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EP2651581B1 - Liant durcissant à froid à faibles émissions pour l'industrie de la fonderie - Google Patents

Liant durcissant à froid à faibles émissions pour l'industrie de la fonderie Download PDF

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Publication number
EP2651581B1
EP2651581B1 EP11808845.9A EP11808845A EP2651581B1 EP 2651581 B1 EP2651581 B1 EP 2651581B1 EP 11808845 A EP11808845 A EP 11808845A EP 2651581 B1 EP2651581 B1 EP 2651581B1
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EP
European Patent Office
Prior art keywords
acid
weight
mixture
mixture according
furfuryl alcohol
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EP11808845.9A
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German (de)
English (en)
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EP2651581A1 (fr
Inventor
Christian Fourberg
Gérard LADÉGOURDIE
Norbert Benz
Eckard Piech
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Huettenes Albertus Chemische Werke GmbH
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Huettenes Albertus Chemische Werke GmbH
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Priority to PL18214344T priority Critical patent/PL3495073T3/pl
Priority to PL11808845T priority patent/PL2651581T3/pl
Priority to EP18214344.6A priority patent/EP3495073B1/fr
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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
    • B22C1/224—Furan polymers

Definitions

  • the present invention relates primarily to a mixture suitable for use in the no-bake process for the production of cores and molds for the foundry industry, and to a reaction mixture comprising such a mixture and an acid hardener (i.e., a catalyst acid). Furthermore, the present invention relates to a method for producing a mixture according to the invention and to a method for producing a casting mold or a core. The invention also relates to a casting mold or a core for producing metal bodies and to a kit comprising a mixture according to the invention and certain acid hardeners. In addition, the invention relates to the use of a mixture according to the invention as cold curing binder and the use of such mixtures or reaction mixtures in a no-bake process for the production of metal bodies. Further aspects of the present invention will become apparent from the description, the embodiments and the claims.
  • the melt liquefied materials, ferrous metals or non-ferrous metals are converted into shaped objects with specific workpiece properties.
  • the casting molds are divided into lost molds that are destroyed after each casting, and permanent molds, with each of which a large number of castings can be produced.
  • the Lost forms usually consist of a refractory, granular molding material, which is solidified with the aid of a hardenable binder.
  • Shapes are negatives, they contain the emptying cavity, which results in the casting to be produced.
  • the inner contours of the future casting are formed by cores. In the manufacture of the mold, the cavity is shaped into the molding material by means of a model of the casting to be manufactured. Inner contours are represented by cores formed in a separate core box.
  • both organic and inorganic binders can be used, the curing of which can be effected by cold or hot processes.
  • Cold processes are processes in which the curing takes place 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 is heated to a sufficiently high temperature after molding to drive off, for example, the solvent contained in the binder, or to initiate a chemical reaction by which the binder is cured by crosslinking.
  • the production of the casting molds can be carried out in such a way that the molding material is first mixed with the binder, so that the grains of the refractory molding material are coated with a thin film of the binder.
  • the molding material mixture obtained from molding material and binder can then be introduced into a corresponding mold and optionally compacted in order to achieve a sufficient stability of the casting mold.
  • the mold is cured, for example by heating it or by adding a catalyst which effects a curing reaction. If the mold has reached at least a certain initial strength, it can be removed from the mold.
  • the internal cavities are therefore imaged by cores solidified by cold box binders, a polyurethane based binder, while the outer contour of the casting is represented by lower cost molds, such as a Green sand mold, a form bound by a furan resin or a phenol resin, or by a steel mold.
  • lower cost molds such as a Green sand mold, a form bound by a furan resin or a phenol resin, or by a steel mold.
  • organic polymers are mostly used as binders for the refractory, granular molding material.
  • granular molding material often washed, classified quartz sand is used, but also other molding materials such. Zirconsande, Chromitsande, chamois, olivine sands, feldspat ambience sands and Andalusitsande.
  • the molding material mixture obtained from mold base and binder is preferably present in a free-flowing form.
  • organic binders such as polyurethane, furan resin or epoxy-acrylate used in which the curing of the binder by addition of a catalyst.
  • Phenol resins acid-curing or - in the Alpha-Set-process ester-curing are also used.
  • binder depends on the shape and size of the casting to be produced, the conditions of production and the material used for the casting. For example, in the production of small castings that are produced in large numbers, polyurethane binders are often used because they allow fast cycle times and thus also a series production.
  • Processes in which the curing of the molding material mixture by heat or by subsequent addition of a catalyst have the advantage that the processing of the molding material mixture is not subject to any special time restrictions.
  • the molding material mixture can first be produced in larger quantities, which are then processed within a longer period of time, usually several hours.
  • the curing of the molding material mixture takes place only after molding, with a rapid reaction is sought.
  • the mold can be removed immediately after curing from the mold so that short cycle times can be realized. However, in order to obtain a good strength of the mold, the curing of the molding material mixture must be uniform within the mold. If the curing of the molding material mixture by subsequent addition of a catalyst, the mold is gassed after molding with the catalyst. For this purpose, the gaseous catalyst is passed through the casting mold.
  • the molding material mixture cures directly after contact with the catalyst and can therefore be removed very quickly from the mold.
  • the gassing times are prolonged, but can still arise sections in the mold, the very poor or not at all of the gaseous catalyst be achieved.
  • the amount of catalyst therefore increases sharply with increasing size of the mold.
  • the weight of the cores is often about 1000 kg or more.
  • methods in which the hardening with gas or by heat such large cores are difficult or impossible to produce from a technical point of view.
  • cold-curing methods are used.
  • the refractory base stock e.g., sand
  • the refractory base stock may be first mixed with the binder and then the hardener added.
  • the refractory base stock e.g., sand
  • it may, especially in the production of molds for large castings, come because of a partial, local too high concentration of the curing agent to partial hardening or crosslinking of the binder, whereby an inhomogeneous molding material would be obtained.
  • the curing of the molding material mixture begins immediately after its preparation.
  • the components of the molding material mixture should be coordinated.
  • the reaction rate for a given amount of the binder and the refractory base molding material for example, by the nature and amount of the catalyst or by Adding delaying components influence.
  • the processing of the molding material mixture should be carried out under very controlled conditions, since the rate of curing is influenced for example by the temperature of the molding material mixture.
  • the "classic" no-bake binders are often based on furan resins and phenolic resins. They are often offered as systems (kits) wherein one component comprises a reactive furan resin and the other component comprises an acid, which acid acts as a catalyst for the curing of the reactive resin component.
  • Furan no-bake binders are most often prepared by first producing precondensates of, for example, urea, formaldehyde, and furfuryl alcohol under acidic conditions. These precondensates are then diluted with furfuryl alcohol.
  • Furan no-bake binders are regularly cured with an acid. This acid catalyzes the crosslinking of the reactive furan resin. It should be noted that, depending on the type of binder, certain amounts of acid should not be exceeded, since alkaline components, which may be present in the refractory base molding material, can partially neutralize the acid.
