EP2249982B1 - Utilisation de diesters ramifiés d'acide carboxylique d'alcanediol dans des liants de fonderie à base de polyuréthane - Google Patents

Utilisation de diesters ramifiés d'acide carboxylique d'alcanediol dans des liants de fonderie à base de polyuréthane Download PDF

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EP2249982B1
EP2249982B1 EP09706370A EP09706370A EP2249982B1 EP 2249982 B1 EP2249982 B1 EP 2249982B1 EP 09706370 A EP09706370 A EP 09706370A EP 09706370 A EP09706370 A EP 09706370A EP 2249982 B1 EP2249982 B1 EP 2249982B1
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material mixture
component
moulding material
binder system
weight
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EP2249982A2 (fr
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Christian Priebe
Dieter Koch
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ASK Chemicals GmbH
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ASK Chemicals GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/2273—Polyurethanes; Polyisocyanates

Definitions

  • the invention relates to a molding material mixture for the production of moldings for the foundry industry, a method for producing a casting mold using the molding material mixture, a casting mold, and the use of the casting mold for metal casting.
  • Molds for the production of metal bodies are essentially produced in two embodiments.
  • a first group are the so-called nuclei and forms. From these, the mold is assembled, which is essentially a negative mold of the casting to be produced, wherein cores serve to form cavities in the interior of the casting, while the molds depict the outer boundary. Often, the inner cavities are imaged by cores, while the outer contour of the casting is represented by a green sand mold or a steel mold.
  • a second group form hollow bodies, so-called feeders, which act as balancing reservoir. These take up liquid metal, whereby appropriate measures are taken to ensure that the metal remains in the liquid phase longer than the metal that is in the negative mold forming mold. If the metal solidifies in the negative mold, liquid metal can flow out of the compensation reservoir to compensate for the volume contraction that occurs when the metal solidifies.
  • Casting molds are made of a refractory material, such as quartz sand, whose grains are connected after molding of the mold by a suitable binder to ensure sufficient mechanical strength of the mold.
  • a refractory molding material which is mixed with a suitable binder.
  • the molding material mixture obtained from molding material and binder is preferably present in a free-flowing form, so that it can be filled into a suitable mold and compacted there.
  • the binder produces a firm cohesion between the particles of the molding base material, so that the casting mold obtains the required mechanical stability.
  • both organic and inorganic binders can be used, the curing of which can be effected by cold or hot processes.
  • Cold processes are processes which are carried out essentially at room temperature without heating the molding material mixture.
  • the curing is usually carried out by a chemical reaction, which can be triggered, for example, by passing a gaseous catalyst through the molding material mixture to be cured, or by adding a liquid catalyst to the molding material mixture.
  • hot processes the molding material mixture after molding on a heated sufficiently high temperature, for example, to drive off the solvent contained in the binder, or to initiate a chemical reaction by which the binder is cured by crosslinking.
  • organic binders e.g. Polyurethane, furan resin or epoxy-acrylate binders used in which the curing of the binder is carried out by adding a catalyst.
  • Polyurethanes based on polyurethanes are generally composed of two components, a first component containing a phenolic resin and a second component containing a polyisocyanate. These two components are mixed with the molding base material and the molding mixture is brought into a mold by ramming, blowing, shooting or another method, compacted and then cured.
  • a distinction is made between the "polyurethane no-bake process" and the "polyurethane cold-box process”.
  • a liquid catalyst generally a liquid tertiary amine
  • phenolic resin, polyisocyanate and curing catalyst are mixed with the refractory molding material.
  • the molding base material is first coated with one component of the binder, and then the other component is added.
  • the curing catalyst is added to one of the components.
  • the ready-made molding material mixture must have a sufficiently long processing time, so that the molding material mixture can be plastically deformed for a sufficient time and processed into a molding.
  • the polymerization must be correspondingly slow run so that not already in the storage tanks or supply lines hardening of the molding material mixture.
  • the curing should not be too slow to achieve a sufficiently high throughput in the production of molds.
  • the processing time can be influenced for example by adding retarders, which slow down the curing of the molding material mixture.
  • a suitable retarder is, for example, phosphorus oxychloride.
  • the molding material mixture is first brought into a mold without catalyst.
  • a gaseous tertiary amine is then passed, which may optionally be mixed with an inert carrier gas.
  • the binder binds very quickly, so that a high throughput in the production of molds is achieved.
  • a binder composition comprising a mixture of a resin component, a curing component and a curing agent.
  • the resin component comprises a phenolic resin obtained by condensing a phenol and an aldehyde.
  • the phenolic resin is dissolved in an organic solvent.
  • the curing component comprises a liquid polyisocyanate having at least two isocyanate groups.
  • the binder comprises a tertiary amine.
  • the gaseous curing agent is passed through this.
  • Suitable curing agents are, for example, trimethylamine, dimethylethylamine, dimethylisopropylamine or triethylamine.
  • the tertiary amine can be heated. After curing, the mold can be removed from the mold.
  • a resin composition comprising a phenol resin component dissolved in organic solvents, a curing agent component, and a curing catalyst.
  • the hardener component used is a liquid polyisocyanate comprising at least two isocyanate groups.
  • the polyisocyanate is used in an amount of 10 to 15 wt .-%, based on the weight of the resin.
  • a base having a pK b in the range of about 7 to about 11 and used in an amount of 0.01 to 10% by weight based on the resin is used.
  • a binder comprising a polyhydroxy component, an isocyanate component and a catalyst for the reaction between said components.
  • the polyhydroxy component is dissolved in a liquid ester of an aliphatic alkoxycarboxylic acid.
  • Example 6 describes a binder which contains, as solvent for the resin, an aromatic solvent in a proportion of 19% by weight, ethyl 3-ethoxypropionate in an amount of 15% by weight, "Red Oil” in an amount of 1 wt .-%, and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB) in a proportion of 5 wt .-%.
