EP1955791A1 - Verfahren zur Herstelung von Giessereikerne und Giessereiverfahren - Google Patents

Verfahren zur Herstelung von Giessereikerne und Giessereiverfahren Download PDF

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Publication number
EP1955791A1
EP1955791A1 EP07100919A EP07100919A EP1955791A1 EP 1955791 A1 EP1955791 A1 EP 1955791A1 EP 07100919 A EP07100919 A EP 07100919A EP 07100919 A EP07100919 A EP 07100919A EP 1955791 A1 EP1955791 A1 EP 1955791A1
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EP
European Patent Office
Prior art keywords
weight
foundry
dema
resins
sand
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.)
Withdrawn
Application number
EP07100919A
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English (en)
French (fr)
Inventor
Diether Koch
Jens Muller
Jean-Claude Roze
Pierre-Henri Vacelet
Bruno Van Hemelryck
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Arkema France SA
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Arkema France SA
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 Arkema France SA filed Critical Arkema France SA
Priority to EP07100919A priority Critical patent/EP1955791A1/de
Priority to PCT/EP2008/050720 priority patent/WO2008090159A1/en
Publication of EP1955791A1 publication Critical patent/EP1955791A1/de
Withdrawn legal-status Critical Current

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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
    • B22C1/162—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 use of a gaseous treating agent for hardening the binder

Definitions

  • This invention relates to binder compositions useful in the foundry art for making cores which harden at room temperature. It relates also to combination of a foundry aggregate such as sand and a binder based generally on phenolic (phenol-aldehyde) resins and polyisocyanates which, on being formed into a coherent mass with the aggregate in a mould, generally a steel mould, is capable of being cured at room temperature by a curing agent. The self-supported as obtained, the cores, can be used in making metal castings.
  • a foundry aggregate such as sand and a binder based generally on phenolic (phenol-aldehyde) resins and polyisocyanates
  • a two-component polyurethane binder system is used for the bonding of sand.
  • the first component consists of a solution of a polyol, which contains at least two OH groups per molecule.
  • the second component is a solution of an isocyanate having at least two NCO groups per molecule.
  • tertiary volatile amines as curing agents has long been known in PUCB: see for example, US 3,429,848 ; US3,485,797 ; US 3,676,392 ; and US 3,432,457 .
  • These tertiary amines are sometimes utilized with metal salts and provide a fast curing of phenol formaldehyde and polyisocyanate resins at room temperature. They can be added to the binder system before the moulding stage, in order to bring the two components to reaction ( US. 3,676,392 ) or they can pass in a gaseous form through a shaped mixture of an aggregate and the binder ( US 3,409,579 )
  • phenolic resins are used as polyols, which are prepared through condensation of phenol with aldehydes, preferably formaldehyde, in the liquid phase, at temperatures of up to around 130 °C, in the presence of divalent metal catalysts.
  • aldehydes preferably formaldehyde
  • divalent metal catalysts The manufacture of such phenolic resins is described in detail in US 3,485,797 .
  • substituted phenols especially o-cresol and p-nonyl phenol, can be used (for example, EP-A-1 83 782 ).
  • alkoxylated phenolic resins As additional reaction components, according to EP-B-O 177 871 , aliphatic monoalcohols with one to eight carbon atoms can be used to prepare alkoxylated phenolic resins. According to this patent, the use of alkoxylated phenolic resins in the binder results in binders that have a higher thermal stability.
  • solvents for the phenolic components mixtures of high-boiling point polar solvents (for example, esters and ketones) and high boiling point aromatic hydrocarbons are typically used.
  • Preferred tertiary amines for curing polyurethane cold box (PUCB) processes are trimethylamine (TMA), dimethylethylamine (DMEA), dimethylisopropylamine (DMIPA), triethylamine (TEA). They are used individually.
  • the catalyst is usually introduced as a combination of one inert gas and one amine gas.