  • acids are sulfonic acids, phosphoric acid or sulfuric acid. In some specific cases, combinations of these are used, inter alia, in combination with other carboxylic acids. Further, certain "curing moderators" can be added to the furan no-bake binder.
  • the selection of the acid catalyst for curing has a significant influence on the curing behavior of the binder, the properties of the molding material mixture and the casting mold or the core obtainable therefrom.
  • the rate of curing can be influenced by the amount and the strength of the acid.
  • High amounts of acid or stronger acids lead to an increase in the curing rate.
  • the processing time of the molding material mixture is shortened too much, so that the workability is greatly impaired or even processing is no longer possible.
  • the binder such as a furan resin
  • the binder also become brittle upon curing, which adversely affects the strength of the mold.
  • too small amounts of acid catalyst the resin is not completely cured (or the curing takes a long time), resulting in lower strength of the mold.
  • reclaimed mold base material eg sand
  • refractory Form base materials that have been solidified with furan no-bake binders can be worked up very well again.
  • the workup is carried out either mechanically by mechanically rubbing off a shell formed from residual binder or by thermally treating the used sand. With mechanical workup or with combined mechanical / thermal processes, return rates of up to almost 100% can be achieved.
  • Phenolic resins the second large group of acid-catalyzed curable no-bake binders, contain resoles as reactive resin components, ie phenolic resins prepared with a molar excess of formaldehyde. Phenolic resins show lower reactivity compared to furan resins and require strong sulfonic acids as catalysts. Phenolic resins show a relatively high viscosity, which increases even more with prolonged storage of the resin.
  • the molding compound After the phenol no-bake binder has been applied to the refractory base molding material, the molding compound should be processed as promptly as possible so as not to suffer deterioration in the quality of the molding compound due to premature curing, resulting in deterioration of the strength of the molding compound mixture produced molds can lead.
  • the flowability of the molding material mixture is usually worse than a comparatively produced molding material with a furan no-bake binder. In the production of the mold, the molding material mixture must therefore be carefully compacted in order to achieve a high strength of the mold can.
  • the preparation and processing of such a molding material mixture should take place at temperatures in the range of 15 to 35 ° C. If the temperature is too low, the molding material mixture can be processed worse because of the high viscosity of the phenol no-bake resin. At temperatures of more than 35 ° C, the processing time is shortened by premature curing of the binder.
  • the acid used as catalyst in the case of furan or phenol no-bake processes has a very great influence on the properties of the casting mold.
  • the acid must have sufficient strength to ensure a sufficient rate of reaction in the curing of the mold.
  • the curing should be well controllable, so that also sufficiently long processing times can be set. This is particularly important in the production of molds for very large castings, the construction requires a longer period.
  • the acid must not accumulate in the regenerate in the regeneration of scrap materials (i.e., mold materials already used to make lost molds or cores, such as old sands). If acid is introduced into the molding material mixture via the regenerate, this shortens the processing time and leads to a deterioration in the strength of the casting mold produced from the regenerate.
  • scrap materials i.e., mold materials already used to make lost molds or cores, such as old sands.
  • Phosphoric acid is, as already explained, only for the curing of certain furan resin qualities.
  • phosphoric acid is not suitable for the curing of phenolic resins.
  • phosphoric acid tends to accumulate in the regenerate, making it difficult to reuse the regenerate.
  • Sulfuric acid during casting and during thermal regeneration leads to the emission of sulfur dioxide, which has corrosive properties, is harmful to health and represents an odor nuisance.
  • sulfuric acid see below.
  • no-bake binders have one or more of the following disadvantages or undesirable properties: too high a content of furfuryl alcohol, too high a content of water, too high a content of formaldehyde, too strong an odor, too high a content of ammonia and / or too high total content of nitrogen.
  • US 3,644,274 relates primarily to a no-bake process using certain mixtures of acid catalysts to cure for furfuryl alcohol-formaldehyde-urea resins.
  • US 3,806,491 relates to binders which can be used in the no-bake process.
  • the binders used there include products from the reaction of paraformaldehyde with certain ketones in a basic medium, as well as furfuryl alcohol and / or furan resins.
  • US 5,607,986 describes thermosetting binders for the production of molds and foundry cores in the "hot box” or “hot box” process based on furfuryl alcohol-formaldehyde phenolic resins prepared in the basic medium at pH's in the range of 8 to 9.
  • the binders according to US 5,607,986 also contained furfuryl alcohol and polyvinyl acetate.
  • US 5,491,180 describes resin binders suitable for use in the no-bake process.
  • the binders used there are based on 2,5-bis (hydroxymethyl) furan or methyl or ethyl ethers of 2,5-bis (hydroxymethyl) furan, wherein the binder 0.5 to 30 wt .-% water and regularly contain a high proportion on furfuryl alcohol.
  • EP 0 540 837 proposes low-emission, cold-curing binders based on furan resins and lignin from the Organosolv process.
  • the furan resins described there contain a high proportion of monomeric furfuryl alcohol.
  • EP 1 531 018 relates to no-bake foundry binder systems consisting of a furan resin and certain acid hardeners.
  • the binder systems described therein preferably comprise 60 to 80% by weight of furfuryl alcohol.
  • US 4,176,114 A discloses a method of making sand molds and cores.
  • sand is mixed with an acid-curing resin, which comprises "high viscosity poly furfuryl alcohol”. Curing then takes place by contacting the mixture with gaseous sulfur dioxide in the presence of an oxidizing agent.
  • US 5,741,914 A discloses resin-based binder compositions comprising reaction products of furfuryl alcohol with formaldehyde.
  • the binder compositions comprise, in part, a weak organic acid and in some cases only a small amount of formaldehyde.
  • the lowest possible total nitrogen content is desirable, since in particular a total nitrogen content of 4% by weight or higher in a no-bake binder can lead to casting defects.
  • a no-bake binder should have the lowest possible total nitrogen content, since there surface defects, such as "pinholes" (pinholes) occur as a casting error.
  • pinholes are the "water-nitrogen pinholes,” in which water vapor reacts with the iron and nitrogen-containing components to form metal oxides and nitrogen-hydrogen compounds that diffuse into the liquid metal, resulting in micropores.
  • ammonia content in no-bake binders for large-scale casting processes must also be kept as low as possible, and preference should be given to dispensing with the use of ammonia.
  • mixtures according to the invention and the reaction mixtures according to the invention can also be used in particular in the field of large-scale casting, preferably for producing molds and cores, in particular cores, having a weight of 800 kg or more, preferably 900 kg or more preferably 1000 kg or more.
  • US 2,343,972 describes resins obtained by reacting furfuryl alcohol and formaldehyde under heating in the presence of an acid such as lactic acid, formic acid or chloroacetic acid become. Concrete data on properties that are important for binders in the no-bake process are missing in US 2,343,972 ,
  • the phenol compounds are preferably phenol compounds having 6 to 25 carbon atoms and / or one, two, three or four hydroxyl groups bonded directly to an aromatic ring, preferably selected from the group consisting of phenol, optionally C 1 -C 4 -alkyl- mono- or disubstituted dihydroxybenzenes, trihydroxybenzenes, methylphenols and bisphenols, more preferably selected from the group consisting of phenol, o-dihydroxybenzene, m-dihydroxybenzene (resorcinol), p-dihydroxybenzene, 5-methylresorcinol, 5-ethylresorcinol, 2.5- Dimethylresorcinol, 4,5-dimethylresorcinol, 1,2,3-trihydroxybenzene, 1,3,5-trihydroxybenzene o-cresol, m-cresol, p-cresol and bisphenol A. Particularly preferred are phenol, resorcinol and bisphenol A.
