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EP1137500A1 - Systeme de liants pour produire des noyaux et des moules a fondre a base de polyurethane - Google Patents
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EP1137500A1 - Systeme de liants pour produire des noyaux et des moules a fondre a base de polyurethane - Google Patents

Systeme de liants pour produire des noyaux et des moules a fondre a base de polyurethane

Info

Publication number
EP1137500A1
EP1137500A1 EP99957988A EP99957988A EP1137500A1 EP 1137500 A1 EP1137500 A1 EP 1137500A1 EP 99957988 A EP99957988 A EP 99957988A EP 99957988 A EP99957988 A EP 99957988A EP 1137500 A1 EP1137500 A1 EP 1137500A1
Authority
EP
European Patent Office
Prior art keywords
binder system
phenolic resin
mold
weight
casting
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP99957988A
Other languages
German (de)
English (en)
Other versions
EP1137500B1 (fr
EP1137500B9 (fr
Inventor
Jean-Claude Roze
Günter Weicker
Diether Koch
Andreas Werner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ashland Suedchemie Kernfest GmbH
Original Assignee
Ashland Suedchemie Kernfest GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ashland Suedchemie Kernfest GmbH filed Critical Ashland Suedchemie Kernfest GmbH
Publication of EP1137500A1 publication Critical patent/EP1137500A1/fr
Publication of EP1137500B1 publication Critical patent/EP1137500B1/fr
Application granted granted Critical
Publication of EP1137500B9 publication Critical patent/EP1137500B9/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/2273—Polyurethanes; Polyisocyanates