  • the boiling point of the amine is preferably below 100 °C to permit evaporation and to achieve satisfactory concentration of amine in the amine-inert gas mixture injected into the steel mould. A boiling point below 100 °C also helps to avoid condensation of the amine when it contacts the steel moulds. But the boiling point of the amine preferably must be high enough to facilitate handling of the amine.
  • Trimethylamine (TMA) is a gas at normal ambient temperature (boiling point (Bp) 2,87 °C), which makes it difficult to handle.
  • low boiling tertiary amines the well-known low boiling tertiary amine DMEA (Bp 37°C) has undesirable organoleptic characteristics. In particular, it has a strong ammonia odor. Furthermore, this amine is very easily impregnated in the skin and in the clothing, making an unpleasant working environment when it is utilized.
  • TEA triethylamine
  • TEA with molecular weight of 101 is probably the highest molecular weight amine permissible for the so-called Cold Process; it has a very low odor intensity and very low amine smell but displays lower curing ability than the tertiary amines with lower Molecular weight and lower Boiling point.
  • DMIPA Molecular weight: 87, Bp: 67 °C
  • DMIPA requires less energy input and lower gassing temperatures when carried out in PUCB equipment.
  • DMIPA has a better reactivity than TEA: 1 kg of DMIPA is capable of curing approximately 1200 kg of sand/resin mixture while 1 kg of TEA is capable of curing only 900 kg of the same sand/resin mixture.
  • DMIPA is less odorant than tertiary amine DMEA.
  • the invention relates to a process for preparing a foundry shape by the cold box process.
  • the cores produced according to the present process display a lower water sensitivity than with DMIPA, as seen from higher flexural strength after having been exposed to humidity.
  • the invention relates to a process for preparing a foundry shape by the cold box process, which comprises the following steps
  • the binder system comprises at least a phenolic resin component and at least an isocyanate component.
  • Phenolic resins are manufactured by condensation of phenols and aldehydes ( Ullmann's Encyclopedia of Industrial Chemistry, Bd. A19, page 371 ff, 5th, edition, VCH Publishing House, Weinheim ). Substituted phenols and mixtures thereof can also be used. All conventionally used substituted phenols are suitable.
  • the phenolic binders are not substituted, either in both ortho-positions or in one ortho- and in the para-position, in order to enable the polymerization. The remaining ring sites can be substituted. There is no particular limitation on the choice of substituent, as long as the substituent does not negatively influence 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.
  • substituents have 1 to 26, and preferably 1 to 12, carbon atoms.
  • suitable phenols in addition to the especially preferred unsubstituted phenols, are o-cresol, m-cresol, p-cresol, 3,5-xylol, 3,4-xylol, 3,4,5-trimethyl phenol, 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.
  • aldehydes which are traditionally used for the manufacture of phenolic resins, can be used within the scope of the invention. Examples of this are formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde, and benzaldehyde.
  • the aldehydes commonly used should have the general formula R'CHO, where R' is hydrogen or a hydrocarbon radical with 1-8 carbon atoms. Particularly preferred is formaldehyde, either in its diluted aqueous form or as paraformaldehyde.
  • a molar ratio aldehyde to phenol of at least 1.0 should be used.
  • a molar ratio of aldehyde to phenol is preferred of at least 1:1.0, with at least 1:0.58 being the most preferable.
  • primary and secondary aliphatic alcohols are used having an OH-group containing from 1 to 10 carbon atoms.
  • Suitable primary or secondary alcohols include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, and hexanol.
  • Alcohols with 1 to 8 carbon atoms are preferred, in particular, methanol and butanol.
  • alkoxy-modified phenolic resins are described in EP-B-0 177 871 . They can be manufactured using either a one-step or a two-step process. With the one-step-process, the phenolic components, the aldehyde and the alcohol are brought to a reaction in the presence of suitable catalysts. With the two-step-process, an unmodified resin is first manufactured, which is subsequently treated with alcohol.