  • component (b-1) and, if present, component (b-2) of a mixture according to the invention can prepare component (b-1) and, if present, component (b-2) of a mixture according to the invention separately and in a targeted manner.
  • the constituents (b-1) and (b-2) may initially (preferably in the proportions specified as preferred) initially mixed together and as component (b) or alternatively in separate form as (b-1) and (b-2) be introduced into a mixture according to the invention.
  • a preferred mixture according to the invention is characterized in that the mixture at 20 ° C has a viscosity of at most 300 mPas in accordance with DIN 53019-1: 2008-09, preferably at most 250 mPas, preferably at most 200 mPas, more preferably at most 150 mPas.
  • the speed used in the measurement of the viscosity with the rotational viscometer was at a viscosity of the sample to be examined of less than 100 mPas at 20 ° C and 800 rpm (revolutions / min.); at a viscosity of the test sample of 100 to 800 mPas was measured at a speed of 500 rpm at 20 ° C.
  • Organic acids having a pKa in these ranges are particularly suitable condensation catalysts for preparing the reaction products of formaldehyde with furfuryl alcohol and optionally other constituents of component (b-1).
  • phase compatibility of benzoic acid in the mixture according to the invention has proven to be particularly good in own investigations; no crystallization reaction was observed.
  • the total amount of constituent (d) is from 0.5 to 8% by weight, preferably from 0.75 to 5% by weight, more preferably from 1 to 3% by weight, based in each case on the total mass of the mixture ,
  • a preferred mixture according to the invention is therefore one in which component (d) comprises an acid or a salt selected from the group consisting of benzoic acid, lactic acid, citric acid, phthalic acid, 2,4-dihydroxybenzoic acid, salicylic acid and their salts.
  • Salicylic acid is somewhat less preferred because it adversely affects the shelf life of a mixture according to the invention in some cases and in some cases, a comparatively low water miscibility of mixtures according to the invention prepared with salicylic acid was found.
  • the total content of nitrogen can be determined, for example, by elemental analysis or by the so-called Kjeldahl method (according to DIN 16916-02, point 5.6.4), the elemental analysis for determining the total nitrogen content of a mixture according to the invention being preferred.
  • a preferred mixture according to the invention is a mixture whose total content of compounds having a molecular weight of greater than 5000 daltons (g / mol) is at most 3% by weight, preferably at most 1% by weight, determined by gel permeation chromatography according to DIN 55672-1 (February 1995), where the weight percentages refer to the total mass of the mixture.
  • the total content of compounds having a molecular weight of greater than 3000 daltons (g / mol) is at most 5% by weight, preferably at most 2% by weight.
  • the weight average molecular weight M.sub.w (weight average) of constituent (b-1) is in the range from 200 to 600 g / mol, more preferably in the range from 225 to 500 g / mol, particularly preferably in the range from 250 to 450 g / mol, most preferably in the range of 300 to 425 g / mol.
  • the ratio of molar mass average Mw to molar mass average Mn of the two constituents (a) and (b-1) together is in the range from 5: 1 to 9: 8, more preferably in the range from 4: 1 to 6 : 5, more preferably in the range of 3: 1 to 4: 3, particularly preferably in the range of 2: 1 to 3: 2.
  • the mixtures according to the invention contain one or more adhesion promoters selected from the group of silanes.
  • mixtures according to the invention comprising one or more silanes, in particular one or more silanes from the group of N-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldiethoxysilane and / or N-aminopropyltriethoxysilane have achieved particularly good results in the production of casting molds or cores, especially with N-aminopropylmethyldiethoxysilane and / or N-aminopropyltriethoxysilane.
  • the mixtures according to the invention may contain further additives.
  • they may contain, for example, diols or aliphatic polyols as curing moderators, which lead to a lowering of the reactivity.
  • the proportion of these curing moderators in a mixture according to the invention should not be too high, since such curing moderators can lead to a reduction in the strength of the casting mold in the unfavorable case.
  • the proportion of curing moderators is therefore preferably at most 10 wt .-%, preferably at most 5 wt .-%, based on the total mass of the mixture.
  • Preferred organic curing moderators of component (f) are glycols having 2 to 12 carbon atoms, more preferably glycols having 2 to 6 carbon atoms, especially preferred is ethylene glycol, i. Monoethylene glycol.
  • Component (k) comprises or consists preferably of phenol, resorcinol and / or bisphenol A, since in particular these free phenols show a high affinity for reaction with formaldehyde and react rapidly with any formaldehyde still present, whereby the emission, in particular of formaldehyde, is further reduced can be, especially during the curing process.
  • Bisphenol A is particularly advantageous in this context, since it-presumably because of its diphenylmethane skeleton-leads to a higher strength of the resulting molds and cores after curing of a mixture according to the invention as a constituent of a reaction mixture according to the invention.
  • a higher thermal stability is observed, in particular during the casting process, whereby a further positive effect with respect to the emission can be achieved.
  • benzyl alcohol which serves as component (m) mainly as solvent in a mixture according to the invention, further improves the desired properties of a mixture according to the invention.
  • the advantage lies inter alia in the very good compatibility with the other constituents of a mixture according to the invention. It has also been found that lowering the viscosity, i. Also the viscosity value, takes place and beyond the storage stability of a mixture according to the invention is further improved.
  • the flash point of a mixture according to the invention is increased and at the same time the odor is reduced.
  • the cold curing can be undesirably delayed significantly, which is observed only to a lesser extent in benzyl alcohol.
  • a preferred mixture according to the invention has a pH in the range from 4 to 10 at 25 ° C., preferably in the range from 5 to 9.5.
  • the reaction mixture preferably has a content of free formaldehyde of at most 0.4% by weight, the percentages by weight being based on the total mass of the reaction mixture minus the total mass of refractory granular substances in the reaction mixture.
  • Component (ii) is also referred to as acid hardener.
  • the acid hardener allows the curing of a mixture according to the invention at low temperatures, typically at ambient temperature.
  • the amount of component (ii) used is preferably such that hardening of the mixture according to the invention already results at low temperatures, typically at ambient temperature, in particular at 25 ° C.
  • the total amount of acid used with a pKa of less than 2 at 25 ° C is such that the pH of the resulting reaction mixture is less than 3, preferably even less than 1.
  • the acid hardener then advantageously causes a curing of the mixture according to the invention already at 25 ° C.
  • Component (ii) of a reaction mixture according to the invention preferably comprises or consists preferably of organic sulfonic acids.
