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EP3265254B1 - Procédé de durcissement de liants au polyuréthane dans des mélanges de matériaux ce moulage par introduction d'amines tertiaires et de solvants et kit pour la mise en uvre du procédé - Google Patents

Procédé de durcissement de liants au polyuréthane dans des mélanges de matériaux ce moulage par introduction d'amines tertiaires et de solvants et kit pour la mise en uvre du procédé Download PDF

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Publication number
EP3265254B1
EP3265254B1 EP16722038.3A EP16722038A EP3265254B1 EP 3265254 B1 EP3265254 B1 EP 3265254B1 EP 16722038 A EP16722038 A EP 16722038A EP 3265254 B1 EP3265254 B1 EP 3265254B1
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EP
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Prior art keywords
solvent
weight
molding material
isocyanate
solvents
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EP16722038.3A
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German (de)
English (en)
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EP3265254A1 (fr
Inventor
Christian Priebe
Philip Schneider
Mark STANCLIFF
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ASK Chemicals GmbH
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ASK Chemicals GmbH
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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/02—Sand moulds or like moulds for shaped castings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/10—Cores; Manufacture or installation of cores

Definitions

  • the present invention relates to a method for producing cores and casting molds by exposing molding material mixtures comprising at least one refractory material and at least one polyurethane-based binder with gaseous or aerosol-form tertiary amines and gaseous or aerosol-form solvents for the amine catalysts and a kit for carrying out the process comprising tertiary amines as catalysts and a solvent for the amines as a component of the kit.
  • the core-making method known as the "cold box process” or "Ashland process” has gained great importance in the foundry industry.
  • Two-component polyurethane systems are used to bond a refractory base material.
  • the polyol component consists of a polyol with at least two OH groups per molecule
  • the isocyanate component consists of a polyisocyanate with at least two NCO groups per molecule.
  • the curing of the mixture of, among other things, the basic molding material and binder, also known as the molding material mixture for short takes place with the aid of tertiary amines, which are passed through the molding material mixture in gaseous form or as an aerosol after shaping ( US3409579 ). This is usually done using a carrier gas, for example air, nitrogen or CO 2 , into which the amines are metered.
  • a carrier gas for example air, nitrogen or CO 2
  • the EP 1057554 B1 describes cold box binders that contain an alkyl silicate as a solvent for the phenolic resin or isocyanate component. Gassing with amine is only referred to in the example. Mixtures of alkyl silicates or alkyl silanes with amines are not mentioned.
  • the US6288130B1 discloses the use of orthoesters in cold box binders.
  • the orthoester must be explicitly dissolved in the isocyanate component.
  • US6365646B1 discloses a method for producing a core with improved strength in which - especially in the cold-box method - tertiary amines are passed through the shaped core in a stream of inert gas until it has hardened.
  • the inventors have set themselves the task of looking for other ways of reducing the amine consumption in core/mold manufacture.
  • the aim was a solution that can be used advantageously with all known cold box binders, ie even with those whose amine requirement is already low.
  • the present invention in the method according to the EP 1955792 A1 be usable.
  • the invention relates to a method for producing a shaped body as a cast part or as a core, according to claim 1.
  • the invention further relates to a kit for producing a binder for molding mixtures according to claim 15.
  • Trimethylamine (TMA), dimethylethylamine (DMEA), dimethyl-n-propylamine (DMPA), dimethylisopropylamine (DMIPA), diethylmethylamine (DEMA) and triethylamine (TEA) are known as conventional gassing catalysts for the polyurethane cold box process , whereby mainly DMEA, DMPA, DMIPA and TEA are used in practice.
  • tertiary amines can all be used as catalysts used according to the invention, as can those from EP 1955792 A1 known mixtures of at least two tertiary amines.
  • Solvents within the meaning of the invention are those which are liquid at 25° C. and have a boiling point of 20° C. to 220° C. at 1013 mbar. Solvent further means that the catalyst completely dissolves in the solvent at room temperature (25°C). Furthermore, solvent means that the solvent is not a catalyst for the PU reaction and is different from a catalyst for the PU reaction. Above solvent means that the solvent is inert to an amine catalyst. However, it may well be desirable for the solvent to react with components of the mold material mixture, for example at temperatures of 5° C. to 80° C., in particular with water in the mold material mixture.