Definitions

  • the present invention relates to a binder system for the production of cores and casting molds based on polyurethane.
  • the method of core production known as the "cold box process” or "Ashland process" has taken a leading position in the foundry industry.
  • This method uses two-component polyurethane systems to bind the sand.
  • Component 1 consists of the solution of a polyol which contains at least two OH groups per molecule.
  • Component 2 is the solution of a polyisocyanate with at least two NCO groups per molecule.
  • the binder system is cured with the aid of basic catalysts. Liquid bases can be mixed into the binder system prior to shaping to react the two components (US-A-3,676,392). According to US Pat. No. 3,409,579, another possibility is to pass gaseous tertiary amines after the shaping through the molding material / binder system mixture.
  • phenolic resins are used as polyols, which are obtained by condensing phenol with aldehydes, preferably formaldehyde, in the liquid phase at temperatures up to about 130 ° C. in the presence of catalytic amounts of metal ions.
  • US-A-3,485,797 describes the preparation of such phenolic resins in detail.
  • substituted phenols preferably o-cresol and p-nonylphenol
  • EP-B-0 177 871 aliphatic monoalcohols having one to eight carbon atoms can be used as a further reaction component in the preparation of the phenolic resins.
  • the binder systems are said to have increased thermal stability.
  • Mixtures of high-boiling polar solvents (eg esters and ketones) and high-boiling aromatic hydrocarbons are predominantly used as solvents for the phenol component.
  • the polyisocyanates are preferably dissolved in high-boiling aromatic hydrocarbons.
  • the European patent application EP-A-0 T * 1 599 describes formulations in which the use of fatty acid methyl esters completely or at least largely dispenses with aromatic solvents.
  • the fatty acid methyl esters are used either as sole solvents or with the addition of polarity-increasing solvents (phenol component) or aromatic solvents (isocyanate component).
  • binder systems are particularly easy to remove from the molding tools.
  • binder systems formulated in accordance with EP-A-0 771 599 have a serious disadvantage: during casting, they increasingly develop smoke and smoke, so that in many foundries they were not used beyond the experimental stage.
  • a binder system comprising a phenolic resin component and a polyisocyanate component, characterized in that the phenolic resin component comprises an alkoxy-modified phenolic resin, wherein less than 25 mol% of the phenolic hydroxyl groups are etherified by a primary or secondary aliphatic alcohol having 1 to 10 carbon atoms .
  • the invention further relates to molding compositions which comprise aggregates and up to 15% by weight, based on the weight of the aggregates, of a binder system according to the invention.
  • the invention also relates to a method for producing a mold part comprising a. Mixing aggregates with the binder system according to the invention in a binding amount of up to 15% by weight, based on the amount of the aggregates; b. Placing the casting mixture obtained in step (a) into a mold; c. Curing the casting mixture in the mold to obtain a self-supporting shape; and d. then removing the molded casting mixture from step (c) from the mold and further hardening, whereby a hard, solid, hardened casting mold part is obtained.
  • the casting mold part thus obtained can be used according to the invention for casting metal.
  • the alkoxy-modified phenolic resin which has a low viscosity and favorable polarity, is essential to the invention.
  • the alkoxy-modified phenolic resin enables the total amount of solvent required to be reduced both in the phenolic resin component and in the isocyanate component.
  • the use of aromatic hydrocarbons in one or both binder components can be dispensed with.
  • Phenolic resins are produced by condensation of phenols and aldehydes (Ullmann's Encyclopedia of Industrial Chemistry, Vol. A19, page 371 ff, 5th edition, VCH Verlag, Weinheim).
  • substituted phenols and mixtures thereof can also be used in the context of this invention. All conventionally used substituted phenols are suitable.
  • the phenol compounds are unsubstituted either in both ortho positions or in one ortho and in the para position, to enable the polymerization. The remaining ring carbons can be substituted.
  • the choice of the substituent is not particularly limited unless the substituent adversely affects the polymerization of the phenol and the aldehyde.
  • substituted phenols are alkyl-substituted phenols, aryl-substituted phenols, cycloalkyl-substituted phenols, alkenyl-substituted phenols, alkoxy-substituted phenols, aryloxy-substituted phenols and halogen-substituted phenols.
  • the above-mentioned substituents have 1 to 26, preferably 1 to 12, carbon atoms.