  • organic sulfonic acids such as benzenesulfonic acid, toluenesulfonic acids, xylenesulfonic acids or cumene sulfonic acid [2 (or 4) - (isopropyl) -benzenesulfonic acid ]
  • methanesulfonic acid and ethanesulfonic acid are also preferred.
  • the organic sulfonic acids are readily available and have a sufficiently high acid strength to achieve the desired curing of a mixture according to the invention in the no-bake process. In the context of the present invention, the best results were achieved with p-toluenesulfonic acid.
  • the acid of component (ii) is selected from the group of organic acids, preferably of organic sulfonic acids, preferably selected from the group consisting of benzenesulfonic acid, Toluenesulfonic acids, xylenesulfonic acids, cumene sulfonic acid [2 (or 4) - (isopropyl) benzenesulfonic acid ] and methanesulfonic acid, particularly preferred is p-toluenesulfonic acid.
  • organic acids preferably of organic sulfonic acids, preferably selected from the group consisting of benzenesulfonic acid, Toluenesulfonic acids, xylenesulfonic acids, cumene sulfonic acid [2 (or 4) - (isopropyl) benzenesulfonic acid ] and methanesulfonic acid, particularly preferred is p-toluenesulfonic acid.
  • the reaction mixture comprises (i) no sulfuric acid or (ii) sulfuric acid in an amount of at most 1 wt .-%, preferably at most 0.5 wt .-%, wherein the weight percentages are based on the total mass of the reaction mixture minus the total mass of ( optional) refractory granular substances in the reaction mixture.
  • the reaction mixture comprises no phosphoric acid and no hydrochloric acid; more preferably, the reaction mixture according to the invention comprises no mineral acids at all.
  • sulfuric acid the strength of the acid is in some cases problematic. Experience has shown that binders which are cured only with sulfuric acid, a "spontaneously" generated polymer network with inevitably more defects.
  • Aromatic sulfonic acids are very good resin-miscible (have a good phase compatibility).
  • the ongoing hardening is more orderly, more homogeneous, more complete and also better controllable compared to sulfuric acid.
  • part of the organically bound sulfur evaporates during the casting process as SO 2 from the molding material out. As a result, a lower desulfurization is observed.
  • the less corrosive sulfonic acids are also positive in comparison with sulfuric acid (tool life is positively influenced).
  • a reaction mixture according to the invention preference is given to using acid having a pKa of less than 2 at 25 ° C. in a total amount of from 10 to 80% by weight, preferably from 15 to 70% by weight, preferably from 20 to 60% by weight. -%, particularly preferably from 25 to 50 wt .-%, each based on the total mass of formaldehyde and the components (a), (b), (c), (d), (e), (f), (g ), (h), (j), (k) and (n) the mixture of the invention (component (i)).
  • the total amount of acid or acids having a pKa of less than 2 at 25 ° C. in a reaction mixture according to the invention is preferably in the range from 9 to 45% by weight, preferably from 13 to 41% by weight, preferably from 16 to 38% by weight .-%, particularly preferably from 20 to 33 wt .-%, based on the total mass of the reaction mixture according to the invention less the total mass of any existing refractory granular materials.
  • reaction mixture which additionally comprises (Iii) one or more refractory granular materials, preferably sand, preferably in an amount of 80 wt .-% or more, preferably 95 wt .-% or more, based on the total weight of the reaction mixture.
  • a reaction mixture according to the invention comprises, besides a mixture according to the invention (constituent (i)), an acid hardener (constituent (ii)) and a refractory granular substance (constituent (iii)), a molding material mixture is present.
  • reaction mixtures according to the invention which do not comprise sulfur dioxide or comprise no peroxide (in particular methyl ethyl ketone peroxide), preferably those which comprise neither sulfur dioxide nor a peroxide (in particular methyl ethyl ketone peroxide).
  • Refractory mold raw materials which were solidified using a reaction mixture according to the invention in the no-bake process, can be worked up very well again. This is especially true for sand.
  • a reaction mixture according to the invention preferably comprises sand, preferably having a particle size in the range from 0.063 to 2 mm, preferably with a particle size in the range from 0.1 to 1 mm.
  • a reaction mixture according to the present invention preferably comprises 80% by weight or more of the component (iii), preferably 95% by weight or more, based on the total weight of the reaction mixture (i.e., the molding material mixture).
  • component (iii) comprises or consists of sand, preferably aluminum silicate sand, feldspar sand and / or quartz sand.
  • Component (iii) particularly preferably comprises quartz sand, more preferably component (iii) consists of quartz sand.
  • the invention further relates to a process for the preparation of a mixture according to the invention, preferably in one of the embodiments characterized as being preferred or particularly preferred, with the following step: (S-1) reacting furfuryl alcohol with formaldehyde and optionally further constituents in the presence of one or more organic acids having a pKa of greater than or equal to 2.5, preferably in the range of 2.75 to 6, preferably in the range of 3 to 5, at 25 ° C and / or their salts, wherein the molar ratio of the total amount of furfuryl alcohol used to the total amount of formaldehyde used is greater than or equal to 1, preferably in the range of 5: 1 to 1.1: 1, preferably in the range of 3: 1 to 1.25: 1 , more preferably in the range of 2: 1 to 3: 2.
  • Formaldehyde can be used both in monomeric form, for example in the form of a formalin solution, as well as in the form of its polymers, such as trioxane or paraformaldehyde, wherein according to the invention, the use of paraformaldehyde is preferred.
  • aldehydes can additionally be used. Suitable aldehydes are, for example, acetaldehyde, propionaldehyde, butyraldehyde, acrolein, crotonaldehyde, benzaldehyde, salicylaldehyde, cinnamaldehyde, glyoxal and mixtures of these aldehydes.
  • Particularly preferred organic acids having a pKa in the range of 3 to 5 at 25 ° C are selected from the group consisting of benzoic acid, lactic acid, citric acid, phthalic acid, 2,4-dihydroxybenzoic acid and salicylic acid, wherein benzoic acid, lactic acid, and citric acid more preferred, most preferred is benzoic acid.
  • a pH is adjusted in the range of 2.8 to 5, preferably in the range of 3.5 to 4.5, in each case measured at 20 ° C.
  • step (S-1) is carried out at a temperature in the range of 90 to 160 ° C, preferably at a temperature in the range of 100 to 150 ° C.
  • the total amount of furfuryl alcohol used is at least 50% by weight, preferably at least 55% by weight, and preferably in the range from 60 to 75% by weight, more preferably in the range from 62 to 72% by weight .-%, wherein the weight percentages are based on the total mass of the resulting mixture according to the invention.
  • a preferred mixture according to the invention (as defined above), preferably in one of the preferred embodiments, is a mixture preparable by a process according to the invention, preferably in one of the preferred embodiments.
  • the refractory molding base material according to the invention (constituent (iii) of a reaction mixture according to the invention) is first coated with the acid hardener (constituent (ii) of a reaction mixture according to the invention).
  • the binder ie a mixture according to the invention, component (i) of a reaction mixture according to the invention
  • the molding material mixture can then be shaped into a shaped body. Since binder and acid hardener are evenly distributed in the molding material mixture, the curing is largely uniform even with large moldings.