  • the ratio of alcohol to phenol influences the properties of the resin as well as the speed of the reaction.
  • the molar ratio of alcohol to phenol amounts to less than 0.25.
  • a molar ratio of from 0.18-0.25 is most preferred. If the molar ratio of alcohol to phenol amounts to more than 0.25, the moisture resistance decreases.
  • Suitable catalysts are divalent salts of Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca and Ba. Zinc acetate is preferred.
  • Alkoxylation leads to resins with a low viscosity.
  • the resins predominantly exhibit ortho-ortho benzyl ether bridges and furthermore, in ortho- and para-position to the phenolic OH-groups, they exhibit alkoxymethylene groups with the general formula -(CH 2 O) n R.
  • R is the alkyl group of the alcohol
  • n is a small whole number in the range of 1 to 5.
  • solvents which are conventionally used in binder systems in the field of foundry technology, can be used. It is even possible to use aromatic hydrocarbons in large quantities as essential elements in the solution, except that those solvents are not preferred because of environmental considerations. For that reason, the use of oxygen-rich, polar, organic solvents are preferred as solvents for the phenolic resin components.
  • the most suitable are dicarboxylic acid ester, glycol ether ester, glycol diester, glycol diether, cyclic ketone, cyclic ester (lactone) or cyclic carbonate.
  • Dicarboxylic acid ester exhibits the formula R1OOC-R2-COOR1, where R1, represents an independent alkyl group with 1-12, and preferably 1-6 carbon atoms, and R2 is an alkylene group with 1-4 carbon atoms.
  • R1OOC-R2-COOR1 represents an independent alkyl group with 1-12, and preferably 1-6 carbon atoms
  • R2 is an alkylene group with 1-4 carbon atoms.
  • Examples are dimethyl ester from carboxylic acids with 4 to 6 carbon atoms, which can, for example, be obtained under the name dibasic ester from DuPont.
  • Glycol ether esters are binders with the formula R3-O-R4-OOCR5, where R3 represents an alkyl group with 1-4 carbon atoms, R4 is an alkylene group with 2-4 carbon atoms, and R5 is an alkyl group with 1-3 carbon atoms (for example butyl glycolacetate), with glycol etheracetate being preferred.
  • Glycol diesters exhibit the general formula R5COO-R4-OOCR5 where R4 and R5 are as defined above and the remaining R5, are selected, independent of each other (for example, propyleneglycol diacetate), with glycol diacetate being preferred.
  • Glycol diether is characterized by the formula R3-O-R4-O-R3, where R3 and R4 are as defined above and the remaining R3 are selected independent of each other (for example, dipropyleneglycol dimethyl ether).
  • Cyclic ketone, cyclic ester and cyclic carbonate with 4-5 carbon atoms are likewise suitable (for example, propylene carbonate).
  • the alkyl- and alkylene groups can be branched or unbranched.
  • organic polar solvents can preferably be used either as stand-alone solvents for the phenolic resin or in combination with fatty acid esters, where the content of oxygen-rich solvents in a solvent mixture should predominate.
  • the content of oxygen-rich solvents is preferably at least 50% by weight, more preferably at least 55% by weight of the total solvents.
  • phenolic resins generally contain around 45 % by weight and, sometimes, up to 55 % by weight of solvents, in order to achieve an acceptable process viscosity (of up to 400 mPas)
  • the amount of solvent in the phenolic-component can be restricted to at most 40 % by weight, and preferably even 35 % by weight, through the use of the low viscosity phenolic resins described herein, where the dynamic viscosity is determined by the Brookfield Head Spindle Process.
  • the viscosity with reduced quantities of solvent lies well outside the range, which is favorable for technical applications of up to around 400 mPas. In some parts, the solubility is also so bad that at room temperature phase separation can be observed. At the same time the immediate strength of the cores manufactured with this binder system is very low. Suitable binder systems exhibit an immediate strength of at least 150 N/cm 2 when 0.8 part by weight each of the phenolic resin and isocyanate component are used for 100 parts by weight of an aggregate, like, for example, Quarzsand H32 (see for instance: EP 771,599 or DE 4,327,292 ).