  • suitable phenols in addition to the particularly preferred unsubstituted phenols are o-cresol, m-cresol, p-cresol, 3,5-xylene, 3,4-xylene, 3,4,5-trimethylphenol, 3-ethylphenol, 3,5 -Diethylphenol, p-butylphenol, 3,5-dibutylphenol, p-amylphenol, cyclohexylphenol, p-octylphenol, 3,5-dicyclohexylphenol, p-crotylphenol, p-phenylphenol, 3,5-dimethoxyphenol, 3,4,5-trimethoxyphenol , p-ethoxyphenol, p-butoxyphenol, 3-methyl-4-methoxyphenol and p-phenoxyphenol. Phenol itself is particularly preferred.
  • the phenols can also be described by the general formula:
  • A, B and C can be hydrogen, alkyl radicals, alkoxy radicals or halogen.
  • aldehydes which are conventionally used for the production of phenolic resins can be used in the context of the invention. Examples include formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde and Benzaldehyde.
  • the aldehydes used preferably have the general formula R'CHO, where R "is hydrogen or a hydrocarbon radical having 1-8 carbon atoms. Particular preference is given to formaldehyde either in its aqueous form or as paraformaldehyde.
  • phenolic resins In order to obtain the phenolic resins according to the invention, an at least equivalent number of moles of aldehyde based on the number of moles of the phenolic component should be used.
  • the molar ratio of aldehyde: phenol is preferably at least 1: 1.0, particularly preferably at least 1: 0.58.
  • primary and secondary aliphatic alcohols with an OH group and with 1 to 10 carbon atoms are used.
  • Suitable primary or secondary alcohols include e.g. Methanol, ethanol, n-propanol, iso-propanol, n-butanol and hexanol.
  • alkoxy-modified phenolic resins is described in EP-B-0 177 871. They can be manufactured using either the one-step or two-step process.
  • the phenol component, the aldehyde and the alcohol are reacted in the presence of a suitable catalyst.
  • the two-step process first produces an unmodified resin, which is then treated with alcohol.
  • the ratio of alcohol to phenol affects the properties of the resin as well as the reaction rate.
  • the molar ratio of alcohol to phenol is less than 0.25, so that less than 25 mol% of the phenolic hydroxyl groups are etherified. A molar ratio of 0.18-0.25 is preferred. If the molar ratio of alcohol to phenol is more than 0.25, the moisture resistance drops.
  • Suitable catalysts are salts of divalent ions of Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca and Ba. Zinc acetate is preferably used.
  • the alkoxylation leads to resins with a low viscosity.
  • the resins mainly have ortho-ortho benzyl ether bridges and also have alkoxymethylene groups of the general formula - (CH 2 O) n R in the ortho and para positions to the phenolic OH group.
  • R is the alkyl group of the alcohol and n is a small integer in the range from 1 to 5.
  • Dicarboxylic acid esters have the formula R ⁇ OC-R j -COOR ! where R 1 each independently represents an alkyl group with 1-12 (preferably 1-6) carbon atoms and R 2 is an alkylene group with 1-4 carbon atoms.
  • R 1 each independently represents an alkyl group with 1-12 (preferably 1-6) carbon atoms and R 2 is an alkylene group with 1-4 carbon atoms.
  • Examples are dimethyl esters of carboxylic acids with 4 to 6 carbon atoms, which are available, for example, under the name Dibasic esters from DuPont.
  • Glycol ether esters are compounds of the formula R 3 -O- R 4 -OOCR 5 , where R 3 represents an alkyl group with 1-4 carbon atoms, R 4 is an alkylene group with 2-4 carbon atoms and R 5 is an alkyl group with 1-3 carbon atoms ( eg butyl glycol acetate), preferred are glycol ether acetates.
  • Glycol diesters have the general formula R 5 COO-R 4 -OOCR 5 where R 4 and R 5 are as defined above and the radicals R 5 are each selected independently of one another (for example propylene glycol diacetate), preference being given to glycol diacetates.
  • Glycol diethers can be characterized by the formula R 3 -OR 4 -OR 3 , in which R 3 and R 4 are as defined above and the radicals R 3 are each selected independently of one another (for example dipropylene glycol dimethyl ether). Cyclic ketones, cyclic esters and cyclic carbonates with 4-5 carbon atoms are also suitable (eg propylene carbonate).
  • the alkyl and alkylene groups can each be branched or unbranched.
  • These organic polar solvents are preferably used either as sole solvents for the phenolic resin or in combination with fatty acid esters, the content of the oxygen-rich solvents in the solvent mixture should predominate. The content of oxygen-rich solvents should therefore be more than 50% by weight, preferably more than 55% by weight.
  • the measure to reduce the total content of solvents in the binder system had a positive effect on smoke development. While conventional phenolic resins mostly contain approx. 45% by weight and sometimes up to 55% by weight of solvent in order to achieve a viscosity suitable for processing (up to approx. 400 mPa-s), the solvent content in the solvent can be reduced by using a low-viscosity phenolic resin Phenol component can be limited to at most 40 wt .-%, preferably even to at most 35 wt .-%. The dynamic viscosity is e.g. determined using the Brookfield lathe method.
