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WO2007099038A1 - Résines céto-aldéhydiques sans formaldéhyde à carbonyle hydrogéné, à base de cétones biréactives et de formaldéhyde et procédé de production desdites résines - Google Patents

Résines céto-aldéhydiques sans formaldéhyde à carbonyle hydrogéné, à base de cétones biréactives et de formaldéhyde et procédé de production desdites résines Download PDF

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Publication number
WO2007099038A1
WO2007099038A1 PCT/EP2007/051465 EP2007051465W WO2007099038A1 WO 2007099038 A1 WO2007099038 A1 WO 2007099038A1 EP 2007051465 W EP2007051465 W EP 2007051465W WO 2007099038 A1 WO2007099038 A1 WO 2007099038A1
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Prior art keywords
ketone
carbonyl
aldehyde resins
preparation
formaldehyde
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PCT/EP2007/051465
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German (de)
English (en)
Inventor
Patrick GLÖCKNER
Andreas Wenning
Christian Lettmann
Peter Denkinger
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Evonik Operations GmbH
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Evonik Degussa GmbH
Degussa GmbH
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Publication of WO2007099038A1 publication Critical patent/WO2007099038A1/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-hydrogenated ketone-aldehyde resins based on bi-reactive ketones and formaldehyde with a 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 1 15 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].
  • Formaldehyde can cause health problems. However, an exact classification is not yet made.
  • IARC International Agency for Research on Cancer
  • WHO World Health Organization
  • formaldehyde-free products is indispensable in the sense of "sustainable development” and "responsible handling of chemical substances".
  • 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.
  • this object could be achieved according to the claims by using specially prepared ketone-aldehyde resins based on bi-reactive ketones and formaldehyde in the presence of catalysts which selectively hydrogenate on the one hand, the carbonyl groups of the resins, on the other hand reduce the free formaldehyde, with hydrogen Be brought reaction. It has been shown that a particularly low number of carbonyl groups is particularly advantageous.
  • the carbonyl-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 crystallizable compounds and are virtually free of formaldehyde.
  • the solution viscosity in contrast to the prior art, is low despite the high melting range and can be realized through the use of custom-made Starting resins for the hydrogenation, which have a particularly narrow molecular weight distribution.
  • the invention relates to carbonyl-hydrogenated ketone-aldehyde resins based on reactive ketones and formaldehyde, with a content of free formaldehyde of less than 3 ppm, which essentially contain the structural elements according to formula II,
  • R ' H, aliphatic hydrocarbon radical having 1 to 12 carbon atoms, CH 2 OH,
  • R 1 , R 2 H, aliphatic and / or cycloaliphatic hydrocarbon radical with 1 to
  • the invention relates to carbonyl-hydrogenated ketone-aldehyde resins based on reactive ketones and formaldehyde, with a content of free formaldehyde of less than 3 ppm, which essentially contain the structural elements according to formula II,
  • R ' H, aliphatic hydrocarbon radical having 1 to 12 carbon atoms, CH 2 OH,
  • R 1 , R 2 H, aliphatic and / or cycloaliphatic hydrocarbon radical with 1 to
  • Catalyst and optionally at least one phase transfer catalyst, solvent-free or using a water-miscible organic solvent optionally at least one phase transfer catalyst, solvent-free or using a water-miscible organic solvent
  • Solvent with hydrogen in the presence of a catalyst at pressures between 50 and 350 bar, preferably between 100 and 300 bar, especially preferably between 150 and 300 bar and temperatures between 40 and 140 ° C, preferably between 50 and 140 ° C.
  • a preferred subject of the invention are carbonyl-hydrogenated ketone-aldehyde resins based on bi-reactive ketones and formaldehyde, having a content of free formaldehyde of less than 3 ppm, 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, the content of crystallizable compounds less than 5% by weight, preferably less than 2.5% by weight, particularly preferred is less than 1% by weight,
  • the carbonyl number is between 0 and 100 mg KOH / g, preferably between 0 and 50 mg KOH / g, more preferably between 0 and 25 mg KOH / g,
  • the hydroxyl number is between 0 and 450 mg KOH / g, preferably between 10 and 400 mg KOH / g, more preferably between 20 and 350 mg KOH / g,
  • the Gardner color number (50% in ethyl acetate) is less than 1.5, preferably less than 1.0, more preferably less than 0.75,
  • Gardner color number (50% in ethyl acetate) after thermal loading of the resin (24 h, 150 ° C.) is below 2.0, preferably below 1.5, particularly preferably below 1.0,
  • the polydispersity (Mw / Mn) of the resins is between 1, 35 and 2.0, more preferably between 1, 4 and 1, 9,
  • the solution viscosity, 40% in phenoxyethanol is between 3000 and 14000 mPa.s, more preferably between 4000 and 10000 mPa.s, the melting point / range is between 40 and 150.degree. C., preferably between 50 and 140.degree. more preferably between 60 and 130 ° C and
  • the invention also provides a process for the preparation of carbonyl-hydrogenated ketone-aldehyde resins based on bi-reactive ketones and formaldehyde, having a content of free formaldehyde of less than 3 ppm, which essentially contain the structural elements according to formula II, marked by
  • Typical end groups of the resins are, for example, H, CH 2 OH, CH 3 . In ⁇ -position to the carbonyl group also CH 2 OH groups may be present.
  • cyclic ketones used such as. As cyclohexanone, the carbonyl group is always part of the polymer backbone.
  • linear, birezine ketones such as acetone or 2-butanone, the keto group may be located within the main chain or in the side chain.