  • a polyurethane-based foundry binder is described containing a biphenyl additive.
  • the solvent used is 17% by weight of aromatic solvent and 10% by weight of biphenyl which has been substituted twice or three times.
  • a polyurethane-based foundry binder which contains an epoxy resin and preferably a paraffin oil.
  • a binder system is used, which contains 2 wt .-% of 2, 2, 4-trimethyl-1, 3-pentanediol diisobutyrate as a plasticizer.
  • the solvents used are aromatic hydrocarbons.
  • Example 1 describes a binder system in which the phenolic resin component contains DBE (dibasic ester) and C 6 -C 10 -dialkyl adipate as solvent. As a further component, the phenolic resin component contains 2% by weight of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate. The isocyanate component contains 8.8% by weight of aromatic solvent and 6.2% by weight of petroleum ether as solvent.
  • Example 2 describes a binder system based on polyurethanes, which contains a phosphorus halide as an essential component.
  • Example 2 describes a binder system whose phenolic resin component contains 10% by weight of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate in addition to 27% by weight of aromatic solvent.
  • the phenolic resin component contains linseed oil or polymerized linseed oil.
  • the isocyanate component also contains aromatic solvents.
  • a binder system based on polyurethanes in which the polyisocyanate component has been modified by reaction with an aliphatic alcohol having at least one active hydrogen atom.
  • aliphatic solvents can be used for the isocyanate component.
  • the components are diluted with solvents.
  • solvents usually aromatic solvents are used, which, however, may have a harmful effect.
  • the binder decomposes under the action of heat of the liquid metal. When pouring therefore occurs a strong smoke smoke.
  • the exhaust gases produced during casting must therefore be removed by a complex venting and worked up in order to comply with environmental and occupational safety regulations.
  • the phenolic resin component or the polyisocyanate component comprises a fatty acid ester esterified with an alcohol having a high carbon number. Particular preference is given to using fatty acid butyl esters and fatty acid octyl or fatty acid decyl esters.
  • the phenolic resin component comprises an alkoxy-modified phenolic resin in which less than 25 mole percent of the hydroxymethanol groups are etherified by a primary or secondary aliphatic monoalcohol of from 1 to 10 carbon atoms. Of the Solvent content of the phenolic resin component is at most 40% by weight.
  • the US 4,311,631 A and the US Pat. No. 6,509,392 B1 disclose polyurethane-containing molding material mixtures for the production of moldings for the foundry industry, which make it their mission to use very low solvent amounts. Branched Alkandioldiester but do not use this.
  • the US 2004/176491 A1 discloses the use of diesters, but not in molding compounds formable into moldings for the foundry industry containing refractories, but in polyurethane compositions, including foams, for soil consolidation for building purposes which are applied by injection of the polyurethane compositions into the soil.
  • the smoke and smoke during casting can be significantly reduced. Nevertheless, there is a constant search for further possibilities to further reduce emissions during casting.
  • the components of the binder can be changed so that they lead to a lower smoke development.
  • the binder may be modified to have a higher bonding power, i. the proportion of the binder in the molding material mixture can be reduced.
  • the invention therefore an object of the invention to provide a molding material for the production of moldings for the foundry industry, which allows the use of small amounts of binder, the production of moldings, which have a sufficiently high strength, even in a technical production safely and without Damage to be handled.
  • carboxylic acid diesters of a branched alkanediol have both a good compatibility with the polyisocyanate component and with the polyol component, so that the components of the Sindeffenelsystems can be dissolved in a relatively small amount of solvent.
  • Aromatic solvents are to be understood as meaning aromatic hydrocarbons, such as toluene, xylene and, in particular, high-boiling aromatic hydrocarbons having a boiling point of more than 150.degree.
  • the inventors assume that the carboxylic acid diesters of branched alkanediols used in the binder system of the molding material mixture according to the invention, due to their oxygen content and their non-aromatic character, have a significantly lower tendency to smoke and smoke compared to aromatic solvents.
  • the moldings produced and cured therefrom have a high mechanical stability. This means in a technical application that the proportion of the binder in the molding material mixture can be lowered, and yet the desired strength of the molding remains. By reducing the for sufficient mechanical Stability of the mold required amount of binder, the smoke and smoke during casting can be further reduced.
  • the polyurethane-based binder system comprises at least 3% by weight of a carboxylic acid diester of a branched alkanediol and less than 10% by weight of aromatic solvent, based in each case on the binder system.
  • refractory materials which are customary for the production of moldings for the foundry industry can be used as the refractory molding base material per se.
  • suitable refractory mold bases are quartz sand, zircon sand, olivine sand, aluminum silicate sand and chrome ore sand or mixtures thereof.
  • quartz sand is used.
  • the refractory base molding material should have a sufficient particle size so that the molded article produced from the molding material mixture has a sufficiently high porosity to allow escape of volatile compounds during the casting process.
  • at least 70 wt .-%, more preferably at least 80% by weight of the refractory base molding material has a particle size ⁇ 290 ⁇ m.
  • the average particle size of the refractory base molding material should preferably be between 100 and 350 ⁇ m. The particle size can be determined, for example, by sieve analysis.
  • the molding material mixture according to the invention further contains a binder system based on polyurethane, for whose binder components per se can also be used on known binder systems.
  • the binder system initially contains a polyol component and a polyisocyanate component, in which case known components can likewise be used.
  • the polyisocyanate component of the binder system may comprise an aliphatic, cycloaliphatic or aromatic isocyanate.
  • the polyisocyanate preferably contains at least 2 isocyanate groups, preferably 2 to 5 isocyanate groups per molecule.
  • mixtures of isocyanates can consist of mixtures of monomers, oligomers and polymers and are therefore referred to below as polyisocyanates.
  • the polyisocyanate component per se can be any polyisocyanate which is customary in polyurethane binders for molding mixtures for the foundry industry.
