EP1137500B9 - Bindemittelsystem zur herstellung von kernen und giessformen auf polyurethanbasis - Google Patents

Bindemittelsystem zur herstellung von kernen und giessformen auf polyurethanbasis Download PDF

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Publication number
EP1137500B9
EP1137500B9 EP99957988A EP99957988A EP1137500B9 EP 1137500 B9 EP1137500 B9 EP 1137500B9 EP 99957988 A EP99957988 A EP 99957988A EP 99957988 A EP99957988 A EP 99957988A EP 1137500 B9 EP1137500 B9 EP 1137500B9
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EP
European Patent Office
Prior art keywords
binder system
casting
phenol resin
component
mould
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.)
Expired - Lifetime
Application number
EP99957988A
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German (de)
English (en)
French (fr)
Other versions
EP1137500B1 (de
EP1137500A1 (de
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
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Ashland Suedchemie Kernfest GmbH
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Publication date
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Publication of EP1137500B1 publication Critical patent/EP1137500B1/de
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Publication of EP1137500B9 publication Critical patent/EP1137500B9/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • 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 molds based on polyurethane.
  • the named "cold box method” or "Ashland method” has become known in the foundry industry a top position conquered.
  • the Component 1 consists of the solution of a polyol that at least contains two OH groups per molecule.
  • Component 2 is the solution of a Polyisocyanate with at least two NCO groups per molecule.
  • the Curing of the binder system is carried out using basic Catalysts. Liquid bases can be added to the binder system before Shaping be added to the two components for the reaction to bring (US-A-3,676,392). Another possibility is according to US-A-3,409,579 therein, gaseous tertiary amines after shaping by the To pass molding material / binder system mixture.
  • phenolic resins are used as polyols used by condensation of phenol with aldehydes, preferably Formaldehyde, in the liquid phase at temperatures up to approx. 130 ° C in Presence of catalytic amounts of metal ions can be obtained.
  • aldehydes preferably Formaldehyde
  • the Binder systems have increased thermal stability.
  • Solvents for the phenolic component are predominantly mixtures from high boiling point polar solvents (e.g., esters and ketones) and high-boiling aromatic hydrocarbons used.
  • polyisocyanates are preferred in high-boiling aromatic Hydrocarbons dissolved.
  • European Patent Application EP-A-0 771 599 formulations are described in which by use of fatty acid methyl esters wholly or at least largely aromatic Solvent is omitted.
  • the fatty acid methyl esters are included either as a sole solvent or with the addition of polarity increasing Solvents (phenol component) or aromatic solvents (Isocyanate component) used.
  • the with these binder systems made cores can be particularly easily from the molds remove.
  • Binder systems that have little or no aromatic Contain hydrocarbons.
  • a binder system comprising a Phenolic resin component and a polyisocyanate component in that the phenolic resin component and / or the polyisocyanate component comprises a fatty acid ester and the phenolic resin component comprises an alkoxy-modified phenolic resin wherein less than 25 mol% of the hydroxymethyl groups in the phenolic resin a primary or secondary aliphatic alcohol of 1 to 10 Are etherified carbon atoms and wherein the solvent content of the Phenolic resin component is at most 40 wt .-%.
  • the invention relates to molding compositions, the aggregates and up to 15 Wt .-% based on the weight of the aggregates of an inventive Binder system include.
  • the casting molding thus obtained can according to the invention for casting metal be used.
  • Essential to the invention is the choice of the alkoxy-modified phenolic resin, the has a low viscosity and favorable polarity. According to the invention allows the alkoxy-modified phenolic resin that needed Total solvent amount in both the phenolic resin component as also reduce in the isocyanate component. Furthermore, on the Use of aromatic hydrocarbons in one or both Binder components are dispensed with. By combining the alkoxy-modified phenolic resin with oxygen-rich, polar, organic Solvents are improved with reduced smoke formation Achieved instant strength. The addition of fatty acid ester has a positive effect the release effect and the moisture resistance.
  • Phenolic resins are made 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 may also be used be used. Suitable are all conventionally used substituted phenols.
  • the phenolic compounds are either in both ortho positions or unsubstituted in an ortho and in the para position, to allow the polymerization. The remaining ring carbons may be substituted.
  • the choice of the substituent is not particular if the substituent limited the polymerization of the phenol and the Aldehyds are not adversely affected.
  • 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 abovementioned substituents have 1 to 26, preferably 1 to 12, carbon atoms.
  • suitable phenols besides the most 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.
  • Particularly preferred is phenol itself.
  • the phenols can also be described by the general formula: where A, B and C may be hydrogen, alky
  • Formaldehyde used as aldehyde according to the invention
  • formaldehyde either in its aqueous form or as paraformaldehyde.