  • fatty acid ester to the solvent of the phenolic component leads to especially good release properties.
  • Fatty acids are suitable, such as, for example, those with 8 to 22 carbons, which are esterified with an aliphatic alcohol.
  • fatty acids with a natural origin are used, like, for example, those from tall oil, rapeseed oil, sunflower oil, germ oil, and coconut oil.
  • single fatty acids like palmitic fatty acid or myristic fatty acid can, of course, be used.
  • Aliphatic mono alcohols with 1 to 12 carbons are particularly suitable for the esterification of fatty acids. Alcohols with 1 to 10 carbon atoms are preferred, with alcohols with 4 to 10 carton atoms being especially preferred. Based on the low polarity of fatty acid esters, whose alcohol components exhibit 4 to 10 carbon atoms, it is possible to reduce the quantity of fatty acid esters, and to reduce the buildup of smoke. A line of fatty acid esters is commercially obtainable.
  • Fatty acid esters whose alcohol components contain from 4 to 10 carbon atoms, are especially advantageous, since they also give binder systems excellent release properties, when their content in the solvent component of the phenolic component amounts to less than 50 % by weight based upon the total amount of solvents in the phenolic resin component.
  • fatty acid esters with longer alcohol components are the butyl esters of oleic acids and tall oil fatty acid, as well as the mixed octyl-decylesters of tall oil fatty acids.
  • aromatic hydrocarbons can be avoided as solvents for the phenolic component. This is because of the excellent polarity of the binders. Oxygen-rich organic, polar solvents, can now be used as stand-alone solvents.
  • the quantity of solvents required can be restricted to less than 35 % by weight of the phenolic component. This is made possible by the low viscosity of the resins.
  • the use of aromatic hydrocarbons can, moreover, be avoided.
  • binder systems with at least 50 % by weight of the above named oxygen-rich, polar, organic solvents as components in the solvents of the phenolic components leads, moreover, to a doubtlessly lower development of smoke, in comparison with conventional systems with a high proportion of fatty acid esters in the solvent.
  • the two components of the binder system include an aliphatic, cycloaliphatic or aromatic polyisocyanate, preferably with 2 to 5 isocyanate groups. Based on the desired properties, each can also include mixtures of organic isocyanates.
  • Suitable polyisocyanates include aliphatic polyisocyanates, like, for example, hexamethylenediisocyanate, alicyclic polyisocyanates like, for example, 4,4'-dicyclohexylmethanediisocyanate, and dimethyl derivates thereof.
  • aromatic polyisocyanates examples include toluol-2,4-diisocyanate, toluol-2,6-diisocyanate, 1,5-napththalenediisocyanate, triphenylmethanetriisocyanate, xylylenediisocyanate and its methyl derivatives, polymethylenepolyphenyl isocyanate and chlorophenylene-2,4-diisocyanate.
  • Preferred polyisocyanates are aromatic polyisocyanates, in particular, polymethylenepolyphenyl polyisocyanates such as diphenylmethane diisocyanate.
  • the polyisocyanates In general 10-500 % by weight of the polyisocyanates compared to the weight of the phenolic resins are used. 20-300% by weight of the polyisocyanates is preferred. Liquid polyisocyanates can be used in undiluted form, whereas solid or viscous polyisocyanates can be dissolved in organic solvents. The solvent can consist of up to 80 % by weight of the isocyanate components. As solvents for the polyisocyanate, either the above-named fatty acid esters or a mixture of fatty acid esters and up to 50 % by weight of aromatic solvents can be used.
  • Suitable aromatic solvents are naphthalene, alkyl-substituted naphthalenes, alkyl-substituted benzenes, and mixtures thereof.