  • Suitable polyisocyanates include aliphatic polyisocyanates, eg, hexamethylene diisocyanate, alicyclic polyisocyanates, such as 4,4'-dicyclohexylmethane diisocyanate, and dimethyl derivatives thereof.
  • aromatic polyisocyanates examples include toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and methyl derivatives thereof, Diphenylmethane-4,4'-diisocyanate and polymethylene-polyphenyl-polyisocyanate.
  • aromatic polyisocyanates more preferably polymethylene-polyphenyl polyisocyanate, e.g. commercially available mixtures of diphenylmethane-4,4'-diisocyanate, its isomers and higher homologs.
  • the polyisocyanates can be used both in substance and dissolved in an inert or reactive solvent.
  • a reactive solvent is understood to mean a solvent which has a reactive group, so that it is incorporated into the framework of the binder when the binder is set.
  • the polyisocyanates are preferably used in dilute form, in order to be able to coat the grains of the refractory molding base material better with a thin film of the binder because of the lower viscosity of the solution.
  • the polyisocyanates or their solutions in organic solvents are used in sufficient concentration to effect the curing of the polyol component, usually in a range of from 10 to 500 weight percent, based on the weight of the polyol component. From 20 to 300% by weight, based on the same base, are preferably used.
  • Liquid polyisocyanates can be used in undiluted form while solid or viscous polyisocyanates are dissolved in organic solvents. Up to 80 wt .-%, preferably up to 60 wt .-%, particularly preferably up to 40 wt .-% of the isocyanate component may consist of solvents.
  • the polyisocyanate is used in an amount such that the number of isocyanate groups is 80 to 120%, based on the number of free hydroxyl groups of the polyol component.
  • polyol component all polyols used in polyurethane binders can be used per se.
  • the polyol component contains at least 2 hydroxyl groups, which can react with the isocyanate groups of the polyisocyanate component in order to achieve cross-linking of the binder during curing, and thereby better strength of the cured molding.
  • the polyols used are preferably phenolic resins which are obtained by condensation of phenols with aldehydes, preferably formaldehyde, in the liquid phase at temperatures up to about 180 ° C. in the presence of catalytic amounts of metal.
  • aldehydes preferably formaldehyde
  • the processes for the preparation of such phenolic resins are known per se.
  • the polyol component is preferably used liquid or dissolved in organic solvents in order to allow a homogeneous distribution of the binder on the refractory base molding material.
  • the polyol component is preferably used in anhydrous form because the reaction of the isocyanate component with water is an undesirable side reaction.
  • Non-aqueous or anhydrous in this context means a water content of the polyol component of preferably less than 5 wt .-%, preferably less than 2 wt .-%, mean.
  • phenolic resin is meant the reaction product of phenol, phenol derivatives, bisphenols, and higher phenol condensation products with an aldehyde.
  • the composition of the phenolic resin depends on the specific starting materials selected, the ratio of the starting materials and the reaction conditions. For example, play the type of catalyst, the time and the reaction temperature, as well as the presence of solvents and other substances.
  • the phenolic resin is typically present as a mixture of different compounds and can be in very different proportions Addition products, condensation products and unreacted starting compounds, such as phenols, bisphenol and / or aldehyde.
  • addition product is meant reaction products in which an organic component substitutes at least one hydrogen on a previously unsubstituted phenol or condensation product.
  • condensation product is meant reaction products having two or more phenolic rings.
  • Resoles are mixtures of hydroxymethylphenols which are linked via methylene and methylene ether bridges and can be obtained by reaction of aldehydes and phenols in a molar ratio of 1: ⁇ 1, if appropriate in the presence of a catalyst, for example a basic catalyst. They have a molecular weight M w of ⁇ 10,000 g / mol.
  • phenol resins which are particularly suitable as polyol component are referred to as "o-o” or “high-ortho” novolaks or Benzyl ether resins known. These are obtainable by condensation of phenols with aldehydes in weakly acidic medium using suitable catalysts.
  • Suitable catalysts for the preparation of benzylic ether resins are salts of divalent ions of metals such as Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca and Ba. Preferably, zinc acetate is used. The amount used is not critical. Typical amounts of metal catalyst are 0.02 to 0.3 wt .-%, preferably 0.02 to 0.15 wt .-%, based on the total amount of phenol and aldehyde.
  • phenolic resins For the preparation of phenolic resins, all conventionally used phenols are suitable. In addition to unsubstituted phenols, substituted phenols or mixtures thereof can be used. The phenolic compounds are unsubstituted either in both ortho positions or in an ortho and in the para position to allow polymerization. The remaining ring carbon atoms may be substituted. The choice of the substituent is not particularly limited so long as the substituent does not adversely affect the polymerization of the phenol or the aldehyde. Examples of substituted phenols are alkyl-substituted phenols, alkoxy-substituted phenols and aryloxy-substituted phenols.
  • the abovementioned substituents have, for example, 1 to 26, preferably 1 to 15, carbon atoms.
  • suitable phenols are o-cresol, m-cresol, p-cresol, 3,5-xylene, 3,4-xylene, 3,4,5-trimethylphenol, 3-ethylphenol, 3,5-diethylphenol, p-butylphenol, 3,5-dibutylphenol, p-amylphenol, cyclohexylphenol, p-octylphenol, p-nonylphenol, 3,5-dicyclohexylphenol, p-crotylphenol, p-phenylphenol, 3,5-dimethoxyphenol and p-phenoxyphenol.
  • phenol itself.
  • higher condensed phenols such as bisphenol A, are suitable.
  • polyhydric phenols having more than one phenolic hydroxyl group are also suitable.
  • Preferred polyhydric phenols have 2 to 4 phenolic hydroxyl groups.
  • suitable polyhydric phenols are pyrocatechol, resorcinol, hydroquinone, pyrogallol, fluoroglycine, 2,5-dimethylresorcinol, 4,5-dimethylresorcinol, 5-methylresorcinol or 5-ethylresorcinol.