  • Suitable binder systems have an immediate strength of at least 150 N / cm 2 with a used amount of 0.8 parts by weight of phenolic resin component and isocyanate component based on 100 parts by weight of aggregate such as quartz sand H 32 (see EP-A-0 771 599 or DE-A-4 327 292).
  • fatty acid esters to the solvent of the phenol component leads to particularly good separation properties.
  • Fatty acids are suitable e.g. with 8 to 22 carbons esterified with an aliphatic alcohol.
  • Fatty acids of natural origin e.g. from tall oil, rapeseed oil, sunflower oil, germ oil and coconut oil.
  • individual fatty acids such as e.g. Palmitin fatty acid or myristic fatty acid can be used.
  • Aliphatic monoalcohols with 1 to 12 carbons are suitable for the esterification of the fatty acids. Alcohols with 1 to 10 carbon atoms are preferred, and alcohols with 4 to 10 carbon atoms are particularly preferred. Due to the lower polarity of the fatty acid esters whose alcohol component has 4 to 10 carbon atoms, it is possible to reduce the proportion of fatty acid esters and to reduce smoke formation. A number of fatty acid esters are commercially available.
  • fatty acid esters the alcohol component of which contains 4 to 10 carbon atoms
  • fatty acid esters with longer alcohol components are the butyl esters of oleic acid and tall oil fatty acid and the mixed octyl / decyl ester of tall oil fatty acid
  • aromatic hydrocarbons as solvents of the phenolic component can be avoided. This is due to the balanced polarity of the compounds, which enable the use of oxygen-rich, organic, polar solvents, for example as sole solvents.
  • the amount of solvent required can be limited to less than 35% by weight of the phenolic component. This is made possible by the low viscosity of the resin.
  • aromatic hydrocarbons can also be avoided.
  • the use of the binder system according to the invention with at least 50% by weight of the abovementioned oxygen-rich, polar, organic solvents as a constituent of the solvent of the phenol component also leads to a significantly reduced quality development in comparison to conventional systems with a high proportion of fatty acid esters in the solvent.
  • the second component of the binder system comprises an aliphatic, cycloaliphatic or aromatic polyisocyanate, preferably with 2 to 5 isocyanate groups. Depending on the desired properties, mixtures of organic isocyanates can also be used. Suitable polyisocyanates include aliphatic polyisocyanates such as e.g. Hexamethylene diisocyanate, alicyclic polyisocyanates such as e.g. 4,4'-dicyclohexylmethane diisocyanate and dimethyl derivatives thereof.
  • aromatic polyisocyanates examples include toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate and methyl derivatives thereof,
  • Polymethylene polyphenyl isocyanates and chlorophenylene-2,4-diisocyanate Preferred polyisocyanates are aromatic polyisocyanates, particularly preferred are polymethylene polyphenyl polyisocyanates such as diphenylmethane diisocyanate
  • 10-500 wt .-% polyisocyanate based on the weight of the phenolic resin is used. 20-300% by weight of polyisocyanate are preferably used.
  • Liquid polyisocyanates can be used in undiluted form, while solid or viscous polyisocyanates are dissolved in organic solvents. Up to 80% by weight of the isocyanant component can consist of solvents.
  • aromatic solvents are naphthalene, alkyl-substituted naphthalenes, alkyl-substituted benzenes and mixtures thereof.
  • Aromatic solvents which consist of mixtures of the abovementioned aromatic solvents and have a boiling point range between 140 ° C. and 230 ° C. are particularly preferred.
  • Preferably no aromatic solvent is used.
  • 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 binder systems can conventional additives such.
  • Binder systems are preferably offered as two-component systems, the solution of the phenolic resin being one component and the polyisocyanate, optionally in solution, being the other component.
  • the two components are combined and then mixed with sand or a similar aggregate to produce a molding compound.
  • Molding composition contains an effectively binding amount of up to 15% by weight of the binder system according to the invention, based on the weight of the binder system according to the invention
  • Aggregates It is also possible to first mix the components with parts of the sand or aggregate and then combine these two mixtures. Methods to achieve a uniform mixture of the components and the aggregate are known to the person skilled in the art known
  • the mixture can optionally also contain other conventional ingredients, such as iron oxide, ground flax fibers, wooden parts, pitch and refractory flours.
  • the aggregate In order to produce casting mold parts from sand, the aggregate should have a sufficiently large particle size. As a result, the molded part has sufficient porosity and volatile compounds can escape during the casting process. In general, at least 80% by weight and preferably 90% by weight of the aggregate have an average particle size ⁇ 290 ⁇ m. The average particle size of the aggregate should be between 100 and 300 ⁇ m.