  • 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 carbonyl number of the products according to the invention is between 0 and 100 mg KOH / g, preferably between 0 and 50 mg KOH / g, more preferably between 0 and 25 mg KOH / g, so that the Gardner color number (50% 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% in ethyl acetate) after thermal loading of the products of the invention (24 h, 150 ° C) below 2.0, preferably less than 1, 5, more preferably less than 1, 0.
  • the solution viscosity of the products according to the invention is 40% in phenoxyethanol, between 3000 and 14000 mPa.s, more preferably between 4000 and 10000 mPa.s.
  • the resins according to the invention have polydispersities (Mw / Mn) between 1.35 and 2.0, more preferably between 1.4 and 1.9.
  • 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 the molecular weight the higher the solution viscosity. Therefore, it has been desired to raise the melting point / range without increasing the molecular weight. This could be achieved, in which k always prevails in formula II and is preferably chosen as high as possible.
  • the value of k is 1 to 15, preferably 2 to 12, more preferably 3 to 12.
  • the resins of the invention have melting points / ranges between 40 and 150 ° C, preferably between 50 and 140 ° C, more preferably between 60 and 130 ° C.
  • solubility properties can be adjusted by the ratio of k, I and m.
  • k is chosen such that the hydroxyl number is between 0 and 450 mg KOH / g, preferably between 10 and 400 mg KOH / g, more preferably between 20 and 350 mg KOH / g.
  • the values for k, I and m as well as their sum can be whole numbers (eg 2) but also intermediate values, such as 2. B. 2.6, assume.
  • Suitable ketones for the preparation of the carbonyl-hydrogenated ketone-aldehyde resins based on formaldehyde are all ketones, in particular all bi-reactive ketones which have a reaction possibility both in the ⁇ -position and in the ⁇ '-position to the carbonyl group, such as acetone, Methyl ethyl ketone, heptanone-2, pentanone-3, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-thmethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals, the total 1 to 12 carbon atoms, individually or in mixture.
  • alkyl-substituted cyclohexanones there may be mentioned 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-thymethylcyclohexanone.
  • ketones are contained in the resins of the invention from 70 to 100 mol%.
  • CH-acidic ketones can be used on a subordinate scale mixed with the abovementioned ketones up to 30 mol%, preferably up to 15 mol%, based on the ketone component, which have no possibility of reacting in the ⁇ '-position to the carbonyl group or have only a low reactivity such.
  • acetophenone derivatives of acetophenone such.
  • hydroxyacetophenone alkyl-substituted acetophenone derivatives having 1 to 8 carbon atoms on the phenyl ring, methoxyacetophenone, propiophenone, 3,3-dimethylbutanone and / or methyl isobutyl ketone.
  • ketones usually all CH-acidic ketones.
  • aldehyde component of the carbonyl-hydrogenated ketone-aldehyde resins based on formaldehyde are in principle unsubstituted or branched aldehydes, such as formaldehyde and z.
  • acetaldehyde n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde and dodecanal.
  • all the aldehydes mentioned in the literature as suitable for ketone resin syntheses can be used.
  • formaldehyde is used alone or in mixtures with other aldehydes.
  • the further aldehydes can then 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 forms of formaldehyde are formaldehyde donating compounds such. For example, para-formaldehyde and / or trioxane.
  • 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 carbonyl group-containing base resins A) For the preparation of the carbonyl group-containing base resins A) is the particular ketone or a mixture of different ketones with formaldehyde or a mixture of formaldehyde and additional aldehydes in the presence of at least one basic Catalyst reacted.
  • formaldehyde when using formaldehyde as an aqueous solution and ketones whose water solubility is limited, water-soluble organic solvents can be used advantageously. Because of the better phase mixing associated therewith, the reaction conversion is then faster and more complete.
  • at least one phase transfer catalyst can additionally be used, whereby z. For example, it is possible to reduce the amount of basic 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 compounds such as alkali compounds are used.
  • hydroxides of the cations NH 4 , NR 4 , Li, Na are particularly preferred.
  • 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. As all organic and / or inorganic acids suitable. 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.
  • 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. B. Cl “ , Br “ , J " but also
  • quaternary ammonium salts are cetyldimethylbenzylammonium chloride, tributylbenzylammonium chloride, th-methylbenzylammonium chloride, trimethylbenzylammonium iodide, triethylbenzylammonium chloride or thethylbenzylammonium iodide, tetramethylammonium chloride,
  • Tetraethylammonium chloride Tetrabutylammonium chloride.
  • Benzyltributylammoniumchlorid 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-containing base resin A) is first prepared.
  • 10 mol of ketone in a 50 to 90% strength methanolic solution, 0 to 5% by mass of a phase transfer catalyst and 0.1 to 5 mol of an aqueous formaldehyde solution are introduced and homogenized with stirring.
  • the stirrer is stopped after further 0.5 to 5 h stirring at reflux temperature.
  • an aqueous formaldehyde solution may be added.
  • the pH is kept above 10 by the addition of sodium hydroxide solution over 10.
  • 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 carbonyl group-containing base resin A) is first prepared.
  • 1 to 4 mol of ketone and 0.5 to 8 mol of formaldehyde solution are introduced and heated to 40 to 80 ° C.
  • the reaction is initiated by the addition of 0.1 to 2.0 moles of sodium hydroxide solution.
  • 1 to 4 mol of ketone and 0.5 to 10 mol of formaldehyde solution are added.
  • the stirrer is stopped after further 0.5 to 7 h stirring at reflux temperature. After separation of the phases, the aqueous phase is separated off. 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 group of the ketone-aldehyde resin is converted into a secondary hydroxy group.