  • Suitable solvents for these amines are in principle all solvents which are miscible with the tertiary amines, which dissolve them homogeneously at room temperature and which can be brought into the gaseous state or in aerosol form together with the amines under the conditions prevailing in the gas-introduction apparatus.
  • Polar solvents such as esters, preferably orthoesters, or alkylsilanes, alkoxysilanes or mixed alkylalkoxysilanes are used as solvents, but also aromatic, cycloaliphatic and aliphatic hydrocarbon solvents and mixtures of the classes of substances mentioned.
  • orthoesters are, for example, trimethyl orthoformate or triethyl orthoformate.
  • alkylsilanes or alkylalkoxysilanes are: methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane and/or propyltrimethoxysilane.
  • the weight ratio of (A) to (B) is between 95:5 and 5:95, preferably between 80:20 and 20:80, and more preferably between 70:30 and 30:70.
  • the catalyst mixture according to the invention can be metered into the carrier gas (which can be air or an inert gas or gas mixture) as one component (mixture of A+B), but (A) and (B) can also be added individually to the carrier gas stream at the same time. What is surprising here is the fact that components (A) and (B) need not necessarily be added at the same time. An improvement in the catalysis is also observed when (A) and (B) or (B) and (A) are dosed in succession, the results being particularly good if first the non-catalytic solvent (B) and then the amine catalyst (A) is injected or gassed.
  • refractory basic mold material also referred to below as basic mold material for short
  • quartz, zirconium or chrome ore sand, olivine, vermiculite, bauxite, fireclay and so-called artificial mold raw materials are suitable, i.e. raw mold materials that have been brought into a spherical or almost spherical (e.g. ellipsoidal) shape by industrial shaping processes.
  • glass beads glass granules or artificial, spherical, ceramic sands - so-called Cerabeads ® but also Spherichrome ® , SpherOX ® or "Carboaccucast”, as well as hollow microspheres such as can be isolated as a component from fly ash, such as aluminum silicate hollow spheres (so-called microspheres ). Mixtures of the refractory materials mentioned are also possible.
  • Basic mold materials which contain more than 50% by weight of quartz sand, based on the refractory basic mold material, are particularly preferred.
  • a refractory basic molding material is understood to mean substances that have a high melting point (melting point).
  • the melting point of the refractory basic mold material is preferably greater than 600°C, preferably greater than 900°C, particularly preferably greater than 1200°C and particularly preferably greater than 1500°C.
  • the refractory basic mold material preferably makes up more than 80% by weight, in particular more than 90% by weight, particularly preferably more than 95% by weight, of the mold material mixture.
  • the mean diameter of the refractory basic mold materials is generally between 100 ⁇ m and 600 ⁇ m, preferably between 120 ⁇ m and 550 ⁇ m and particularly preferably between 150 ⁇ m and 500 ⁇ m.
  • the particle size can be determined, for example, by sieving according to DIN ISO 3310. Particular preference is given to particle shapes with the greatest length to the smallest length (at right angles to one another and for all spatial directions) of 1:1 to 1:5 or 1:1 to 1:3, i.e. those which are not fibrous, for example.
  • the refractory basic molding material preferably has a free-flowing state, in particular in order to be able to process the molding material mixture according to the invention in conventional core shooting machines.
  • the components of the binder system can first be combined and then added to the refractory base mold material. However, it is also possible to add the components of the binder simultaneously or one after the other in any order to the refractory base molding material.
  • the polyol component has phenol-aldehyde resins, referred to here as phenolic resins for short. All conventionally used phenolic compounds are suitable for producing the phenolic resins. In addition to unsubstituted phenols, substituted phenols or mixtures thereof can be used. The phenolic compounds are preferably unsubstituted either in both ortho positions or in one ortho and para position. The remaining ring carbons can be substituted. The choice of the substituent is not particularly limited. However, the substituent should not adversely affect the reaction of the phenol with the aldehyde. Examples of substituted phenols are alkyl substituted, alkoxy substituted, aryl substituted and aryloxy substituted phenols.
  • the substituents mentioned above have, for example, 1 to 26, preferably 1 to 15, carbon atoms.