  • the curing is preferably carried out in the absence of sulfur dioxide.
  • a reaction mixture according to the invention is preferably prepared which then hardens without further ado.
  • the remarks on the reaction mixture according to the invention apply correspondingly to the process according to the invention.
  • a preferably molding material mixture is used, which is particularly suitable for the production of large casting molds and cores, wherein these casting molds and cores during casting show a reduced emission of defective compounds.
  • the invention also relates to a casting mold or a core for producing metal bodies, obtainable by curing a reaction mixture according to the invention, preferably in one of the embodiments characterized as being preferred.
  • the invention relates to the use of a mixture according to the invention, preferably in one of the embodiments marked as preferred, as cold-curing binder, preferably as a no-bake binder in the foundry, in particular in the production of metal bodies by means of a casting process, wherein the curing of Binder is preferably carried out without the use of gaseous sulfur dioxide.
  • the invention relates to the use of a mixture according to the invention or of a reaction mixture, preferably in each case in one of the preferred embodiments, in a no-bake process for the production of metal bodies, preferably in a no-bake process, in which no gaseous sulfur dioxide is used for curing, preferably in a no-bake process without gassing step.
  • Furfuryl alcohol (66.98% by weight), paraformaldehyde 91% (12.38% by weight), benzoic acid (1.56% by weight), urea (6.07% by weight), water (6 , 94% by weight), ethanol (2.98% by weight), monoethylene glycol (1.99% by weight), N-aminopropyltriethoxysilane (Dynasilan 1506) (0.40% by weight) sodium hydroxide solution 33% strength in water (0.70% by weight).
  • the reactor contents are stirred.
  • 223.2 kg of furfuryl alcohol and 5.2 kg of benzoic acid are mixed thoroughly (pH value: 3.7 to 4.2) and then 123.8 kg of paraformaldehyde are added.
  • the mixture is then heated to 100 to 110 ° C within 30-60 minutes and held this temperature for 60 minutes.
  • two further portions of furfuryl alcohol and benzoic acid are added to the reaction mixture at intervals.
  • the temperature is increased to about 135 ° C and the reaction mixture heated under reflux (duration: 3 to 5 hours, the reflux temperature drops slowly and continuously to about 125 ° C).
  • the resulting reaction mixture is cooled rapidly, added 60.7 kg of urea and cooled further.
  • the production of the molding material mixture was carried out in a laboratory mixer (BOSCH).
  • BOSCH laboratory mixer
  • the parts by weight of acid hardener specified in Table 2 were added to 100 parts by weight of quartz sand H32 (Quarzwerke Frechen) and mixed for 30 seconds.
  • the parts by weight of binder indicated in Table 2 were added and remixed for a further 45 seconds.
  • the resulting mixture was prepared at room temperature (18-22 ° C) and a relative humidity (RLF) of 20-55%.
  • the sand temperature was 18 - 22 ° C.
  • the molding material mixture was introduced by hand into the Ardriegelform and compacted with a hand plate.
  • the molding material mixture in a form (cup), 80 mm in height and 80 mm in diameter, compacted with a hand plate.
  • the surface is in particular Periods checked with a test nail. If the test nail no longer penetrates into the core surface, the curing time is given.
  • the respective flexural strength values were determined in accordance with the above-mentioned VDG leaflet P 72.
  • the 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.
  • the flexural strengths were after one hour, after two hours, after four hours and after 24 h after the preparation of the test material mixture (storage of the cores after demolding, each at room temperature 18-22 ° C, RLF 20-55%).
  • TRGS Technical Rule for Hazardous Substances
  • the valuation indices BI AGW were determined in accordance with TRGS 402 point 5.2.
  • the valuation indices BI other were determined in accordance with TRGS 402 point 5.3. It was based on the TRGS 402 in the January 2010 issue.
  • the mixtures according to the invention allow compliance with the limit BI total.
  • the storage stability was stored for a period of 6 months at a constant temperature of 20-22 ° C and examined at monthly intervals.
  • the viscosity of the cold resin KH-Y according to the invention was measured and the performance properties of a corresponding molding material mixture determined (as described above).
  • a molding material mixture was first prepared. 0.5 parts by weight of a 65% strength by weight solution of p-toluenesulfonic acid in water were first added to 100 parts by weight of quartz sand H32 (Quarzwerke Frechen) and mixed for 30 seconds. Subsequently, 1 part by weight of binder KH-Y was added and remixed for a further 45 seconds. The resulting molding material mixture was prepared at room temperature (20-22 ° C) and a relative humidity (RLF) of 40-55%. The sand temperature was 20 - 22 ° C.
  • the mixture according to the invention KH-Y2 has a very low total content of nitrogen, which is why this inventive no-bake binder is particularly suitable for iron and steel casting, especially for stainless steel casting.
  • Furfuryl alcohol (70.18 wt%), paraformaldehyde 91% (12.03 wt%), benzoic acid (1.64 wt%), bisphenol A (2.75 wt%), urea ( 1.72 wt.%), Water (5.14 wt.%), Ethanol (3.12 wt.%), Monoethylene glycol (1.00 wt.%), N-aminopropyltriethoxysilane (Dynasilan 1505) ( 0.40 wt%) potassium hydroxide 45% in water (2.02 wt%).

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Claims (20)

  1. Mélange destiné à être utilisé en tant que liant dans le procédé sans cuisson, comprenant
    (a) un alcool furfurylique monomère, dans lequel la quantité en alcool furfurylique monomère est égale à 25 % en poids au maximum,
    (b) 40 % en poids ou plus de produits de réaction de formaldéhyde, dans lequel les produits de réaction comprennent
    (b-1) des produits de réaction de formaldéhyde avec de l'alcool furfurylique et en option d'autres constituants, et
    (b-2) en option des produits de réaction de formaldéhyde avec un ou plusieurs autres composés, qui n'est pas ou ne sont pas de l'alcool furfurylique,
    (c) de l'eau, dans lequel la quantité en eau est égale à 20 % en poids au maximum,
    (d) un ou plusieurs acides organiques avec une valeur pKa supérieure ou égale à 2,5, de préférence située dans la plage allant de 2,75 à 6, de manière préférée située dans la plage allant de 3 à 5, à 25 °C, et/ou leurs sels,
    (e) un ou plusieurs promoteurs d'adhérence choisis parmi le groupe des silanes, de manière préférée du N-aminopropylméthyldiéthoxysilane, du N-aminoéthyl-3-aminopropyl-triméthoxysilane, du N-aminoéthyl-3-aminopropylméthyldiéthoxysilane et/ou du N-aminopropyltriéthoxysilane en une quantité globale allant de 0,1 à 3 % en poids,
    dans lequel le mélange présente une teneur en formaldéhyde libre de 0,5 % en poids au maximum, dans lequel les indications exprimées en pourcentages en poids se rapportent au poids total du mélange.