  • sand is preferably used as the aggregate material, with at least 70% by weight and preferably more than 80% by weight of the sand being silicon dioxide.
  • Zircon, olevin, aluminosilicate sand and chromite sand are also suitable as aggregate materials.
  • the aggregate material is the main component of mold parts.
  • the proportion of the binder is generally up to 10% by weight, frequently between 0.5 and 7% by weight, based on the weight of the aggregate. 0.6 to 5% by weight of binder, based on the weight of the aggregate, is particularly preferably used.
  • the mold part is hardened so that it retains its outer shape after removal of the mold.
  • Conventional liquid or gaseous hardening systems can be used to harden the binder system according to the invention.
  • a volatile tertiary amine such as triethylamine or dimethylethylamine, as described in US Pat. No. 3,409,579, can be passed through the molded part. It is it is also possible to add a liquid amine to the molding composition for curing. After removal from the mold, the casting mold part is brought into the final state by further hardening in a manner known per se.
  • silanes of the general formula (R'0) 3 Si are added to the molding composition before curing.
  • R ' is a hydrocarbon radical, preferably an alkyl radical with 1-6 carbon atoms
  • R is an alkyl radical, an alkoxy-substituted alkyl radical or an alkylamine-substituted amine radical with alkyl groups which have 1-6 carbon atoms.
  • silanes examples include Dow Corning Z6040 and Union Carbide A-187 ( ⁇ -glycidoxypropyltrimethoxysilane), Union Carbide A-1100 ( ⁇ -aminopropyltriethoxysilane), Union Carbide A-1120 (N-ß- (aminoethyi) - ⁇ -amino- propyltrimethoxysilane) and Union Carbide A-1160 (ureidosilane).
  • additives including wetting agents and additives that extend the use of the sand mixture (English bench life additives), as described in US Pat. No. 4,683,252 or US Pat. No. 4,540,724, can be used.
  • Additional mold release agents such as Fatty acids, fatty alcohols and their derivatives can be used, but are usually not required.
  • the raw materials listed in Table I are placed in a reaction vessel equipped with a reflux condenser, thermometer and stirrer. With stirring, the temperature is increased evenly to 105-115 ° C and held until a refractive index of 1.5590 is reached. The condenser is then switched to distillation and the temperature is raised to 124-126 ° C within one hour. At this temperature, distillation is continued until a refractive index of 1.5940 is reached. A vacuum is then applied and the mixture is distilled to a refractive index of 1,600 under reduced pressure. The yield is approximately 83% in Example 1 and approximately 78% in Example 2.
  • the phenolic resin solution 1A separates into two phases after cooling to room temperature and is therefore not used for further tests.
  • the viscosity of the phenolic resin solutions 1B-1 D is far outside the application-technically favorable range (up to approx. 400 mPa-s)
  • the bending strengths of the test specimens are determined using the GF method.
  • the flexural strength of the test specimens is tested immediately after their manufacture (immediate strength) and after 1, 2 and 24 hours.
  • the binder systems formulated with the conventional phenolic resin have significantly lower initial strengths than the binder systems according to the invention (experiments 4-13). The increase in strength is also significantly slower.
  • GF test bars are stored in the oven at 650 ° C for 1 minute. After removal, the smoke development is observed against a dark background and rated with the marks 10 (very strong) - 1 (hardly noticeable).
  • Table V shows that the smoke development diminishes if the fatty acid esters are reduced in favor of oxygen-rich solvents.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mold Materials And Core Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un système de liants comprenant un constituant de résine phénolique et un constituant de polyisocyanate. Ce système se caractérise en ce que le constituant de résine phénolique comprend une résine phénolique modifiée par alcoxy, moins de 25 % en mole des groupes hydroxy phénoliques étant éthérifiés par un alcool aliphatique primaire ou secondaire ayant entre 1 et 10 atomes de carbone.
EP99957988A 1998-11-04 1999-11-04 Systeme de liants pour produire des noyaux et des moules a fondre a base de polyurethane Expired - Lifetime EP1137500B9 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19850833 1998-11-04
DE19850833A DE19850833C2 (de) 1998-11-04 1998-11-04 Bindemittelsystem zur Herstellung von Kernen und Gießformen auf Polyurethanbasis, deren Verwendung und Verfahren zur Herstellung eines Gießformteils auf Polyurethanbasis
PCT/EP1999/008419 WO2000025957A1 (fr) 1998-11-04 1999-11-04 Systeme de liants pour produire des noyaux et des moules a fondre a base de polyurethane