  • Mixtures of various mono- and polyhydric and / or substituted and / or condensed phenolic components can also be used for the preparation of the polyol component.
  • phenols of general formula I for the preparation of the phenolic resin component, wherein A, B and C independently of one another from a hydrogen atom, a branched or unbranched alkyl radical, which may have, for example 1 to 26, preferably 1 to 15 carbon atoms, a branched or unbranched alkoxy radical, for example 1 to 26, preferably having from 1 to 15 carbon atoms, a branched or unbranched alkenoxy radical which may, for example, have 1 to 26, preferably 1 to 15, carbon atoms, an aryl or alkylaryl radical, such as, for example, bisphenyls.
  • a branched or unbranched alkyl radical which may have, for example 1 to 26, preferably 1 to 15 carbon atoms, a branched or unbranched alkoxy radical, for example 1 to 26, preferably having from 1 to 15 carbon atoms, a branched or unbranched alkenoxy radical which may, for example, have 1 to 26, preferably 1 to 15, carbon atoms,
  • Suitable aldehydes for the production of the phenolic resin component are aldehydes of the formula: R-CHO, wherein R is a hydrogen atom or a carbon atom radical having preferably 1 to 8, particularly preferably 1 to 3 carbon atoms.
  • R is a hydrogen atom or a carbon atom radical having preferably 1 to 8, particularly preferably 1 to 3 carbon atoms.
  • Specific examples are formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde and benzaldehyde. It is particularly preferred to use formaldehyde, either in its aqueous form, as para-formaldehyde or trioxane.
  • the molar ratio of aldehyde to phenol is preferably 1: 1.0 to 2.5: 1, more preferably 1.1: 1 to 2.2: 1, particularly preferably 1.2: 1 to 2.0: 1.
  • the production of the phenolic resin component takes place by methods known to the person skilled in the art.
  • the phenol and the aldehyde are reacted under substantially anhydrous conditions in the presence of a divalent metal ion at temperatures of preferably less than 130 ° C.
  • the resulting water is distilled off.
  • a suitable entraining agent may be added, for example toluene or xylene, or the distillation is carried out at reduced pressure.
  • the phenol component is reacted with an aldehyde, preferably benzyl ether resins.
  • the reaction with a primary or secondary aliphatic alcohol to an alkoxy-modified phenolic resin in the one-stage or two-stage process is also possible.
  • the phenol, the aldehyde and the alcohol are in the presence a suitable catalyst reacted.
  • an unmodified resin is first prepared, which is subsequently reacted with an alcohol.
  • the alcohol component is preferably used in a molar ratio of alcohol: phenol of less than 0.25 so that less than 25% of the hydroxymethyl groups are etherified.
  • Suitable alcohols are primary and secondary aliphatic alcohols having one hydroxy group and 1 to 10 carbon atoms. Suitable primary and secondary alcohols are, for example, methanol, ethanol, propanol, n-butanol and n-hexanol. Particularly preferred are methanol and n-butanol.
  • the phenolic resin is preferably selected so that crosslinking with the polyisocyanate component is possible.
  • phenolic resins comprising molecules having at least two hydroxyl groups in the molecule are particularly suitable.
  • the phenolic resin component or the isocyanate component of the binder system is preferably used as a solution in an organic solvent or a combination of organic solvents. Solvents may be required to keep the components of the binder in a sufficiently low viscosity state. This is u.a. required to obtain a uniform crosslinking of the refractory molding material and its flowability.
  • the polyurethane-based binder system comprises at least 3% by weight of a carboxylic acid diester of a branched alkanediol and less than 10% by weight of aromatic solvent, based in each case on the binder system. It is possible that only the polyol component or only the polyisocyanate component comprises a portion of the carbonic acid diester of a branched alkanediol. However, it is also possible that both binder components comprise a portion of the carboxylic acid diester of a branched alkanediol.
  • the polyurethane-based binder system preferably comprises a carboxylic acid diester content of a branched alkanediol of more than 5% by weight.
  • the polyurethane-based binder system has a carboxylic acid diester content of more than 8% by weight of a branched alkanediol.
  • the polyurethane-based binder system comprises less than 30% by weight of a carboxylic acid diester of a branched alkanediol, and in another embodiment less than 20% by weight of a carboxylic acid diester of a branched alkanediol.
  • At least one of the polyol component and the polyisocyanate component preferably contains at least 3% by weight, preferably at least 5% by weight, particularly preferably at least 8% by weight, of the carboxylic acid diester of a branched alkanediol.
  • the solvent of the respective component can be completely formed by the carboxylic acid diester of a branched alkanediol.
  • the proportion of aromatic solvents is preferably chosen as low as possible.
  • the proportion of the aromatic solvent is based on the binder system less than 10 wt .-%, preferably less than 5 wt .-%, more preferably less than 3 wt .-%. Most preferably, the binder system does not comprise any aromatic solvents.
  • Based on the polyol component or the polyisocyanate component, at least one of these components contains less than 10 wt .-%, preferably less than 5 wt .-%, more preferably less than 3 wt .-% of aromatic solvents.
  • solvents can be used as a further solvent all solvents which are conventionally used in binder systems for foundry technology. Suitable further solvents are, for example, oxygen-rich, polar, organic solvents. Particularly suitable are dicarboxylic acid esters, glycol ether esters, glycol diesters, glycol diethers, cyclic ketones, cyclic esters or cyclic carbonates. Dicarboxylic acid esters, cyclic ketones and cyclic carbonates are preferably used.
  • Dicarboxylic acid esters have the formula R a OOC-R b -COOR a , wherein the radicals R a are each independently an alkyl group having 1 to 12, preferably 1 to 6 carbon atoms and R b is an alkylene group, ie a divalent alkyl group, with 1 to 12, preferably 1 to 6 carbon atoms. R b may also include one or more carbon-carbon double bonds. Examples are dimethyl esters of carboxylic acids having 4 to 10 carbon atoms, which are available, for example, under the name "dibasic ester" (DBE) from Invista International S.à.rl, Geneva, CH.