  2. Mélange selon la revendication 1, comprenant
    (a) un alcool furfurylique monomère, dans lequel la quantité en alcool furfurylique est égale à 24,75 % en poids au maximum, de préférence à 24,60 % en poids au maximum,
    et/ou
    (c) de l'eau, dans lequel la quantité en eau est égale à 15 % en poids au maximum,
    dans lequel les indications exprimées en pourcentages en poids se rapportent au poids total du mélange.
  3. Mélange selon la revendication 1 ou 2, dans lequel la quantité du constituant (b) est égale à 45 % en poids ou plus, de préférence à 50 % en poids ou plus, dans lequel les indications exprimées en pourcentages en poids se rapportent au poids total du mélange.
  4. Mélange selon l'une quelconque des revendications précédentes, dans lequel le constituant (b) comprend ou est constitué de
    (b-1) 40 % en poids ou plus, de préférence 45 % en poids ou plus, de manière préférée 50 % en poids ou plus, de produits de réaction d'alcool furfurylique avec du formaldéhyde et en option d'autres constituants, de préférence d'un ou de plusieurs autres aldéhydes, dont de préférence du glyoxal,
    (b-2) de produits de réaction, différents du constituant (b-1), de formaldéhyde avec un ou plusieurs autres composés, qui n'est ou ne sont pas de l'alcool furfurylique, dans lequel la quantité en lesdits autres produits de réaction est égale à 15 % en poids au maximum, de préférence à 12 % en poids au maximum, de manière préférée de 10 % en poids au maximum,
    dans lequel les indications exprimées en pourcentages en poids se rapportent au poids total du mélange.
  5. Mélange selon l'une quelconque des revendications précédentes, dans lequel le mélange présente à 20 °C une viscosité de 300 mPas au maximum selon la norme DIN 53019-1:2008-09, de préférence de 250 mPas au maximum, de manière préférée de 200 mPas au maximum, de manière davantage préférée de 150 mPas au maximum.
  6. Mélange selon l'une quelconque des revendications précédentes, dans lequel la teneur en formaldéhyde libre est égale à 0,4 % en poids au maximum, de préférence à 0,3 % en poids au maximum, dans lequel les indications exprimées en pourcentages en poids se rapportent au poids total du mélange.
  7. Mélange selon l'une quelconque des revendications précédentes, dans lequel le constituant (d) comprend un acide ou un sel choisi parmi le groupe constitué d'acide benzoïque, d'acide lactique, d'acide citrique, d'acide phtalique, d'acide 2,4-dihydroxybenzoïque, d'acide salicylique, et de leurs sels.
  8. Mélange selon l'une quelconque des revendications précédentes, dans lequel le constituant (b-1) comprend du bis(2,5-hydroxyméthyl)furane (BHMF), de préférence en une quantité d'au moins 1 % en poids, de manière préférée en une quantité allant de 5 à 40 % en poids, par rapport au poids total d'un mélange selon l'invention.
  9. Mélange selon l'une quelconque des revendications précédentes, dans lequel la teneur totale en composés avec un poids molaire supérieur à 5000 Daltons (g/mol), déterminé au moyen d'une chromatographie par perméation de gel selon la norme DIN 55672-1 (février 1995), est de l'ordre de 3 % en poids au maximum par rapport au poids total du mélange.
  10. Mélange selon l'une quelconque des revendications précédentes, dans lequel le rapport entre la valeur moyenne de poids molaire Mw et la valeur moyenne de poids molaire Mn du constituant (b-1) se situe dans la plage allant de 5:1 à 9:8, de manière davantage préférée dans la plage allant de 4:1 à 6:5, de manière particulièrement préférée dans la plage allant de 3:1 à 4:3, notamment de manière préférée dans la plage allant de 2:1 à 3:2.
  11. Mélange selon l'une quelconque des revendications précédentes, comprenant en supplément un ou plusieurs autres constituants, choisis parmi le groupe
    (f) des modérateurs de durcissement organiques, de préférence choisis parmi le groupe des glycols avec 2 à 12 atomes de C, de préférence en une quantité de 10 % en poids au maximum, par rapport au poids total du mélange,
    (g) des agents de solubilisation organiques inertes, de préférence choisis parmi le groupe des alcools R-OH, dans lequel R représente un radical alkyle en C1-C4, dont de préférence de l'éthanol,
    (h) des produits de réaction de l'alcool furfurylique et d'un ou de plusieurs aldéhydes avec 2 atomes de C ou plus, de préférence des produits de réaction d'alcool furfurylique et de glyoxal,
    (j) des composés organiques, qui présentent un ou plusieurs groupes H2N et/ou un ou plusieurs groupes HN, de préférence de l'urée,
    (k) des composés phénoliques, de préférence des composés phénoliques avec 6 à 25 atomes de C et/ou un, deux, trois ou quatre groupes hydroxyle liés directement à un cycle aromatique, de manière préférée choisis parmi le groupe constitué de phénol, éventuellement de dihydroxybenzènes mono- ou disubstitués par un alkyle en C1-C4, de trihydroxybenzènes, de méthylphénols et de bisphénols, de manière particulièrement préférée choisis parmi le groupe constitué de phénol, de o-dihydroxybenzène, de m-dihydroxybenzène, de p-dihydroxybenzène, de 5-méthylrésorcinol, de 5-éthylrésorcinol, de 2,5-diméthylrésorcinol, de 4,5-diméthylrésorcinol, de 1,2,3-trihydroxybenzène, de 1,3,5-trihydroxybenzène, de o-crésol, de m-crésol, de p-crésol et de bisphénol A,
    (m) de l'alcool benzylique,
    (b) des aldéhydes avec 2 atomes de C ou plus, de préférence choisis parmi le groupe constitué d'acétaldéhyde, de propionaldéhyde, de butyraldéhyde, d'acroléine, de crotonaldéhyde, de benzaldéhyde, de salicylaldéhyde, de zimtaldéhyde, de glyoxal et de mélanges desdits aldéhydes, de manière préférée de glyoxal.
  12. Mélange de réaction, comprenant
    (i) un mélange selon l'une quelconque des revendications précédentes,
    (ii) un acide, dans lequel l'acide présente à 25 °C une valeur pKa inférieure à 2, de préférence inférieure à 1,5, de manière préférée inférieure à 1,
    dans lequel le mélange de réaction présente de préférence une teneur en formaldéhyde libre de 0,4 % en poids au maximum, dans lequel les indications exprimées en pourcentages en poids se rapportent au poids total du mélange de réaction.
  13. Mélange de réaction selon la revendication 12, dans lequel le mélange de réaction ne comprend aucun acide sulfurique ou comprend de l'acide sulfurique en une quantité de 1 % en poids au maximum, de préférence en une quantité de 0,5 % en poids au maximum, dans lequel les indications exprimées en pourcentages en poids se rapportent au poids total du mélange de réaction moins le poids total en substances granulaires réfractaires dans le mélange de réaction.
  14. Mélange de réaction selon la revendication 12, dans lequel l'acide du composant (ii) est choisi parmi le groupe des acides organiques, de préférence des acides sulfoniques organiques, de préférence choisis parmi le groupe constitué d'acide benzènesulfonique, d'acides toluènesulfoniques, d'acides xylènesulfoniques, d'acide cumènesulfonique [acide 2(ou 4)-benzènesulfonique (isopropylique)] et d'acide méthanesulfonique, notamment de manière préférée est de l'acide p-toluènesulfonique.