  • an at least equivalent number of moles of formaldehyde based on the number of moles of Phenol component, can be used.
  • the molar ratio is preferably Formaldehyde: Phenol, therefore, at least 1: 1.0, more preferably at least 1: 0.58.
  • primary and secondary aliphatic alcohols having one OH group and from 1 to 10 Carbon atoms used.
  • Suitable primary or secondary alcohols include e.g. Methanol, ethanol, n-propanol, iso-propanol, n-butanol and Hexanol.
  • the phenol component in the one-step process, the phenol component, the formaldehyde and the alcohol in the presence of a suitable catalyst for the reaction brought.
  • a suitable catalyst for the reaction brought.
  • a non-modified Resin prepared, which is then treated with alcohol.
  • Suitable catalysts are salts of divalent ions of Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca and Ba.
  • zinc acetate is used.
  • the alkoxylation leads to resins with a low viscosity.
  • the resins have mainly ortho-ortho Benzylethermaschinen and also have ortho and para to the phenolic OH group alkoxymethylene groups of the general formula - (CH 2 O) n R on.
  • R is the alkyl group of the alcohol and n is a small integer in the range of 1 to 5.
  • solvents which are conventionally used in binder systems for foundry technology can be used in the systems according to the invention. It is even possible to use aromatic hydrocarbons as a solvent component in larger proportions, but this does not avoid the above-mentioned, potentially environmentally and health-endangering solvents.
  • aromatic hydrocarbons As solvents for the phenolic resin component therefore oxygen-rich, polar, organic solvents are preferably used.
  • Particularly suitable are dicarboxylic acid esters, glycol ether esters, glycol diesters, glycol diethers, cyclic ketones, cyclic esters (lactones) or cyclic carbonates. Dicarboxylic acid esters, cyclic ketones and cyclic carbonates are preferably used.
  • Dicarboxylic acid esters have the formula R 1 OOC-R 2 -COOR 1 , wherein each R 1 independently represents an alkyl group having 1-12 (preferably 1-6) carbon atoms and R 2 is an alkylene group having 1-4 carbon atoms.
  • R 1 independently represents an alkyl group having 1-12 (preferably 1-6) carbon atoms
  • R 2 is an alkylene group having 1-4 carbon atoms.
  • dimethyl esters of carboxylic acids having 4 to 6 carbon atoms which are obtainable, for example, under the name Dibasic Ester from DuPont.
  • Glycol ether esters are compounds of the formula R 3 -OR 4 -OOCR 5 where R 3 is an alkyl group of 1-4 carbon atoms, R 4 is an alkylene group of 2-4 carbon atoms and R 5 is an alkyl group of 1-3 carbon atoms (eg butyl glycol acetate ), preferred are glycol ether acetates.
  • Glycol diesters correspondingly have the general formula R 5 COO-R 4 -OOCR 5 , wherein R 4 and R 5 are as defined above and the radicals R 5 are each independently selected (eg propylene glycol diacetate), glycol diacetates are preferred.
  • 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 independently selected (eg dipropylene glycol dimethyl ether). Cyclic ketones, cyclic esters and cyclic carbonates of 4-5 carbon atoms are also suitable (eg, propylene carbonate).
  • the alkyl and alkylene groups may each be branched or unbranched.
  • These organic polar solvents are preferably used either as a sole solvent for the phenolic resin or in combination with fatty acid esters, wherein the content of the oxygen-rich solvents in the solvent mixture should predominate.
  • the content of oxygen-rich solvents should thus be more than 50% by weight, preferably more than 55% by weight.
  • the measure had a positive effect on the development of quality, the To reduce the total content of solvents in the binder system. While conventional phenolic resins predominantly about 45 wt .-% and partially up to 55 wt .-% solvent to a Processing-compatible viscosity (up to about 400 mPa ⁇ s) can be achieved by Use of a low-viscosity phenolic resin of the invention Solvent content in the phenol component to at most 40 wt .-%, preferably even limited to at most 35 wt .-%.
  • the dynamic Viscosity is e.g. determined by the Brookfield rotary spindle method.
  • Suitable binder systems have an instantaneous strength of at least 150 N / cm 2 at a used amount of each 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 ester to the solvent of the phenolic component leads to particularly good release properties.
  • Suitable fatty acids are 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.
  • the natural oils which are mostly mixtures of different fatty acids,
  • single fatty acids e.g. palmitic or myristic fatty acid.
  • Aliphatic monoalcohols with 1 to 12 carbons are suitable for Esterification of fatty acids. Preference is given to alcohols having 1 to 10 Carbon atoms, particularly preferred are alcohols having 4 to 10 Carbon atoms. 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 fatty acid ester content and reduce the formation of smoke. A number of fatty acid esters are commercially available.
  • fatty acid esters whose Alcohol component contains 4 to 10 carbon atoms particularly advantageous because they are excellent for the binder system Impart release properties when their content in the solvent of the Phenol component is less than 50 wt .-% is.
  • 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 Called tall oil fatty acid.
  • the alkoxy-modified Phenolic resins can be aromatic hydrocarbons as a solvent avoid the phenol component. This is due to the balanced polarity of the Due to the use of oxygenated, organic, polar solvents e.g. as a sole solvent.
  • By the use of the alkoxy-modified Phenolic resins can reduce the amount of solvent needed to less than 35 wt .-% of phenol component are limited. This is done by the low viscosity of the resin allows.