  • DBE dibasic ester
  • Glycol ether esters are compounds of the formula R c -OR d -OOCR e wherein R c is an alkyl group having 1 to 4 carbon atoms, R d is an ethylene group, a propylene group or an oligomeric ethylene oxide or propylene oxide and R e is an alkyl group having 1 to 3 carbon atoms , Preference is given to glycol ether acetates, for example butylglycol acetate. Glycol diesters accordingly have the general formula R e COO-R d OOCR e , where R d and R e are as defined above and the radicals R e are each independently selected. Preferred are glycol diacetates such as propylene glycol diacetate.
  • Glycol diethers can be characterized by the formula R c -OR d -OR c , where R c and R d are as defined above and the radicals R c are each independently selected.
  • a suitable glycol diether is, for example, dipropylene glycol dimethyl ether. Cyclic ketones, cyclic esters and cyclic carbonates of 4 to 5 carbon atoms are also suitable.
  • a suitable cyclic carbonate is, for example, propylene carbonate.
  • the alkyl and Alkylene groups may each be branched or unbranched.
  • the proportion of the solvent in the binder system is preferably not chosen too high, since the solvent evaporates during the production and application of the molded article produced from the molding compound and thus, for example, can lead to unpleasant odors or leads to smoke during the casting.
  • the proportion of the solvent in the binder system is less than 50 wt .-%, more preferably less than 40 wt .-%, more preferably less than 35 wt .-%, selected.
  • the dynamic viscosity of the polyol component or of the polyisocyanate component which can be determined, for example, by the Brookfield rotary spindle method, is preferably less than 1000 mPas, more preferably less than 800 mPas and particularly preferably less than 600 mPas.
  • any carboxylic acid can be used per se.
  • the carboxylic acid may have a branched or unbranched alkyl radical. Further, the carboxylic acid may also include carbon-carbon double bonds. However, saturated carboxylic acids are preferred.
  • the chain length of the carboxylic acid can be selected within wide limits. Preference is given to using carboxylic acids which contain 2 to 20 carbon atoms, more preferably 4 to 18 carbon atoms.
  • a branched carboxylic acid is used for the carboxylic acid diester of a branched alkanediol. Preference is given to using monocarboxylic acids. But it is also possible to use half esters of dicarboxylic acids.
  • the hydroxy groups of the alkanediol can be arranged terminal as a primary hydroxyl group or also within the carbon chain as a secondary or tertiary hydroxyl group.
  • a Secondary hydroxy group is understood to mean a hydroxy group which is bonded to a carbon atom which is connected to a hydrogen atom and two carbon atoms.
  • a tertiary hydroxy group is understood to mean a hydroxy group which is bonded to a carbon atom which is bonded to three further carbon atoms, and, under a primary hydroxy group, a hydroxy group which is bonded to a carbon atom which is bonded to one carbon atom and two hydrogen atoms.
  • the alkanediol comprises a primary and a secondary hydroxy group.
  • R 1 or R 2 is a methyl group or an ethyl group and the other is a hydrogen atom.
  • radicals R 4 can be chosen independently of each other and preferably comprise 1 to 3 carbon atoms. Both radicals R 4 are preferably identical and are particularly preferably a methyl group.
  • R 5 and R 6 represent a hydrogen atom.
  • R 3 and R 8 may be different groups.
  • R 3 and R 8 are the same.
  • R 3 and R 8 may be saturated, unsaturated or aromatic hydrocarbon radicals comprising 1 to 19, preferably 2 to 10, more preferably 3 to 6 carbon atoms.
  • One or more hydrogen atoms of the hydrocarbon group may be replaced by other substituents.
  • Other substituents are generally understood to mean atoms or groups of atoms which are not hydrogen. Suitable other substituents are halogen atoms, in particular chlorine, a glycidyl radical, and an epoxy group.
  • at most 3 hydrogen atoms of the hydrocarbon radical preferably at most 2 hydrogen atoms of the hydrocarbon radical are replaced by other substituents.
  • no hydrogen atom of the hydrocarbon radical is replaced by another substituent.
  • the hydrocarbon radicals R 3 and R 8 may also be an unsaturated hydrocarbon residue, said 1 to 4, preferably 1 to 3, particularly preferably precisely comprises a double bond.
  • the groups R 3 and R 8 particularly preferably represent a saturated, aliphatic hydrocarbon radical having 1 to 19, preferably 2 to 10, particularly preferably 2 to 5, hydrocarbon atoms.
  • the saturated hydrocarbon radical can be straight-chain or branched, with branched hydrocarbon radicals being preferred.
  • R 3 and R 8 are preferably an iso-butyl group.
  • the indices a, b and c can, independently of one another, assume the values 0, 1, 2, 3 and 4, the sum a + b + c being at least 2. More preferably, the value for the indices a and c is at least 1. The sum of a + b + c is preferably less than 10, preferably less than 8.
  • alkanediol may have a large structural variation. Exemplary alkanediols are shown below:
  • alkanediol is 2,2,4-trimethyl-1,3-pentanediol and further preferably carboxylic acid, isobutyric acid, acetic acid, and benzoic acid.
  • Exemplary carboxylic diesters of a branched alkanediol are 2,2,4-trimethyl-1,3-pentanediol diacetate and 2,2,4-trimethyl-1,3-pentanediol dibenzoate.
  • the polyurethane-based binder system contains at least a portion of a fatty acid ester as solvent.
  • Suitable fatty acids preferably contain 8 to 22 carbon atoms which are esterified with an aliphatic alcohol.
  • the fatty acids may be present as a homogeneous compound or as a mixture of different fatty acids.
  • fatty acids of natural origin are used, such as tall oil, rapeseed oil, sunflower oil, germ oil and coconut oil.