  • aromatic solvents which consist of mixtures of the above named aromatic solvents and which have a boiling point range of between 140 and 230 °C.
  • no aromatic solvents are used.
  • the amount of polyisocyanate used results in the number of the isocyanate group being from 80 to 120 % with respect to the number of the free hydroxyl group of the resin.
  • the binder systems can include conventional additives, like, for example, silane (see for instance US 4,540,724 ), drying oils ( US 4,268,425 ) or "Komplex Kunststoffner” ( WO 95/03903 ).
  • the binder systems are offered, preferably, as two-component-systems, whereby the solution of the phenolic resin represents one component and the polyisocyanate, also in solution, if appropriate, is the other component. Both components are combined and subsequently mixed with sand or a similar aggregate, in order to produce the moulding compound.
  • the moulding compound contains an effective binding quantity of up to 15 % by weight of the binder system with respect to the weight of the aggregate.
  • the mixture can contain other conventional ingredients, like iron oxide, ground flax fiber, xylem, pitch and refractory meal (powder).
  • the aggregate In order to manufacture foundry moulded pieces from sand, the aggregate should exhibit a sufficiently large particle size. In this way, the founded piece has sufficient porosity, and fugitive gasses can escape during the casting process. In general at least 80 % by weight and preferably 90 % by weight of the aggregate should have an average particle size of less than or equal to 290 ⁇ m. The average particle size of the aggregate should have between 100 and 300 ⁇ m.
  • sand is preferred as the aggregate material to be used, where at least 70 % by weight, and preferably more than 80 % by weight of the sand is silicon dioxide.
  • Zircon, olivine, aluminosilicate sands and chromite sands are likewise suitable as aggregate materials.
  • the aggregate material is the main component in founded pieces.
  • the proportion of binder in general amounts to up to 15 % by weight, and often between 0.5 and 7 % by weight, with respect to the weight of the aggregate.
  • Especially preferred is 0.6 to 5 % by weight of binder compared to the weight of the aggregate.
  • the founded piece is cured so that it retains its exterior shape after being removed from the mold.
  • the liquid or gaseous curing system used for hardening in the binder system is based on diethylmethylamine (DEMA).
  • DEMA diethylmethylamine
  • DEMA appears to cure phenol formaldehyde and polyisocyanate resins faster than DMIPA. This is a main advantage for foundry cores having complex molding shapes.
  • DEMA can be carried out in a liquid state or preferably in a gaseous state and in any desired predetermined concentration, alone or preferably in combination with an inert carrier.
  • the inert gaseous carrier can be nitrogen or air, but carbon dioxide, less expensive than nitrogen, is sometimes utilized.
  • a liquid carrier can optionally be utilized.
  • a mixture comprising, in addition to DEMA, up to 25 %, and preferably up to 10 % by weight of at least another amine, primary, secondary and/or tertiary, although the concentration of the at least another amine impurities represents preferably less than 0.5 % by weight of the mixture comprising DEMA.
  • the DEMA can also contain small amounts of water: the concentration of water in DEMA is preferably kept below 0.2 % by weight.
  • silane with the general formula therefore -(R'-O)3-Si-R-is added to the moulding compound before the curing begins.
  • 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 alkyl amine-substituted amine radical with alkyl groups, which have 1-6 carbon atoms.
  • silanes examples include Dow Corning Z6040 and Union Carbide A-187 ([gamma]-glycidoxypropyltrimethoxysilane), Union Carbide A-1100 ([gamma]-aminopropyl triethoxysilane), Union Carbide A-1120 (N-[beta]-(aminoethyl)-[gamma]-aminopropyltrimethoxysilane) and Union Carbide A1160 (ureidosilane).
  • additives can be used, including wetting agents and sand mixture extending additives (English Benchlife-additives), such as those disclosed in US 4,683,252 or US 4,540,724 .
  • mould release agents like fatty acids, fatty alcohols and their derivatives can be used, but as a rule, they are not necessary.