Publications (3)

Publication Number Publication Date
EP1137500A1 true EP1137500A1 (fr) 2001-10-04
EP1137500B1 EP1137500B1 (fr) 2004-03-24
EP1137500B9 EP1137500B9 (fr) 2005-12-14

Family

ID=7886667

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99957988A Expired - Lifetime EP1137500B9 (fr) 1998-11-04 1999-11-04 Systeme de liants pour produire des noyaux et des moules a fondre a base de polyurethane

Country Status (16)

Country Link
EP (1) EP1137500B9 (fr)
KR (1) KR100871534B1 (fr)
AT (1) ATE262387T1 (fr)
AU (1) AU757432B2 (fr)
BG (1) BG64942B1 (fr)
BR (1) BR9915076A (fr)
CA (1) CA2349878C (fr)
CZ (1) CZ296809B6 (fr)
DE (2) DE19850833C2 (fr)
DK (1) DK1137500T3 (fr)
ES (1) ES2217841T3 (fr)
HU (1) HU223611B1 (fr)
NO (1) NO20012166L (fr)
PL (1) PL191929B1 (fr)
TR (1) TR200101240T2 (fr)
WO (1) WO2000025957A1 (fr)

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DE102004057671A1 (de) * 2004-11-29 2006-06-01 Hüttenes-Albertus Chemische Werke GmbH Niedrigviskose Phenol-Formaldehydharze
DE102008007181A1 (de) 2008-02-01 2009-08-06 Ashland-Südchemie-Kernfest GmbH Verwendung von verzweigten Alkandiolcarbonsäurediestern in Gießereibindemitteln auf Polyurethanbasis
DE102008025311A1 (de) 2008-05-27 2009-12-03 Ashland-Südchemie-Kernfest GmbH Geruchs- und schadstoffadsorbierende Beschichtungsmasse für den kastengebundenen Metallguss
DE102013004663A1 (de) 2013-03-18 2014-09-18 Ask Chemicals Gmbh Epoxyverbindungen und Fettsäureester als Bestandteile von Gießereibindemitteln auf Polyurethanbasis
DE102013004662A1 (de) 2013-03-18 2014-09-18 Ask Chemicals Gmbh Verwendung von Monoestern epoxidierter Fettsäuren in PU-Bindemitteln zur Herstellung von Kernen und Formen für den Metallguss
DE102013004661A1 (de) 2013-03-18 2014-09-18 Ask Chemicals Gmbh Verwendung von Carbonsäuren und Fettaminen in PU-Bindemitteln zur Herstellung von Kernen und Formen für den Metallguss
WO2016008467A1 (fr) 2014-07-18 2016-01-21 Ask Chemicals Gmbh Co-catalyseurs pour liants polyuréthane-boîte froide
US9493602B2 (en) 2010-11-18 2016-11-15 Ask Chemicals Gmbh Polyurethaner-based binder for producing cores and casting molds using isocyanates containing a uretonimine and/or carbodiimide group, a mold material mixture containing said binder, and a method using said binder
DE102006037288B4 (de) 2006-08-09 2019-06-13 Ask Chemicals Gmbh Formstoffmischung enthaltend Cardol und/oder Cardanol in Gießereibindemitteln auf Polyurethanbasis, Verfahren zur Herstellung eines Formkörpers sowie Verwendung desselben
DE102018100694A1 (de) 2018-01-12 2019-07-18 Ask Chemicals Gmbh Formaldehydreduziertes Phenolharzbindemittel
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
US11253912B2 (en) 2017-06-08 2022-02-22 Ask Chemicals Gmbh Method for producing three-dimensionally layered shaped bodies
DE102021003265A1 (de) 2021-06-24 2022-12-29 Ask Chemicals Gmbh Beschichteter körniger stoff, verfahren zum beschichten eines körnigen stoffs und verwendung eines bindemittels zum beschichten eines körnigen stoffs
DE102021003264A1 (de) 2021-06-24 2022-12-29 Ask Chemicals Gmbh Zwei-komponenten-polyurethanzusammensetzungen
EP4389789A1 (fr) 2022-12-21 2024-06-26 Prefere Resins Holding GmbH Utilisation d'acide hydroxybenzoique pour modifier une resine de type ether benzylique