  • suitable phenols are o-cresol, m-cresol, p-cresol, 3,5-xylenol, 3,4-xylenol, 3,4,5-trimethylphenol, 3-ethylphenol, 3,5-diethylphenol, p-butylphenol, 3,5-dibutyl phenol, p-amyl phenol, cyclohexyl phenol, p-octyl phenol, p-nonyl phenol, cardanol, 3,5-dicyclohexyl phenol, p-crotyl phenol, p-phenyl phenol, 3,5-dimethoxy phenol and p-phenoxy phenol.
  • Phenol itself is particularly preferred. Higher condensed phenols, such as bisphenol A, are also suitable. In addition, polyhydric phenols which have more than one phenolic hydroxyl group are also suitable.
  • Preferred polyhydric phenols have 2 to 4 phenolic hydroxyl groups.
  • suitable polyhydric phenols are catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 2,5-dimethylresorcinol, 4,5-dimethylresorcinol, 5-methylresorcinol or 5-ethylresorcinol.
  • Mixtures of different mono- and polyhydric and/or substituted and/or condensed phenol components can also be used for the production of the polyol component.
  • phenols of general formula I used to produce the phenolic resin component, where A, B and C are independently selected from: a hydrogen atom, a branched or unbranched alkyl radical which can have, for example, 1 to 26, preferably 1 to 15 carbon atoms, a branched or unbranched alkoxy radical which, for example, has 1 can have up to 26, preferably 1 to 15 carbon atoms, a branched or unbranched alkenoxy radical, which can have, for example, 1 to 26, preferably 1 to 15 carbon atoms, an aryl or alkylaryl radical, which can have, for example, 6 (7 for aryl) to 26, preferably 6 (7) to 15 carbon atoms, such as bisphenols
  • Aldehydes of the formula are suitable as aldehydes for the production of the phenolic resin component: R-CHO, where R is a hydrogen atom or a carbon atom residue having preferably 1 to 8, more preferably 1 to 3 carbon atoms.
  • R is a hydrogen atom or a carbon atom residue having preferably 1 to 8, more preferably 1 to 3 carbon atoms.
  • Specific examples are formaldehyde, acetaldehyde, propionaldehyde, furfuryl aldehyde and benzaldehyde.
  • Formaldehyde is particularly preferably used, either in its aqueous form, as paraformaldehyde, or trioxane.
  • an at least equivalent number of moles of aldehyde based on the number of moles of the phenol component, is preferably used.
  • the molar ratio of aldehyde to phenol is preferably from 1:1.0 to 2.5:1, particularly preferably from 1.1:1 to 2.2:1, particularly preferably from 1.2:1 to 2.0:1.
  • reaction component can after EP 0177871 A2 aliphatic monoalcohols with one to eight carbon atoms are added.
  • the alkoxylation is said to give the phenolic resins increased thermal stability.
  • the phenolic resin is produced by methods known to those skilled in the art.
  • the phenol and the aldehyde are reacted under essentially anhydrous conditions, in particular in the presence of a divalent metal ion, at temperatures of preferably less than 130°C.
  • the water formed is distilled off.
  • a suitable entraining agent for example toluene or xylene, can be added to the reaction mixture, or the distillation is carried out under reduced pressure.
  • the phenolic resin is chosen so that crosslinking with the polyisocyanate component is possible.
  • Phenolic resins which contain molecules with at least two hydroxyl groups in the molecule, are necessary for the construction of a network.
  • phenolic resins are known under the designation “ortho-ortho” or “high-ortho” novolaks or benzyl ether resins. These can be obtained by condensing phenols with aldehydes in a weakly acidic medium using suitable catalysts.
  • Catalysts useful in the production of benzyl ether resins are divalent ion salts of metals such as Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca and Ba. Zinc acetate is preferably used. The amount used is not critical. Typical amounts of metal catalyst are 0.02 to 0.3% by weight, preferably 0.02 to 0.15% by weight, based on the total amount of phenol and aldehyde.
  • Such resins are, for example, in US3485797 and in EP 1137500 B1 described, the disclosure of which is hereby expressly referred to both with regard to the definition of the resins and with regard to their production.
  • the isocyanate component of the binder system comprises an aliphatic, cycloaliphatic or aromatic isocyanate with at least 2 isocyanate groups per molecule (polyisocyanates), preferably with 2 to 5 isocyanate groups per molecule. Depending on the desired properties, mixtures of isocyanates can also be used. In addition to the polyisocyanates, monoisocyanates can also be used in one embodiment with a smaller proportion by weight.
  • Suitable polyisocyanates include aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate and dimethyl derivatives thereof.
  • suitable aromatic polyisocyanates are toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate and methyl derivatives thereof, and polymethylene polyphenyl isocyanates.