  • the aliphatic alcohols used are preferably primary alcohols having 1 to 12 carbon atoms, particularly preferably 1 to 10 carbon atoms, particularly preferably 4 to 10 carbon atoms, with methanol, isopropanol and n-butanol being particularly preferred.
  • Such fatty acid esters are for example in the EP-A-1 137 500 described.
  • the proportion of the at least one fatty acid ester in the polyurethane-based binder system is preferably less than 50% by weight, more preferably less than 40% by weight, particularly preferably less than 35% by weight. According to one embodiment, the proportion of the at least one fatty acid ester on the binder system more than 3 wt .-%, preferably more than 5 wt .-%, particularly preferably more than 8 wt .-%.
  • the proportion of the binder system in the molding material mixture based on the weight of the refractory molding material, preferably between 0.5 and 10 wt .-%, preferably selected between 0.6 and 7 wt .-%.
  • the binder systems may contain conventional additives, eg silanes ( EP-A-1 137 500 ), or internal release agents, for example fatty alcohols ( EP-B-0 182 809 ), drying oils ( US-A-4,268,425 ) or complexing agent ( WO 95/03903 ), or mixtures thereof.
  • silanes EP-A-1 137 500
  • internal release agents for example fatty alcohols ( EP-B-0 182 809 ), drying oils ( US-A-4,268,425 ) or complexing agent ( WO 95/03903 ), or mixtures thereof.
  • Suitable silanes are, for example, aminosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and ureidosilanes, such as ⁇ -hydroxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) trimethoxysilane and N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane.
  • the molding material mixture according to the invention may comprise a binder system which comprises a proportion of cassava nut shell oil, at least one component of the cassava nut oil and / or at least one derivative of the cashew nut shell oil.
  • a binder system which comprises a proportion of cassava nut shell oil, at least one component of the cassava nut oil and / or at least one derivative of the cashew nut shell oil.
  • a cashew nut shell oil is understood to mean both the oil obtained from seed casings of the cashew tree, which comprises about 90% anacardic acid and about 10% cardol, and the technical cashew nut shell oil which is obtained from the natural product by heat treatment acidic environment, and contains as main ingredients Cardanol and Cardol.
  • Suitable components of the binder are the cashew nut shell oil itself, in particular the technical cashew nut shell oil, as well as the components obtained therefrom, in particular Cardol and Cardanol, and mixtures thereof and their oligomers, such as those remaining in the bottoms during the distillation of cashew nut shell oil. These compounds can also be used in technical quality.
  • the mixture of essentially cardanol and cardol, which is also known as cashew nutshell liquid (CNSL), formed during the distillation of cashew nut shell oil is preferably used.
  • the double bonds of cardanol and cardol contained in the side chain may be partially or fully reacted with hydroxyl groups, epoxide groups, halogens, acid anhydrides, diclyclopentadiene or hydrogen. These groups can in turn be reacted with nucleophiles.
  • the phenolic OH groups can also be completely or partially derivatized, for example by addition of ethylene oxide or propylene oxide units.
  • the cashew nut shell oil or the compounds derived therefrom may be present as a separate component in the binder. These components act as a reactive solvent, which reacts with the curing of the binder in the resulting crosslinked polymer.
  • a high stability of the molded body is achieved at elevated temperature.
  • the at least one component of the cashew nut shell oil and / or the at least one derivative of the cashew nut shell oil preferably forms at least a portion of the polyol component.
  • the at least one component of the cashew nut shell oil and / or the at least one derivative of the cashew nut shell oil is added during the synthesis of the polyol component so that they are incorporated into the polyol component during the synthesis.
  • the synthesis of the polyol component is carried out in a known manner, wherein the at least one component of the cashew nut shell oil and / or the at least one derivative of cashew nut shell oil can be added to the reaction mixture already at the beginning of the synthesis or only at a later point in time of the synthesis.
  • the polyol component is formed by condensation of a phenolic component and an oxo component, wherein the cashew nut shell oil containing at least one component of the cashew nut shell oil and / or the at least one derivative of the cashew nut shell oil Cashew nut shell oil forms at least a portion of the phenolic component.
  • the synthesis of the polyol component is carried out in the manner described above for the preparation of the phenolic resin, wherein, however, in addition to the phenolic component, the cashew nut shell oil or the at least one component of cashew nut shell oil or the at least one derivative of cashew nut shell oil is added as a further component.
  • the phenol component the phenols described above, as the oxo component, the above-described aldehydes can be used.
  • the proportion of the cashew nut shell oil, the at least one component of the cashew nut shell oil and / or the at least one derivative of the cashew nut shell oil in the phenolic component is preferably from 0.5 to 20% by weight, more preferably from 0.75 to 15% by weight, particularly preferably 1 to 10 wt .-%.
  • the cashew nut shell oil, its components or derivatives may be added to the reaction mixture at any time during the synthesis. Preferably, the addition takes place already at the beginning of the synthesis.
  • Cashew nut shell oil, cashew nut shell components, and cashew nut oil derivatives may also be added to the isocyanate component, and may also react with a portion of the isocyanate groups.
  • the components of the binder system can first be combined and then added to the refractory molding material. However, it is also possible to add the components of the binder simultaneously or sequentially to the refractory base molding material. To obtain a uniform mixture of the components of the molding material mixture, conventional methods can be used.
  • the molding material mixture may additionally optionally contain other conventional ingredients such as iron oxide, milled flax fibers, wood flour granules, pitch and refractory metals.
  • the binder is first mixed with the refractory molding base material to form a molding material mixture as described above. If the molding is to be produced by the PU-No-Bake process, a suitable catalyst can also already be added to the molding material mixture. For this purpose, liquid amines are preferably added to the molding material mixture. These amines preferably have a pK b value of 4 to 11.