  • a part of the hydroxy 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.
  • n k + 1 + m
  • catalysts in principle all compounds can be used which catalyze the hydrogenation of carbonyl groups and the hydrogenation of free formaldehyde to methanol with hydrogen. It can be homogeneous or heterogeneous Catalysts are used, particularly preferred are heterogeneous catalysts.
  • 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, copper-chromium and 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 used solvent additional Purification steps for complete or partial removal of light or less volatile by-products, such.
  • methanol and water may be necessary.
  • 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%, preferably between 10 and 50%.
  • the total pressure in the reactor is between 50 and 350 bar, preferably 100 to 300 bar.
  • the optimum hydrogenation temperature depends on the hydrogenation catalyst used. Thus, for rhodium catalysts already temperatures of 40 to 75 ° C, preferably from 40 to 60 ° C is sufficient, whereas with Cu or Cu / Cr catalysts higher temperatures are necessary, which are typically between 100 and 140 ° 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 formaldehyde content is determined after post-column dehumidification by the lutidine method by means of HPLC.
  • non-volatile fraction is given as the mean value of a duplicate determination.
  • a cleaned aluminum dish (Taramasse mi) are weighed on an analytical balance about 2 g of the sample (mass ⁇ m 2 of the substance). Subsequently, the aluminum dish is placed for 24 h at 150 ° 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:
  • nfa m3 ⁇ mi - 100 [mass%] m 2
  • the Gardner color number is determined in 50% strength solution of the resin in ethyl acetate on the basis of DIN ISO 4630. Also, the color number after thermal exposure is determined in this way. For this purpose, the resin is first stored for 24 hours 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 solution of the thermally loaded resin in ethyl acetate on the basis of DIN ISO 4630.
  • the resin is dissolved 40% in phenoxyethanol.
  • the viscosity is measured at 20 ° C using a plate / cone rotation viscometer (1 / 40s).
  • 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
  • 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.
  • R is H
  • the non-hydrogenated base resin has an OH number of 0 mg KOH / g
  • the molecular weight (Mn) is 1000 g / mol
  • the OH number is 300 mg KOH / g
  • the carbonyl number is 10 mg KOH /G.
  • the synthesis of the resin is carried out by 1030 g of cyclohexanone, 210 g of an approximately 30% formaldehyde solution, 280 ml of methanol and 3.8 g Benzyltributyl- ammonium chloride in a three-necked flask with stirrer, reflux condenser and thermosensor are placed in a nitrogen atmosphere.
  • the reaction is initiated by the addition of 8.7 g of a 25% sodium hydroxide solution. By cooling the temperature of the mixture is kept below 60 ° C. Then, within 100 min, 1350 g of an approximately 30% strength formaldehyde solution and then 25.2 g of a 25% sodium hydroxide solution are added. After stirring under reflux, 100 g of an approx.
  • the synthesis of the resin is carried out by adding 267 ml of 2-butanone and 570 ml of an approx.
  • the reaction is initiated by the addition of 96 g of a 25% sodium hydroxide solution. Then, within 120 minutes, 267 ml of 2-butanone and 570 ml of an approximately 30% strength formaldehyde solution are added.
  • a yellowish, clear and brittle resin which is 10% soluble in ethanol, methyl ethyl ketone, acetone and ethyl acetate and has a melting point of 108 ° C. is obtained.
  • Example 2 300 g of the resin from Example I) are dissolved in 700 g of tetrahydrofuran (water content about 7%). Then, the hydrogenation is carried out at 260 bar and 120 ° C in an autoclave (Parr) with a catalyst basket, which is filled with 100 ml_ of a commercially available Ru catalyst (3% Ru on alumina). After 15 hours, the reaction mixture is drained from the reactor via a filter.
  • Example I The resin of Example I was dissolved in 30% i-butanol with heating.
  • the hydrogenation takes place in a continuously operated fixed bed reactor which is filled with 400 ml of a commercially available, silicon-supported copper-chromium contact. At 300 bar and 130 ° C 500 ml_ of the reaction mixture is driven hourly from top to bottom through the reactor (trickle). The pressure is kept constant by the addition of hydrogen.
  • Example 4 The resin from Example I) was dissolved by heating at 30% in i-butanol. The hydrogenation takes place in a continuously operated fixed bed reactor which is filled with 400 ml of a commercially available, Raney-type nickel catalyst. At 300 bar and 130 ° C., 400 ml of the reaction mixture are passed through the reactor from top to bottom every hour (trickle-free operation). The pressure is kept constant by the addition of hydrogen.
  • All resins are soluble in common paint solvents.
  • the resins are soluble in ethanol, dichloromethane, ethyl acetate, butyl acetate, isopropanol and acetone.
  • Comparative Example A is partially soluble in water, resulting in poor water resistance in paint films.
  • Comparative Example A has a high formaldehyde content and, in spite of the low melting point, a very high viscosity.
  • the color number is relatively high and increases significantly due to thermal stress.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne des résines céto-aldéhydiques sans formaldéhyde à carbonyle hydrogéné, à base de cétones biréactives et de formaldéhyde à faible teneur en composés cristallisables, de faible viscosité, à très faible indice de coloration et présentant une résistance à la chaleur et à la lumière très élevée. L'invention concerne également un procédé de production desdites résines.
PCT/EP2007/051465 2006-02-28 2007-02-15 Résines céto-aldéhydiques sans formaldéhyde à carbonyle hydrogéné, à base de cétones biréactives et de formaldéhyde et procédé de production desdites résines Ceased WO2007099038A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200610009080 DE102006009080A1 (de) 2006-02-28 2006-02-28 Formaldehydfreie, carbonylhydrierte Keton-Aldehydharze auf Basis bi-reaktiver Ketone und Formaldehyd und ein Verfahren zu ihrer Herstellung
DE102006009080.2 2006-02-28