  • polyisocyanates are aromatic polyisocyanates, particularly preferred are polymethylene polyphenyl polyisocyanates such as technical 4,4'-diphenylmethane diisocyanate, i.e. 4,4'-diphenylmethane diisocyanate with a proportion of isomers and higher homologues.
  • the polyisocyanates can also be derivatized by reacting difunctional isocyanates with one another in such a way that some of their isocyanate groups are derivatized to form isocyanurate, biuret, allophanate, uretdione or carbodiimide groups.
  • difunctional isocyanates with one another in such a way that some of their isocyanate groups are derivatized to form isocyanurate, biuret, allophanate, uretdione or carbodiimide groups.
  • dimerization products containing uretdione groups for example of MDI or TDI.
  • the polyisocyanate is preferably used in an amount such that the number of isocyanate groups is from 80 to 120%, based on the number of free hydroxyl groups in the resin.
  • 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 necessary, for example, to keep the components of the binder in a sufficiently low-viscosity state. This is necessary, among other things, to ensure that the refractory mold material is evenly cross-linked and that it is free-flowing.
  • oxygen-rich polar organic solvents can also be used as solvents for the phenolic resin or the phenolic resin component.
  • dicarboxylic acid esters, glycol ether esters, glycol diesters, glycol diethers, cyclic ketones, cyclic esters (lactones), cyclic carbonates or silicic acid esters or mixtures thereof are suitable.
  • Dicarboxylic acid esters, cyclic ketones and cyclic carbonates are preferably used.
  • the proportion of oxygen-rich polar solvents in the total binder can be up to 30%.
  • Typical dicarboxylic acid esters have the formula R 1 OOC-R 2 -COOR 1 where each R 1 is independently an alkyl group having 1 to 12, preferably 1 to 6, carbon atoms and R 2 is an alkylene group having 1 to 4 carbon atoms.
  • R 1 is independently an alkyl group having 1 to 12, preferably 1 to 6, carbon atoms
  • R 2 is an alkylene group having 1 to 4 carbon atoms.
  • dimethyl esters of carboxylic acids having 4 to 6 carbon atoms which are available, for example, from DuPont under the name Dibasic Ester.
  • Typical glycol ether esters are compounds of the formula R 3 -OR 4 -OOCR 5 where R 3 is an alkyl group of 1 to 4 carbon atoms, R 4 is an alkylene group of 2 to 4 carbon atoms and R 5 is an alkyl group of 1 to 3 carbon atoms, e.g Butyl glycol acetate, glycol ether acetates are preferred.
  • Typical glycol diesters accordingly have the general formula R 3 COO-R 4 -OOCR 5 , where R 3 to R 5 are as defined above and the radicals are each selected independently of one another (eg propylene glycol diacetate).
  • Glycol diacetates are preferred.
  • Glycol diethers can be characterized by the formula R 3 -OR 4 -OR 5 in which R 3 to R 5 are as defined above and the radicals are each selected independently of one another (eg dipropylene glycol dimethyl ether).
  • Typical cyclic ketones, cyclic esters and cyclic carbonates having 4 to 5 carbon atoms are also suitable (e.g. propylene carbonate).
  • the alkyl and alkylene groups can each be branched or unbranched.
  • Fatty acid esters such as rapeseed oil fatty acid methyl ester or oleic acid butyl ester are also suitable.
  • Either aromatic solvents, the polar solvents mentioned above or mixtures thereof are used as solvents for the polyisocyanate or the polyisocyanate component.
  • Fatty acid esters and silicic acid esters are also suitable.
  • the binder systems can contain additives, e.g. B. silanes (e.g. according to EP 1137500 B1 ), internal release agents, e.g. B. Fatty alcohols (e.g. according to US4602069 ), drying oils (e.g. according to US4268425 ), complexing agents (e.g. according to US5447968 ) and additives to extend the processing time (e.g. according to US4540724 ) or mixtures thereof.
  • additives e.g. B. silanes (e.g. according to EP 1137500 B1 )
  • internal release agents e.g. B. Fatty alcohols (e.g. according to US4602069 )
  • drying oils e.g. according to US4268425
  • complexing agents e.g. according to US5447968
  • additives to extend the processing time e.g. according to US4540724 or mixtures thereof.
  • the mold material mixture can also optionally contain sand additives to avoid casting defects.
  • the catalyst according to the invention is generally passed through the shaped mold material mixture in gaseous form or as an aerosol by means of a carrier gas. All known gassing apparatuses can be used
  • the moldings produced using the process according to the invention can have any shape that is customary in the field of foundry work.
  • the moldings are in the form of foundry molds or cores. These are characterized by high mechanical stability.
  • Table 2 shows that the amount by weight of amine required for complete curing of the test core is reduced with the catalysts according to the invention. This applies both to formulations with aromatic solvents (Isocure X 16 / Isocure X 28) and to formulations without aromatic solvents (Ecocure 30 HE 1 LF / Ecocure 60 HE 12 LF).

