur hydrogéné sans formaldéhyde à base d'alkylarylcétones et de formaldéhyde avec une fonctionnalité oh faible et son procédé de fabrication

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US (1) US20090198024A1 (fr)
EP (1) EP2027171A1 (fr)
JP (1) JP2009540027A (fr)
CN (1) CN101085824A (fr)
DE (1) DE102006026758A1 (fr)
WO (1) WO2007141114A1 (fr)

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DE102014203231A1 (de) 2014-02-24 2015-08-27 Evonik Degussa Gmbh Dispergierharze für Pigmentpräparationen mit geringem flüchtigem organischem Anteil
EP3075788A1 (fr) 2015-04-02 2016-10-05 Evonik Degussa GmbH Résines de condensation de cétone-aldéhydes fonctionnalisées
US10287448B2 (en) 2016-07-08 2019-05-14 Evonik Degussa Gmbh Universal pigment preparation

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Publication number Priority date Publication date Assignee Title
DE870022C (de) * 1944-07-16 1953-03-09 Chemische Werke Huels Ges Mit Verfahren zur Herstellung von Harzen
DE826974C (de) * 1951-11-29 1952-01-07 Chemische Werke Huels G M B H Verfahren zur kontinuierlichen Hydrierung von Harzen aus fettaromatischen Ketonen und Formaldehyd
DE3334631A1 (de) * 1982-11-11 1984-05-17 Chemische Werke Hüls AG, 4370 Marl Benzinloesliche, hydrierte alkylarylketon/formaldehyd-harze sowie deren herstellung
DE3324287A1 (de) * 1983-07-06 1985-01-17 Chemische Werke Hüls AG, 4370 Marl Kondensationsharze auf basis von alkylarylketonen und formaldehyd
DE10338559A1 (de) * 2003-08-22 2005-04-14 Degussa Ag Verfahren zur Herstellung von Keton-Formaldehydharzen
DE10338560A1 (de) * 2003-08-22 2005-03-17 Degussa Ag Strahlenhärtbare Harze auf Basis hydrierter Keton- und Phenol-Aldehydharze und ein Verfahren zu ihrer Herstellung
DE10338561A1 (de) * 2003-08-22 2005-04-14 Degussa Ag Keton-Aldehydharze, insbesondere Cyclohexanon-Formaldehydharze mit geringem Wassergehalt und hoher thermischer Bestätigkeit und Vergilbungsbeständigkeit sowie ein Verfahren zur Herstellung und Verwendung
DE102004005208A1 (de) * 2004-02-03 2005-08-11 Degussa Ag Verwendung strahlenhärtbarer Harze auf Basis hydrierter Keton- und Phenol-Aldehydharze
DE102004005207A1 (de) * 2004-02-03 2005-08-11 Degussa Ag Verwendung strahlenhärtbarer Harze auf Basis von Keton- und/oder Harnstoff-Aldehydharzen
DE102004020740A1 (de) * 2004-04-27 2005-11-24 Degussa Ag Polymerzusammensetzungen von carbonylhydrierten Keton-Aldehydharzen und Polylsocyanaten in reaktiven Lösemitteln
DE102004039083A1 (de) * 2004-08-12 2006-02-23 Degussa Ag Zinnfreie, hochschmelzende Reaktionsprodukte aus carbonylhydrierten Keton-Aldehydharzen, hydrierten Ketonharzen sowie carbonyl- und kernhydrierten Keton-Aldehydharzen auf Basis von aromatischen Ketonen und Polyisocyanten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007141114A1 *

Also Published As

Publication number Publication date
CN101085824A (zh) 2007-12-12
WO2007141114A1 (fr) 2007-12-13
JP2009540027A (ja) 2009-11-19
US20090198024A1 (en) 2009-08-06
DE102006026758A1 (de) 2008-01-10

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