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EP1955792B1 (fr) 2007-01-22 2019-06-05 Arkema France Procédé de manufacture d'un noyau de fonderie et procédé de fonderire
DE102007031376A1 (de) 2007-07-05 2009-01-08 GTP Schäfer Gießtechnische Produkte GmbH Alternatives Cold-Box-Verfahren mit Rohölen
DE102010032734A1 (de) 2010-07-30 2012-02-02 Ashland-Südchemie-Kernfest GmbH Bindemittelsystem auf Polyurethanbasis zur Herstellung von Kernen und Gießformen unter Verwendung cyclischer Formale, Formstoffmischung und Verfahren
DE102010046981A1 (de) 2010-09-30 2012-04-05 Ashland-Südchemie-Kernfest GmbH Bindemittel enthaltend substituierte Benzole und Napthaline zur Herstellung von Kernen und Formen für den Metallguss, Formstoffmischung und Verfahren
DE102014117284A1 (de) 2014-11-25 2016-05-25 Ask Chemicals Gmbh Polyurethan-Bindemittelsystem zur Herstellung von Kernen und Gießformen, Formstoffmischung enthaltend das Bindemittel und ein Verfahren unter Verwendung des Bindemittels
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DE102004057671A1 (de) * 2004-11-29 2006-06-01 Hüttenes-Albertus Chemische Werke GmbH Niedrigviskose Phenol-Formaldehydharze
DE102004057671B4 (de) * 2004-11-29 2007-04-26 Hüttenes-Albertus Chemische Werke GmbH Phenol-Formaldehydharze und Verfahren zu deren Herstellung
DE102006037288B4 (de) 2006-08-09 2019-06-13 Ask Chemicals Gmbh Formstoffmischung enthaltend Cardol und/oder Cardanol in Gießereibindemitteln auf Polyurethanbasis, Verfahren zur Herstellung eines Formkörpers sowie Verwendung desselben
DE102008007181A1 (de) 2008-02-01 2009-08-06 Ashland-Südchemie-Kernfest GmbH Verwendung von verzweigten Alkandiolcarbonsäurediestern in Gießereibindemitteln auf Polyurethanbasis
DE102008025311A1 (de) 2008-05-27 2009-12-03 Ashland-Südchemie-Kernfest GmbH Geruchs- und schadstoffadsorbierende Beschichtungsmasse für den kastengebundenen Metallguss
US8215373B2 (en) 2008-05-27 2012-07-10 Ask Chemicals Gmbh Coating composition which adsorbs adourous and harmful substances and is intended for the box casting of metals
US9493602B2 (en) 2010-11-18 2016-11-15 Ask Chemicals Gmbh Polyurethaner-based binder for producing cores and casting molds using isocyanates containing a uretonimine and/or carbodiimide group, a mold material mixture containing said binder, and a method using said binder
WO2014146942A1 (fr) 2013-03-18 2014-09-25 Ask Chemicals Gmbh Utilisation de monoesters d'acides gras époxydés dans des liants à base de polyuréthane servant à fabriquer des noyaux et des moules de fonderie
WO2014146945A1 (fr) 2013-03-18 2014-09-25 Ask Chemicals Gmbh Composés époxy et ester d'acide gras faisant office de composants de liants à base de polyuréthane utilisés dans la technique de la fonderie
WO2014146940A1 (fr) 2013-03-18 2014-09-25 Ask Chemicals Gmbh Utilisation d'acides carboniques et d'amines grasses dans des liants à base de polyuréthane aux fins de la fabrication de noyaux et de moules pour la coulée de métaux
DE102013004661A1 (de) 2013-03-18 2014-09-18 Ask Chemicals Gmbh Verwendung von Carbonsäuren und Fettaminen in PU-Bindemitteln zur Herstellung von Kernen und Formen für den Metallguss
DE102013004662A1 (de) 2013-03-18 2014-09-18 Ask Chemicals Gmbh Verwendung von Monoestern epoxidierter Fettsäuren in PU-Bindemitteln zur Herstellung von Kernen und Formen für den Metallguss
DE102013004663A1 (de) 2013-03-18 2014-09-18 Ask Chemicals Gmbh Epoxyverbindungen und Fettsäureester als Bestandteile von Gießereibindemitteln auf Polyurethanbasis
DE102013004663B4 (de) 2013-03-18 2024-05-02 Ask Chemicals Gmbh Bindemittelsystem, Formstoffmischung enthaltend dasselbe, Verfahren zur Herstellung der Formstoffmischung, Verfahren zur Herstellung eines Gießformteils oder Gießkerns, Gießformteil oder Gießkern sowie Verwendung des so erhältlichen Gießformteils oder Gießkerns für den Metallguss
WO2016008467A1 (fr) 2014-07-18 2016-01-21 Ask Chemicals Gmbh Co-catalyseurs pour liants polyuréthane-boîte froide
US11253912B2 (en) 2017-06-08 2022-02-22 Ask Chemicals Gmbh Method for producing three-dimensionally layered shaped bodies
DE102018100694A1 (de) 2018-01-12 2019-07-18 Ask Chemicals Gmbh Formaldehydreduziertes Phenolharzbindemittel
WO2021254953A1 (fr) 2020-06-15 2021-12-23 Ask Chemicals Gmbh Procédé pour la production couche par couche d'un corps façonné tridimensionnel durci, corps façonné pouvant être obtenu par le procédé et utilisation de celui-ci
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
DE102021003265A1 (de) 2021-06-24 2022-12-29 Ask Chemicals Gmbh Beschichteter körniger stoff, verfahren zum beschichten eines körnigen stoffs und verwendung eines bindemittels zum beschichten eines körnigen stoffs
WO2022268943A1 (fr) 2021-06-24 2022-12-29 Ask Chemicals Gmbh Substance granulaire revêtue, procédé de revêtement d'une substance granulaire et utilisation d'un liant pour le revêtement d'une substance granulaire
DE102021003264A1 (de) 2021-06-24 2022-12-29 Ask Chemicals Gmbh Zwei-komponenten-polyurethanzusammensetzungen
EP4389789A1 (fr) 2022-12-21 2024-06-26 Prefere Resins Holding GmbH Utilisation d'acide hydroxybenzoique pour modifier une resine de type ether benzylique