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mold Materials And Core Materials (AREA)

Claims (17)

  1. Procédé de fabrication d'un corps moulé en tant que pièce de coulée ou en tant que noyau, comprenant les étapes consistant à :
    (i) mélanger les matières de base de moulage réfractaires avec un liant contenant
    (P) un ou plusieurs composés polyol ayant au moins 2 groupes hydroxy par molécule et
    (I) un ou plusieurs composés isocyanate ayant au moins 2 groupes isocyanate par molécule,
    pour l'obtention d'un mélange de matière de moulage, et
    (ii) introduire le mélange de matières de moulage ou ses composants dans un outil de moulage ;
    (iii) durcir le mélange de matières de moulage dans l'outil de moulage avec au moins une amine tertiaire (A) comme catalyseur pour obtenir un moule autoportant ; et
    (iv) séparer ensuite le moule durci de l'outil et le cas échéant poursuivre le durcissement, moyennant quoi on obtient un corps moulé durci,
    le durcissement du mélange de matières de moulage s'effectuant dans l'outil de moulage en introduisant l'amine tertiaire ou un mélange d'amines tertiaires sous forme de gaz dans le mélange de matières de moulage se trouvant dans un outil de moulage,
    - conjointement avec au moins un solvant gazeux (B) soit
    - en introduisant d'abord l'amine tertiaire gazeuse dans le mélange de matières de moulage et par la suite au moins un solvant gazeux (B), soit
    - en introduisant d'abord le solvant gazeux (B) dans le mélange de matières de moulage et par la suite l'amine tertiaire gazeuse,
    le cas échéant, à chaque fois, conjointement avec un gaz support et
    (A) et (B) étant mis en œuvre en un rapport en poids de 95 : 5 à 5 : 95 et l'amine (A) se dissolvant totalement dans le solvant (B) à température ambiante (25°C) et le solvant (B) présentant un point d'ébullition compris entre 20°C et 220°C, mesuré sous pression normale (1013 mbar), des solvants polaires, des alkylsilanes, des alcoxysilanes, des alkylalcoxysilanes mixtes, des solvants hydrocarbonés aromatiques, cycloaliphatiques et aliphatiques ainsi que des mélanges de classes de substances citées étant utilisés comme solvants (B).
  2. Procédé selon la revendication 1, dans lequel les amines tertiaires (A) sont choisies à partir d'un ou de plusieurs éléments du groupe : triméthylamine (TMA), diméthyléthylamine (DMEA), diméthyl-n-propylamine (DMPA), diméthyl-iso-propylamine (DMIPA), diéthylméthylamine (DEMA), triéthylamine (TEA), tri-n-propylamine, triisopropylamine, tri-n-butylamine et tri-iso-butylamine.
  3. Procédé selon la revendication 1 ou 2, dans lequel le solvant (B) est caractérisé par au moins l'une des caractéristiques suivantes, indépendamment les unes des autres :
    a) le solvant (B) présente un point d'ébullition compris entre 20°C et 190°C et de préférence entre 20°C et 160°C, respectivement mesuré sous pression normale (1013 mbar) ;