  • aromatic Hydrocarbons can also be avoided.
  • binder system according to the invention with at least 50 wt .-% of above-mentioned oxygen-rich, polar, organic solvent as Part of the solvent of the phenol component also leads to a significantly reduced smoke development compared 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 can also Mixtures of organic isocyanates are used.
  • suitable Polyisocyanates include aliphatic polyisocyanates, e.g. Hexamethylene diisocyanate, alicyclic polyisocyanates such as e.g. 4,4'-dicyclohexylmethane 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 polyphenylisocyanate and chlorophenylene-2,4-diisocyanate.
  • Preferred polyisocyanates are aromatic polyisocyanates, especially preferred are polymethylene polyphenyl polyisocyanates, e.g. Diisocyanate.
  • polyisocyanate is by weight used the phenolic resin.
  • Liquid polyisocyanates can be undiluted Form while solid or viscous polyisocyanates in be dissolved organic solvents. Up to 80% by weight of the isocyanate component may consist of solvents.
  • a solvent for the Polyisocyanate will be either the above-mentioned fatty acid esters or a Mixture of fatty acid esters and up to 50% by weight of aromatic solvents used. Suitable aromatic solvents are naphthalene, alkyl-substituted Naphthalenes, alkyl-substituted benzenes and mixtures thereof.
  • aromatic solvents consisting of mixtures of consist of above-mentioned aromatic solvents and a Boiling point range between 140 ° C and 230 ° C have.
  • no aromatic solvent used Preferably no aromatic solvent used.
  • the binder systems conventional additives, such. B. silanes (US 4,540,724), drying oils (US 4,268,425) or complexing agents (WO 95/03903).
  • the Binder systems are preferred as two-component systems offered, wherein the solution of the phenolic resin is a component and the polyisocyanate, optionally in solution, is the other component.
  • the two components are combined and then sand or a similar aggregate mixed to produce a molding material.
  • the Molding composition contains an effective binding amount of up to 15 wt .-% of binder system according to the invention, based on the weight of Aggregates. It is also possible to use the components first with each Mixing of the sand or aggregate and then this to unite both mixtures. Method to a uniform mixture to achieve the components and the aggregate are those skilled in the art known.
  • the mixture may optionally contain other conventional Ingredients, such as iron oxide, ground flax fibers, wood pieces, and pitch refractory flours, included.
  • the aggregate should have enough have large particle size.
  • the mold part has a Sufficient porosity and volatile compounds may occur during the Casting escape.
  • at least 80% by weight and preferably 90% by weight of the aggregate an average Particle size ⁇ 290 microns on.
  • the average particle size of the Aggregates should be between 100 and 300 ⁇ m.
  • sand is preferred as aggregate material used, wherein at least 70 wt .-% and preferably more than 80 wt .-% of the sand are silica.
  • Zircon, olefin, aluminosilicate sand and Chromite sand are also suitable as aggregate materials.
  • the aggregate material is the main ingredient in molded parts.
  • In Molded sand moldings for standard applications account for the share of Binder generally up to 10 wt .-%, often between 0.5 and 7 Wt .-%, based on the weight of the aggregate. Especially preferred are 0.6 to 5 wt .-% of binder, based on the weight of Aggregates, used.
  • the aggregate is preferably dried, up to 0.1 wt .-%, based on the weight of the aggregate, tolerated by moisture become.
  • the mold part is hardened so that it conforms to its external shape the removal of the mold retains.
  • Conventional liquid or gaseous Hardening systems can be used to cure the invention
  • Binder system can be used.
  • a volatile one tertiary amine e.g. Triethylamine or dimethylethylamine as described in US-A-3,409,579 described, are passed through the mold part. It is furthermore possible to add a liquid amine to the molding compound for curing. After removal from the mold is in a conventional manner the Molded part converted by further hardening in the final state.
  • silanes of the general formula (R'O) 3 Si are added to the molding compound before curing.
  • R ' is a hydrocarbon radical, preferably an alkyl radical of 1-6 carbon atoms
  • R is an alkyl radical, an alkoxy-substituted alkyl radical or an alkylamine-substituted amine radical having alkyl groups having 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- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane) and Union Carbide A-1160 (ureidosilane).
  • additives including wetting agents and the use of the sand mixture extending additives (engl. Benchlife additives), as described in US 4,683,252 or US 4,540,724, be used.
  • Additional mold release agents such as e.g. fatty acids, Fatty alcohols and their derivatives can be used, but are used in usually not needed.
  • example 1 not according to the invention inventively phenol 2130.7 g 1770.6 g Paraformaldehyde 91% 865.3 g 984.3 g n-butanol - 279.6 g Zinc acetate dihydrate 1.0 g 1.5 g
  • the phenol resin solution 1A separates after cooling to room temperature in two phases and is therefore not used for further tests.
  • the viscosity of the phenol resin solutions 1B-1D is far outside the application-favorable range (up to approx. 400 mPa ⁇ s)
  • the flexural strengths of the specimens are determined by the GF method. The bending strength of the specimens immediately after their Production (immediate strength) as well as tested after 1, 2 and 24 hours.