  • Suitable catalysts are 4-alkylpyridines wherein the alkyl group comprises 1 to 4 carbon atoms, isoquinoline, arylpyridines such as phenylpyridine, pyridine, acryline, 2-methoxypyridine, pyridazine, 3-chloropyridine, quinoline, n-methylimidazole, 4,4'-dipyridine , Phenylpropylpyridine, 1-methylbenzimidazole, 1,4-thiazine, N, N-dimethylbenzylamine, triethylamine, tribenzylamine, N, N-dimethyl-1,3-propanediamine, N, N-dimethylethanolamine and triethanolamine.
  • arylpyridines such as phenylpyridine, pyridine, acryline, 2-methoxypyridine, pyridazine, 3-chloropyridine, quinoline, n-methylimidazole, 4,4'-dipyridine , Phen
  • the catalyst may optionally be diluted with an inert solvent, for example, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, or a fatty acid ester.
  • an inert solvent for example, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, or a fatty acid ester.
  • the amount of catalyst added is selected in the range of 0.1 to 15% by weight, based on the weight of the polyol component.
  • the molding material mixture is then introduced by conventional means into a mold and compacted there.
  • the molding material mixture is then cured to a shaped body.
  • the shaped body should preferably retain its outer shape.
  • the curing takes place according to the PU cold box method.
  • a gaseous catalyst is passed through the molded molding material mixture.
  • catalyst the usual catalysts in the field of cold-box process can be used.
  • amines as catalysts, in particular preferably dimethylethylamine, dimethyl-n-propylamine, dimethylisopropylamine, dimethyl-n-butylamine, triethylamine and trimethylamine in their gaseous form or as aerosol.
  • the molded article produced by the process may per se have any shape customary in the field of foundry.
  • the shaped body is in the form of foundry molds or cores.
  • the invention relates to a shaped body, as can be obtained by the method described above. This is characterized by a high mechanical stability and by a low quality development during metal casting.
  • the invention relates to the use of this molding for metal casting, in particular iron and cast aluminum.
  • Polyol component (binder component 1):
  • Table 2 Composition of the polyisocyanate component (binder component 2) (% by weight) Not according to the invention inventively B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 B11 Polymer tech. 4,4'-MDI 80 80 80 80 80 80 80 80 80 80 Rapsölfett Acidmethylester 20 10 isopropyl 20 10 2-ethylhexyl 2-ethylhexanoate 20 10 tetraethylorthosilicate 20 10 DBE 20 10 2,2,4-trimethyl-1,3-pentanediol diisobutyrate 20 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
  • test bars were placed in a Georg Fischer strength tester equipped with a three-point bending device (DISA-Industrie AG, Schaffhausen, CH) and the force was measured, which resulted in the breakage of the test bars.
  • test bars were 10 min. immersed after its preparation for 3 seconds in a water sizing MIRATEC ® DC 3 (ASK-Chemicals GmbH, Hilden, DE), and then stored for 30 min at room temperature. A portion of the size-coated test bar was subjected to the strength test after storage for 30 minutes at room temperature. Another portion of the test bars was dried after storage for 30 minutes at room temperature, at 150 ° C for 30 minutes. After cooling to room temperature, these test bars were also tested for their strength.
  • Table 3 The results of the strength test are summarized in Table 3.
  • Table 3 Strength tests Not according to the invention inventively Component 1 A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 Component 2 B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 B11 Strengths N / cm 2 Immediately 145 110 115 150 110 175 180 200 175 160 135 24 hours 460 415 410 440 440 490 500 495 470 455 440 24 hours at 98% rel.
  • Test bars prepared using a binder system containing 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, show higher strength. Higher strengths are obtained when only 2,2,4-trimethyl-1,3-pentanediol diisobutyrate is used as the solvent. However, high strengths are also obtained if the solvent contains fatty acid esters which have an average polarity, or else strongly polar esters and also dibasic esters or tetraethyl orthosilicate.
  • Table 4 Composition of the polyol component (% by weight) A2 A12 A8 A13 A6 phenolic resin 67.5 67.5 67.5 67.5 isopropyl 32 22.4 16 9.6 2,2,4-trimethyl-1,3-pentanediol diisobutyrate 9, 6 16 22.4 32 silane 0.5 0.5 0.5 0.5 0.5 0.5 B2 B12 B8 B13 B6 Polymer tech. 4,4 '- MDI 80 80 80 80 80 80 80 isopropyl 20 14 10 6 2,2,4-trimethyl-1,3-pentanediol diisobutyrate 6 10 14 20
  • Test bars were produced and their strength tested analogously to Example 3. The results are summarized in Table 6.
  • Table 6 Strength tests using mixed solvents Component 1 A2 A12 A8 A13 A6 Component 2 B2 B12 B8 B13 B6 Strengths N / cm 2 Immediately 110 190 200 200 175 24 hours 415 450 495 485 490 24 hours at 98% rel. humidity 310 360 365 340 335 Water-based (wet) 295 310 330 335 325 Water-based (dried) 455 500 530 490 510
  • composition of the polyol component is shown in Table 7 and the composition of the polyisocyanate component in Table 8.
  • Table 7 Composition of the polyol component (% by weight) A14 A15 A16 A17 A18 A19 phenolic resin 67.5 67.5 67.5 67.5 67.5 isopropyl 19.8 11 2.2 19.8 11 2.2 DBE 10 10 10 tetraethylorthosilicate 10 10 10 2,2,4-trimethyl-1,3-pentanediol diisobutyrate 2.2 11 19.8 2.2 11 19, 8 silane 0.5 0.5 0.5 0.5 0.5 0.5 0.5 B14 B15 B16 B17 B18 B19 phenolic resin 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 isopropyl 9 5 1 9 5 1 DBE 10 10 10 tetraethylorthosilicate 10 10 10, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate 1 5 9 1 5 9
  • Test bars were prepared analogously to Example 3 using the binders indicated in Table 10. The test bars were 1 min. long stored at 650 ° C in the oven. After taking the test bars, the development of the smoke was determined against a dark background and rated subjectively with grades 10 (very strong) to 1 (barely perceptible). The result is summarized in Table 10. Table 10: Evaluation of smoke development Component 1 A2 A8 A6 A15 Component 2 B2 B8 B6 B15 rating 10 8th 5 4

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Claims (17)

  1. Mélange de matières moulables pour la fabrication de corps moulés destinés au domaine de la fonderie, comprenant au moins :
    - une matière moulable de base aux propriétés réfractaires ; et
    - un système de liants à base de polyuréthane, comprenant un composant polyisocyanate ainsi que qu'un composant polyol,
    caractérisé en ce que ledit système de liants à base de polyuréthane comprend une proportion d'au moins 3 % en poids d'un diester d'acide carboxylique d'un alkandiol ramifié ainsi qu'une proportion inférieure à 10 % en poids d'un solvant aromatique, toujours par rapport audit système de liants.