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WO2000025957A1 (fr) 2000-05-11
TR200101240T2 (tr) 2001-10-22
DE59908972D1 (de) 2004-04-29
EP1137500B1 (fr) 2004-03-24
NO20012166L (no) 2001-06-11
BG64942B1 (bg) 2006-10-31
ES2217841T3 (es) 2004-11-01
AU757432B2 (en) 2003-02-20
AU1550900A (en) 2000-05-22
CZ296809B6 (cs) 2006-06-14
PL348642A1 (en) 2002-06-03
EP1137500B9 (fr) 2005-12-14
CZ20011334A3 (cs) 2002-05-15
KR20010113634A (ko) 2001-12-28
ATE262387T1 (de) 2004-04-15
DE19850833C2 (de) 2001-06-13
DK1137500T3 (da) 2004-05-10
PL191929B1 (pl) 2006-07-31
CA2349878C (fr) 2009-06-09
HU223611B1 (hu) 2004-10-28
CA2349878A1 (fr) 2000-05-11
NO20012166D0 (no) 2001-05-02
HUP0104315A3 (en) 2002-05-28
KR100871534B1 (ko) 2008-12-05
HUP0104315A2 (hu) 2002-03-28
BG105554A (en) 2001-12-29
BR9915076A (pt) 2001-10-23
DE19850833A1 (de) 2000-05-11

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