    b) le solvant (B) est un solvant polaire et de préférence un orthoester ou un alkylsilane ayant le cas échéant jusqu'à 3 groupes de H ou un alkylalcoxysilane ayant au moins un groupe alkyle ou un alcoxysilane ayant au moins un groupe H ou leurs mélanges ;
    c) le solvant (B) est un solvant hydrocarboné aromatique, cycloaliphatique ou aliphatique, y compris leurs mélanges.
  4. Procédé selon au moins l'une des revendications précédentes, dans lequel le solvant (B) est choisi parmi un ou plusieurs éléments du groupe triméthylorthoformiate, triéthylorthoformiate, méthyltriméthoxysilane, méthyltriéthoxysilane, éthyltriméthoxysilane, éthyltriéthoxysilane et propyltriméthoxysilane.
  5. Procédé selon au moins l'une des revendications précédentes, dans lequel au moins l'un des composants (P) et/ou (I) contient un solvant, de préférence un ester ou un hydrocarbure aromatique ou les deux, notamment au moins le composant polyol (P), et de préférence le composant isocyanate (I) contient jusqu'à 40 % en poids de solvant, notamment jusqu'à 30 % en poids, par rapport au composant isocyanate.
  6. Procédé selon au moins l'une des revendications précédentes, dans lequel le mélange de matières de moulage contient au moins :
    plus de 20 % en poids, de préférence de 30 % à 60 % en poids, de composés isocyanate (I) ayant au moins 2 groupes isocyanate par molécule par rapport au liant.
  7. Procédé selon au moins l'une des revendications précédentes, dans lequel (A) et (B) sont mis en œuvre en un rapport en poids de 80 : 20 à 20 : 80, et de manière particulièrement préférée de 70 : 30 à 30 : 70.
  8. Procédé selon au moins l'une des revendications précédentes, dans lequel le composant isocyanate contient des di- ou polyisocyanates aromatiques.
  9. Procédé selon au moins l'une des revendications précédentes, dans lequel la résine phénolique peut être obtenue par conversion d'un composé phénol avec un composé aldéhyde dans un milieu faiblement acide en utilisant des catalyseurs de métaux de transition,
    i) le composé phénol étant de préférence choisi parmi parmi un ou plusieurs éléments du groupe suivant : phénol, o-crésol, p-crésol, bisphénol-A ou cardanol ; ou
    ii) le catalyseur de métaux de transition étant de préférence un composé de zinc, en particulier de l'acétate de zinc dihydraté.
  10. Procédé selon au moins l'une des revendications précédentes, dans lequel la résine phénolique est une résine d'éther benzylique, les groupes méthylol sont de préférence éthérifiés totalement ou partiellement avec un alcool en C1 à C8, de préférence au moins 20 % en mole de groupes méthylol, et indépendamment de cela, avec de préférence respectivement une teneur en eau inférieure à 0,5 % en poids.
  11. Procédé selon la revendication 9, dans lequel le composé aldéhyde est un aldéhyde de formule :