  2. Mélange de matières moulables selon la revendication 1, caractérisé en ce que la proportion dudit diester d'acide carboxylique d'un alkandiol ramifié est supérieure à 5 % en poids.
  3. Mélange de matières moulables selon les revendications 1 ou 2, caractérisé en ce que ledit diester d'acide carboxylique d'un alkandiol ramifié présente une structure de la formule
    Figure imgb0010
     dans laquelle signifient, indépendamment l'un de l'autre, à chaque incidence :
    R1, R7: H, CH3, C2H5, C3H7, CH2OC(O)R3, OC(O)R3;
    R2, R4, R5, R6 : H, CH3, C2H5, C3H7 ;
    R3 : un radical hydrocarboné saturé, insaturé ou aromatique, avec 1 à 19 atomes d'hydrocarbure, chez lequel un ou plusieurs atomes d'hydrogène peuvent être remplacés par d'autre substituants ;
    a, b, c : un nombre entier entre 0 et 4 ;
    x 0, 1 ou 2 ;
    - au moins un des radicaux R1, R2 et R4 n'étant pas de l'hydrogène ;
    - x étant = 0 si R1 et R7 représentent CH2OC(O)R3, OC(O)R3; et
    - la somme a + b + c étant supérieure ou égale à 2.
  4. Mélange de matières moulables selon l'une des revendications précédentes, caractérisé en ce que ledit diester d'acide carboxylique d'un alkandiol ramifié est le diisobutyrate de 2,2,4-triméthyl-1,3-pentanediol.
  5. Mélange de matières moulables selon l'une des revendications 1 à 4, caractérisé en ce que ledit système de liants à base de polyuréthane comprend au moins un ester d'acide gras.
  6. Mélange de matières moulables selon la revendication 4, caractérisé en ce que, au sein dudit système de liants à base de polyuréthane, la proportion de l'au moins un ester d'acide gras est inférieure à 90 % en poids.
  7. Mélange de matières moulables selon les revendications 5 ou 6, caractérisé en ce que ledit ester d'acide gras est un ester de méthyle, un ester de butyle et/ou un ester d'isopropyle.
  8. Mélange de matières moulables selon l'une des revendications précédentes, caractérisé en ce que le composant polyol est formé par réaction de condensation entre un composant phénolique et un composant oxo.
  9. Mélange de matières moulables selon la revendication 8, caractérisé en ce que ledit composant oxo est formé par un aldéhyde.
  10. Mélange de matières moulables selon l'une des revendications précédentes, caractérisé en ce que le composant polyol est une résine d'éther de benzyle.
  11. Mélange de matières moulables selon l'une des revendications précédentes, caractérisé en ce que le composant isocyanate est un isocyanate aliphatique, aromatique ou hétérocyclique ayant par molécule au moins deux groupes isocyanate, ou ses oligomères ou polymères.
  12. Mélange de matières moulables selon l'une des revendications précédentes, caractérisé en ce qu'il contient ledit système de liants dans une proportion comprise entre 0,5 et 10 % en poids, par rapport au poids de ladite matière moulable de base aux propriétés réfractaires.
  13. Procédé de fabrication d'un corps moulé destiné au domaine de la fonderie, caractérisé par les étapes :
    - mise à disposition d'un mélange de matières moulables selon l'une des revendications 1 à 12 ;
    - moulage dudit mélange de matières moulables, de façon à obtenir un corps moulé ;
    - durcissement dudit corps moulé par ajout d'un catalyseur de durcissement.
  14. Procédé selon la revendication 13, caractérisé en ce que ledit catalyseur de durcissement est ajouté sous forme gazeuse.
  15. Procédé selon l'une des revendications 13 ou 14, caractérisé en ce que ledit durcissement est réalisé essentiellement à température ambiante.
  16. Corps moulé destiné au domaine de la fonderie, obtenu par un procédé selon l'une des revendications 13 à 15.
  17. Utilisation d'un corps moulé selon la revendication 16 pour la coulée de métaux.
EP09706370A 2008-02-01 2009-01-30 Utilisation de diesters ramifiés d'acide carboxylique d'alcanediol dans des liants de fonderie à base de polyuréthane Active EP2249982B1 (fr)

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US8813830B2 (en) 2014-08-26
JP2011510818A (ja) 2011-04-07
EP2249982A2 (fr) 2010-11-17
KR20100112189A (ko) 2010-10-18
JP5408805B2 (ja) 2014-02-05
DE102008007181A1 (de) 2009-08-06
WO2009095251A8 (fr) 2010-09-16
WO2009095251A3 (fr) 2010-02-25
EA201070885A1 (ru) 2011-02-28
UA99174C2 (ru) 2012-07-25
MX2010008276A (es) 2010-08-26
US20110005702A1 (en) 2011-01-13
ATE521436T1 (de) 2011-09-15
BRPI0906725A2 (pt) 2019-05-07
WO2009095251A2 (fr) 2009-08-06
CN101932394A (zh) 2010-12-29
CA2712656A1 (fr) 2009-08-06
ES2372666T3 (es) 2012-01-25
EA018307B1 (ru) 2013-07-30
ZA201004919B (en) 2011-02-23

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