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WO2007099038A1 true WO2007099038A1 (fr) 2007-09-07

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
US7700664B2 (en) 2004-04-27 2010-04-20 Degussa Ag Polymer compositions of carbonyl-hydrated ketone-aldehyde resins and polyisocyanates in reactive solvents
WO2021169015A1 (fr) * 2020-02-28 2021-09-02 宁波工程学院 Procédé de catalyse d'hydrogénation de résine en c9
GB2595369A (en) * 2020-02-28 2021-11-24 Univ Ningbo Technology Method for hydrogenation catalysis of C9 resin

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DE102007018812A1 (de) 2007-04-20 2008-10-23 Evonik Goldschmidt Gmbh Polyether enthaltende Dispergier- und Emulgierharze
CN116515061A (zh) * 2023-05-10 2023-08-01 滁州市润达溶剂有限公司 一种高软化点的醛酮树脂的制备方法及其应用
CN116925304A (zh) * 2023-07-26 2023-10-24 岳阳和盛新材料有限公司 一种氢化酮醛树脂的制备方法
CN117986902B (zh) * 2024-01-11 2024-07-26 佛山市中瑞工业材料有限公司 一种长效抗菌抗病毒除醛粉及其制备方法

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EP0133451A1 (fr) * 1983-07-06 1985-02-27 Hüls Aktiengesellschaft Résines de condensation basées sur alkylarylcétones et formaldéhyde
JPH1112338A (ja) * 1997-06-19 1999-01-19 Arakawa Chem Ind Co Ltd ポリアルコール樹脂の製造法

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