            R-CHO,

    dans laquelle R représente un atome d'hydrogène ou un reste de carbone avec de préférence 1 à 8, particulièrement préférentiellement 1 à 3 atomes de carbone.
  12. Procédé selon au moins l'une des revendications précédentes, dans lequel le mélange de matières de moulage contient, par rapport au liant :
    de 8 % en poids à 70 % en poids, en particulier 10 à 62 % en poids, de composés polyol, en particulier de résines phénoliques, ou leurs produits de conversion ;
    de 13 à 78 % en poids, en particulier 17 à 70 % en poids, de composés isocyanate, et/ou leurs produits de conversion ; et
    de 2 à 57 % en poids, en particulier 3 à 53 % en poids, de solvant pour le ou les composés polyol et/ou le ou les composés isocyanate.
  13. Procédé selon au moins l'une des revendications précédentes, dans lequel la matière de base de moulage réfractaire est choisie parmi l'olivine, la chamotte, la bauxite, les microsphères creuses de silicate d'aluminium, les perles de verre, le granulé de verre, les matières de base de moulage céramiques synthétiques et/ou le dioxyde de silicium, en particulier sous la forme de sable de minerai de quartz, de zirconium ou de chrome.
  14. Procédé selon au moins l'une des revendications précédentes, dans lequel un gaz support est mis en œuvre et le gaz support est l'air, l'argon ou l'azote ou le dioxyde de carbone ou de l'air enrichi en dioxyde de carbone.
  15. Kit pour la fabrication d'un liant pour des mélanges de matière de moulage, comprenant, présentés séparément les uns des autres, les composants suivants :
    (a) au moins un composé polyol, qui est exempt de composés isocyanate, contenant au moins une résine phénolique (P) comme composé polyol ayant au moins 2 groupes hydroxy par molécule ;
    (b) au moins un composé isocyanate, qui est exempt de composés polyol, contenant un ou plusieurs composés isocyanate (I) ayant au moins 2 groupes isocyanate par molécule,
    (c) au moins un composant catalyseur contenant une ou plusieurs amines tertiaires (A) comme catalyseur,
    caractérisé en ce que le kit contient en outre
    (d) un composant de solvant, contenant un ou plusieurs solvants (B) pour l'amine tertiaire (A) ou
    un ou plusieurs solvants (B) faisant partie du composant catalyseur,
    (A) et (B) étant mis en œuvre en un rapport en poids de 95 : 5 à 5 : 95 et le solvant (B) présentant un point d'ébullition compris entre 20°C et 220°C, mesuré sous pression normale (1013 mbar), et l'amine (A) se dissolvant totalement dans le solvant (B) à température ambiante (25°C) et
    des solvants polaires, des alkylsilanes, des alcoxysilanes, des alkylalcoxysilanes mixtes, des solvants hydrocarbonés aromatiques, cycloaliphatiques et aliphatiques ainsi que des mélanges des classes de substances citées étant utilisés comme solvants (B).
  16. Kit selon la revendication 15, dans lequel le solvant (B) est un solvant polaire et est de préférence
    - un orthoester ou
    - un alkylsilane ayant jusqu'à 3 groupes de H ou
    - un alkylalcoxysilane ayant au moins un groupe alkyle ou
    - un alcoxysilane ayant au moins un groupe de H ou
    - leurs mélanges.
  17. Kit selon la revendication 15 ou 16, dans lequel le solvant (B) est choisi parmi un ou plusieurs éléments du groupe triméthylorthoformiate, triéthylorthoformiate, méthyltriméthoxysilane, méthyltriéthoxysilane, éthyltriméthoxysilane, éthyltriéthoxysilane et propyltriméthoxysilane.
EP16722038.3A 2015-03-02 2016-03-02 Procédé de durcissement de liants au polyuréthane dans des mélanges de matériaux ce moulage par introduction d'amines tertiaires et de solvants et kit pour la mise en uvre du procédé Active EP3265254B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015102952.9A DE102015102952A1 (de) 2015-03-02 2015-03-02 Verfahren zur Aushärtung von Polyurethan-Bindemitteln in Formstoffmischungen durch Einleiten tertiärer Amine und Lösungsmittel und Kit zur Durchführung des Verfahrens
PCT/DE2016/000092 WO2016138886A1 (fr) 2015-03-02 2016-03-02 Procédé de durcissement de liants au polyuréthane dans des mélanges de matériaux ce moulage par introduction d'amines tertiaires et de solvants et kit pour la mise en œuvre du procédé