  15. Mélange de réaction selon l'une quelconque des revendications précédentes, comprenant en supplément
    (iii) une ou plusieurs substances granulaires réfractaires, de préférence du sable, de manière préférée en une quantité de 80 % en poids ou plus, de manière préférée de 95 % en poids ou plus, par rapport au poids total du mélange de réaction.
  16. Procédé servant à fabriquer un mélange selon l'une quelconque des revendications 1 à 11, avec une étape suivante
    (S-1) de mise en réaction d'alcool furfurylique avec du formaldéhyde et en option d'autres constituants en présence d'un ou de plusieurs acides organiques avec une valeur pKa supérieure ou égale à 2,5 à 25 °C, et/ou de leurs sels, dans ce cadre de préférence d'un ou de plusieurs acides organiques tels que définis dans la revendication 7,
    dans lequel le rapport molaire entre la quantité utilisée au total en alcool furfurylique et la quantité utilisée au total de formaldéhyde est supérieur ou égal à 1, de préférence se situe dans la plage allant de 5:1 à 1,1:1, de manière préférée dans la plage allant de 3:1 à 1,25:1, de manière davantage préférée dans la plage allant de 2:1 à 3:2.
  17. Procédé servant à fabriquer un moule de coulée ou une partie centrale, de préférence un moule de coulée sans cuisson ou une partie centrale sans cuisson, pour fabriquer des corps métalliques, comprenant l'étape :
    - de durcissement, de préférence de durcissement catalysé par acide, d'un mélange selon l'une quelconque des revendications 1 à 11,
    ou
    - de durcissement du mélange de réaction selon l'une quelconque des revendications 12 à 15,
    dans lequel le durcissement est effectué de préférence à une température inférieure à 60 °C, de préférence située dans la plage allant de 0 à 50 °C, de manière préférée dans la plage allant de 10 à 40 °C.
  18. Utilisation d'un mélange selon l'une quelconque des revendications 1 à 11 en tant que liant durcissant à froid, de préférence en tant que liant sans cuisson dans un équipement de fonderie, en particulier lors de la fabrication de corps métalliques au moyen d'un procédé de coulée, dans laquelle le durcissement du liant est effectué de préférence sans utilisation de dioxyde sulfurique sous forme gazeuse.
  19. Utilisation d'un mélange selon l'une quelconque des revendications 1 à 11 ou d'un mélange de réaction selon l'une quelconque des revendications 12 à 15 dans un procédé sans cuisson servant à fabriquer des corps métalliques, de préférence dans un procédé sans cuisson, dans lequel aucun dioxyde sulfurique sous forme gazeuse n'est utilisé aux fins du durcissement, de préférence dans un procédé sans cuisson sans étape de gazage.
  20. Ensemble comprenant
    - en tant qu'un premier composant, un mélange selon l'une quelconque des revendications 1 à 11,
    - en tant qu'un deuxième composant une solution aqueuse d'un acide, dans lequel l'acide présente à 25 °C une valeur pKa inférieure à 2.
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Families Citing this family (23)

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Publication number Priority date Publication date Assignee Title
FR2997849B1 (fr) * 2012-11-09 2015-01-16 Oreal Composition comprenant un derive dicarbonyle et procede de lissage des cheveux a partir de cette composition
JP6363938B2 (ja) * 2013-12-25 2018-07-25 花王株式会社 鋳型造型用組成物
DE102014002679A1 (de) 2014-02-28 2015-09-03 Hexion GmbH Umsetzungsprodukt und Verwendung für die Herstellung von Gießereiformen und -kernen
KR101592882B1 (ko) * 2014-06-27 2016-02-15 주식회사 퓨어스피어 구형 푸란 수지 입자 제조방법
DE102014220632A1 (de) * 2014-10-10 2016-04-14 Hüttenes-Albertus Chemische Werke GmbH Verwendung einer basischen Zusammensetzung als Infiltrationsmittel für den Formstoff einer Gießform zur Vermeidung von weißen Belägen
US9725552B2 (en) 2014-10-14 2017-08-08 Industrial Technology Research Institute HMF-based phenol formaldehyde resin
EP3056296A1 (fr) 2015-02-13 2016-08-17 Cavenaghi SPA Mélange pour liant pour sable de fonderie
ITUB20150307A1 (it) 2015-04-24 2016-10-24 Cavenaghi S P A Sistema legante per fonderia a basso contenuto di formaldeide e procedimento per il suo ottenimento
CN106694793B (zh) * 2015-11-17 2019-12-03 胡坦斯·阿尔伯图斯化学厂有限公司 碱性组合物的应用、相应的方法、铸模和体系
DE102016202795A1 (de) 2016-02-23 2017-08-24 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Verwendung einer Zusammensetzung als Bindemittelkomponente zur Herstellung von Speiserelementen nach dem Cold-Box-Verfahren, entsprechende Verfahren und Speiserelemente
DE102016211971A1 (de) * 2016-06-30 2018-01-04 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Wässrige alkalische Bindemittelzusammensetzung zur Aushärtung mit Kohlendioxidgas sowie deren Verwendung, eine entsprechende Formstoffmischung zur Herstellung eines Gießereiformkörpers, ein entsprechender Gießereiformkörper sowie ein Verfahren zur Herstellung eines Gießereiformkörpers
DE102016211970A1 (de) * 2016-06-30 2018-01-18 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Wässrige alkalische Bindemittelzusammensetzung zur Aushärtung mit Kohlendioxidgas sowie deren Verwendung, eine entsprechende Formstoffmischung zur Herstellung eines Gießereiformkörpers, ein entsprechender Gießereiformkörper sowie ein Verfahren zur Herstellung eines Gießereiformkörpers
DE102016123051A1 (de) 2016-11-29 2018-05-30 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Aminosäure enthaltende Formstoffmischung zur Herstellung von Formkörpern für die Gießereiindustrie
DE102017112681A1 (de) * 2017-06-08 2018-12-13 Ask Chemicals Gmbh Verfahren zur Herstellung von dreidimensional geschichteten Formkörpern
CN108296426A (zh) * 2017-12-29 2018-07-20 天津宁康科技有限公司 一种铸造呋喃树脂用增强剂及其制备方法
CN108587537B (zh) * 2018-04-23 2021-01-15 太尔化工（南京）有限公司 一种用于单板层积材高强度粘胶剂的制备及使用方法
JP2020022985A (ja) * 2018-08-08 2020-02-13 花王株式会社 鋳型造型用粘結剤組成物