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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)
EP99957988A 1998-11-04 1999-11-04 Bindemittelsystem zur herstellung von kernen und giessformen auf polyurethanbasis Expired - Lifetime EP1137500B9 (de)

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 (de) 1998-11-04 1999-11-04 Bindemittelsystem zur herstellung von kernen und giessformen auf polyurethanbasis

Publications (3)

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

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

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DE102021003264A1 (de) 2021-06-24 2022-12-29 Ask Chemicals Gmbh Zwei-komponenten-polyurethanzusammensetzungen
EP4389789A1 (en) 2022-12-21 2024-06-26 Prefere Resins Holding GmbH Use of hydroxybenzoic acid to modify a benzyl ether type resin

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HUP0104315A2 (hu) 2002-03-28
KR20010113634A (ko) 2001-12-28
CA2349878C (en) 2009-06-09
WO2000025957A1 (de) 2000-05-11
HU223611B1 (hu) 2004-10-28
AU1550900A (en) 2000-05-22
NO20012166D0 (no) 2001-05-02
PL191929B1 (pl) 2006-07-31
DE19850833C2 (de) 2001-06-13
ATE262387T1 (de) 2004-04-15
PL348642A1 (en) 2002-06-03
NO20012166L (no) 2001-06-11
KR100871534B1 (ko) 2008-12-05
EP1137500B1 (de) 2004-03-24
BR9915076A (pt) 2001-10-23
DK1137500T3 (da) 2004-05-10
TR200101240T2 (tr) 2001-10-22
BG64942B1 (bg) 2006-10-31
DE19850833A1 (de) 2000-05-11
HUP0104315A3 (en) 2002-05-28
AU757432B2 (en) 2003-02-20
DE59908972D1 (de) 2004-04-29
ES2217841T3 (es) 2004-11-01
CZ296809B6 (cs) 2006-06-14
EP1137500A1 (de) 2001-10-04
CA2349878A1 (en) 2000-05-11
BG105554A (en) 2001-12-29

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