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EP3265254A1 EP3265254A1 (fr) 2018-01-10
EP3265254B1 true EP3265254B1 (fr) 2022-02-02

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EP (1) EP3265254B1 (fr)
DE (1) DE102015102952A1 (fr)
WO (1) WO2016138886A1 (fr)

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CN108467279A (zh) * 2018-05-31 2018-08-31 武汉钢铁有限公司 用于中间包包盖的轻量化保温浇注料及其制备方法

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US3485797A (en) 1966-03-14 1969-12-23 Ashland Oil Inc Phenolic resins containing benzylic ether linkages and unsubstituted para positions
US3429848A (en) 1966-08-01 1969-02-25 Ashland Oil Inc Foundry binder composition comprising benzylic ether resin,polyisocyanate,and tertiary amine
FR2031636A5 (en) * 1969-01-16 1970-11-20 Plastimer Composition for foundry sand binders and - preparation of cores and moulds by cold rapid
GB1365094A (en) * 1971-08-03 1974-08-29 Ciba Geigy Ag Synthetic resin compositions
US4268425A (en) 1979-05-14 1981-05-19 Ashland Oil, Inc. Phenolic resin-polyisocyanate binder systems containing a drying oil and use thereof
US4540724A (en) 1984-01-30 1985-09-10 Ashland Oil Inc. Phenolic resin-polyisocyanate binder systems containing a phosphorus halide and use thereof
US4602069A (en) 1984-04-11 1986-07-22 Ashland Oil, Inc. Phenolic resin-polyisocyanate binder systems containing a phosphorus based acid
US4546124A (en) 1984-10-12 1985-10-08 Acme Resin Corporation Polyurethane binder compositions
US5447968A (en) 1993-07-23 1995-09-05 Ashland Inc. Polyurethane-forming binder systems containing 2,2'-dipyridyl, 1,10-phenanthroline, and their substituted alkyl derivatives
DE19713096A1 (de) 1997-03-27 1998-10-01 Sueddeutsche Kalkstickstoff Ölfreie Glycerophospholipid-Formulierungen und Verfahren zu deren Herstellung
DE19850833C2 (de) 1998-11-04 2001-06-13 Ashland Suedchemie Kernfest Bindemittelsystem zur Herstellung von Kernen und Gießformen auf Polyurethanbasis, deren Verwendung und Verfahren zur Herstellung eines Gießformteils auf Polyurethanbasis
DE19925115A1 (de) 1999-06-01 2000-12-07 Huettenes Albertus Bindemittelsystem für Formstoff-Mischungen zur Herstellung von Formen und Kernen
US6365646B1 (en) * 1999-12-08 2002-04-02 Borden Chemical, Inc. Method to improve humidity resistance of phenolic urethane foundry binders
WO2002060985A1 (fr) * 2001-01-31 2002-08-08 Borden Chemical, Inc. Liants de fonderie a base d'urethane phenolique contenant du benzoate de methyle
US20050020723A1 (en) 2003-07-24 2005-01-27 Chia-Hung Chen Stabilized phenolic resole resin compositions and their use
PL1955792T3 (pl) 2007-01-22 2019-11-29 Arkema France Sposób wytwarzania kształtowanych rdzeni odlewniczych i odlewania metali
US9327346B2 (en) 2011-07-19 2016-05-03 Ask Chemicals L.P. Method for curing cold-box foundry shape with gaseous catalyst

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DE102015102952A1 (de) 2016-09-08
WO2016138886A1 (fr) 2016-09-09

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