DE102020003562A1 (de) 2020-06-15 2021-12-16 Ask Chemicals Gmbh Verfahren zum schichtweisen Aufbau eines ausgehärteten dreidimensionalen Formkörpers, Formkörper, welcher dadurch erhalten werden kann, sowie dessen Verwendung
WO2022102089A1 (fr) * 2020-11-13 2022-05-19 花王株式会社 Composition de liant pour formation de moule
CN114669718B (zh) * 2020-12-24 2024-08-30 金隆化学工业股份有限公司 黏结材积层制造的方法
EP4349506A4 (fr) 2021-05-31 2024-07-31 Kao Corporation Procédé de production de résine adhésive pour moulage
EP4628231A1 (fr) 2022-11-29 2025-10-08 Kao Corporation Composition de liant pour moule de coulée
WO2025173559A1 (fr) * 2024-02-16 2025-08-21 花王株式会社 Composition pour moule

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4634723A (en) 1984-03-31 1987-01-06 Rutgerswerke Aktiengesellschaft Furfuryl alcohol binders, methods for their production and use
US5486557A (en) 1994-08-16 1996-01-23 Qo Chemicals, Inc. Furfuryl alcohol-formaldehyde resins
US5741914A (en) 1987-02-09 1998-04-21 Qo Chemicals, Inc. Resinous binder compositons
US6077883A (en) 1992-05-19 2000-06-20 Johns Manville International, Inc. Emulsified furan resin based glass fiber binding compositions, process of binding glass fibers, and glass fiber compositions
DE102008024727A1 (de) 2008-05-23 2009-11-26 Ashland-Südchemie-Kernfest GmbH Methansulfonsäurehaltige Katalysatoren für das Säurehärtungsverfahren

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE216800C (fr)
US2343972A (en) 1943-02-24 1944-03-14 Harvel Res Corp Novel furfuryl alcohol-formaldehyde acid condensation resinous product and method for preparing the same
US2874148A (en) 1954-07-29 1959-02-17 Quaker Oats Co Resinification of furfuryl alcohol and formaldehyde at high hydrogen-ion concentrations
NL295300A (fr) 1963-02-05
US3360492A (en) 1964-08-05 1967-12-26 Ford Motor Co Molding composition comprising a refractory material and as a binder the reaction product of formaldehyde, furfuryl alcohol and a urea
DE1252853B (de) 1965-06-26 1967-10-26 Dr Arno Mueller Bindemittel fuer Giessereisande
NL137597C (fr) 1967-12-26
US3594345A (en) 1968-05-31 1971-07-20 Quaker Oats Co Fiber glass laminates containing furfuryl resin binder
US3644274A (en) 1969-12-22 1972-02-22 Cpc International Inc Furan no-bake foundry binders
BE794700A (fr) 1972-01-31 1973-07-30 Quaker Oats Co Procede de durcissement d'un liant a base de furanne prepolymerise
JPS5126122B2 (fr) * 1972-08-30 1976-08-04
US3806491A (en) 1972-11-17 1974-04-23 Ashland Oil Inc Foundry binder composition comprising a ketone-aldehyde product
DE2411297C2 (de) * 1974-03-09 1983-03-24 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung und Härtung von Kitten
US4176114A (en) 1978-01-24 1979-11-27 C L Industries, Inc. Process for manufacturing sand cores or molds
NZ197438A (en) 1980-09-22 1984-05-31 Quaker Oats Co Making composite articles using furanformaldehyde condensation products
US4336342A (en) * 1981-03-16 1982-06-22 Ashland Oil, Inc. Cost reduction of acid curing foundry binders with alkylated aromatic hydrocarbon solvents
DE59204253D1 (de) 1991-11-07 1995-12-14 Ruetgerswerke Ag Ligninmodifizierte Bindemittel.
IL108362A (en) * 1993-02-02 1998-12-27 Qo Chemicals Inc Liquid resinous binder compositions of furfuryl alcohol and formaldehyde and their preparation
JP2826588B2 (ja) * 1993-12-27 1998-11-18 花王株式会社 鋳型成型用粘結剤−硬化剤組成物
EP0739257A4 (fr) 1994-01-12 2002-04-03 Ashland Inc Liants de fonderie thermodurcis et leur utilisation
US5491180A (en) 1994-08-17 1996-02-13 Kao Corporation Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold
DE19856778A1 (de) 1997-12-03 1999-06-10 Huettenes Albertus Formstoff-Bindemittel
JP3174034B2 (ja) 1999-03-03 2001-06-11 花王株式会社 鋳型用酸硬化性粘結剤の製法
US6391942B1 (en) * 2000-04-27 2002-05-21 Ashland Inc. Furan no-bake foundry binders and their use
WO2004103607A2 (fr) * 2003-05-13 2004-12-02 Ashland Inc. Procede de production de formes pour la fonderie
ITMI20032217A1 (it) 2003-11-14 2005-05-15 Cavenaghi Spa Sistema legante per fonderia a basso sviluppo di idrocarburi aromatici
US7211137B2 (en) * 2004-10-15 2007-05-01 Ashland Licensing And Intellectual Property Llc Binder composition comprising condensed tannin and furfuryl alcohol and its uses
US20080207796A1 (en) 2006-09-29 2008-08-28 Clingerman Michael C Furanic resin aggregate binders and method
CN101199983B (zh) * 2007-11-27 2010-06-23 宁夏共享集团有限责任公司 一种铸钢用低氮呋喃树脂的制作工艺
JP5429516B2 (ja) * 2008-07-01 2014-02-26 日立化成株式会社 鋳型製造用フラン樹脂組成物及びその用途

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4634723A (en) 1984-03-31 1987-01-06 Rutgerswerke Aktiengesellschaft Furfuryl alcohol binders, methods for their production and use
US5741914A (en) 1987-02-09 1998-04-21 Qo Chemicals, Inc. Resinous binder compositons
US6077883A (en) 1992-05-19 2000-06-20 Johns Manville International, Inc. Emulsified furan resin based glass fiber binding compositions, process of binding glass fibers, and glass fiber compositions
US5486557A (en) 1994-08-16 1996-01-23 Qo Chemicals, Inc. Furfuryl alcohol-formaldehyde resins
DE102008024727A1 (de) 2008-05-23 2009-11-26 Ashland-Südchemie-Kernfest GmbH Methansulfonsäurehaltige Katalysatoren für das Säurehärtungsverfahren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PAUL R. CAREY: "Sand Binder Systems Part V- Furan No-Bake", FOUNDRY MANAGEMENT & TECHNOLOGY, July 1995 (1995-07-01), pages 26 - 30, XP055722474

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EP3495073A2 (fr) 2019-06-12
ES2746190T3 (es) 2020-03-05
CN103379971B (zh) 2015-09-30
TW201235374A (en) 2012-09-01
PL3495073T3 (pl) 2020-11-30
US20140048740A1 (en) 2014-02-20
JP5913359B2 (ja) 2016-04-27
TWI564317B (zh) 2017-01-01
US9993863B2 (en) 2018-06-12
EP3495073B1 (fr) 2020-07-15
ES2816451T3 (es) 2021-04-05
WO2012080454A1 (fr) 2012-06-21
JP2014501175A (ja) 2014-01-20
EP3495073A3 (fr) 2019-07-10
DE202011110617U1 (de) 2015-04-29
CN103379971A (zh) 2013-10-30
PL2651581T3 (pl) 2020-01-31
EP2651581A1 (fr) 2013-10-23

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