  • the present invention also relates to a process of casting a metal, which comprises:
  • a tertiary amine either DMEA or DEMA or DMIPA
  • the amine concentrations used in the present test are on purpose at a default level i.e lower than the amount necessary to the full curing of the sand-resin mixtures.
  • the resins used for this test are commercial resins from Ashland-Avbbbne (Usine du Goulet- 20, rue Croix du Vallot, 27600 St Pierre-La Garenne - France) sold under the trade name Avecure®; these resins are composed of a formo-phenolic polyol and an isocyanate resins in accordance with the present description.
  • a fixed amount of sand-resins mixture with a predetermined amount of resins per mass unit of sand (normally between 0.5 and 2% by weight of each resin based on the amount of sand mixed) is placed in a long cylindrical shaped mould, the amine is poured as liquid ahead of the sand-resins cylinder in a U tube; a heated stream of carrier gas (normally nitrogen) at a fixed and predetermined rate is passed through the amine loaded U tubing.
  • the carrier gas stream brings the volatilised amine to the cylinder filled with sand-resin during a fixed time.
  • Test cores were prepared as follows:
  • water sensitivity of a cured sand-binder core is evaluated through of its mechanical resistance.
  • the resistance test is achieved on a cured (sand-binder) sample which has been exposed to a 98 % water saturated atmosphere at 20 °C for 24 hours just after the curing.
  • Conditions of gassing are the same as for table 1 and 2, excepted that 0.5 mL of each amine catalyst was used.
  • PU Part 1 and 2 as indicated in Table 3 are the polyol and polyisocyanate components respectively of each PU resin type indicated as Resin 1, 2, 3.
  • the resins used for this test are commercial resins from Ashland Sod-Chemie sold under the trade names Askocure® or Ecocure ®; these resins are composed of a formo-phenolic polyol and an isocyanate resins in accordance with the present description.
  • Transverse strength values have been measured twice for each resin and each amine curing and both results are mentioned in the table 3 (for instance, 290/300 for Resin 1 with DMIPA), the higher the value, the better in terms of mechanical resistance, so the better in terms of water resistance (ex. 460/470 for Resin 2 cured with DEMA indicates less water sensitivity than for the same resin cured with DMIPA as indicated by lower transverse strength values 420/440.
  • DEMA gives less water sensitivity than very reactive DMEA.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
EP07100919A 2007-01-22 2007-01-22 Verfahren zur Herstelung von Giessereikerne und Giessereiverfahren Withdrawn EP1955791A1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP07100919A EP1955791A1 (de) 2007-01-22 2007-01-22 Verfahren zur Herstelung von Giessereikerne und Giessereiverfahren
PCT/EP2008/050720 WO2008090159A1 (en) 2007-01-22 2008-01-22 Catalytic system for making foundry shaped cores and casting metals

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EP07100919A EP1955791A1 (de) 2007-01-22 2007-01-22 Verfahren zur Herstelung von Giessereikerne und Giessereiverfahren

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3429848A (en) * 1966-08-01 1969-02-25 Ashland Oil Inc Foundry binder composition comprising benzylic ether resin,polyisocyanate,and tertiary amine
US3432457A (en) * 1967-07-12 1969-03-11 Ashland Oil Inc Resinous composition comprising benzylic ether resin,polyisocyanate,and tertiary amine
EP0177871B1 (de) * 1984-10-12 1990-06-06 Acme Resin Corporation Polyurethan-Binder-Zusammensetzungen
EP0854159A1 (de) * 1997-01-21 1998-07-22 Sumitomo Bayer Urethane Co., Ltd. Verfahren zur Herstellung von Polyrethanhartschaum mit geringer Rauchentwicklung
WO1999043455A1 (en) * 1998-02-28 1999-09-02 Ashland Inc. Polyurethane forming no-bake foundry binders
US5981622A (en) * 1995-10-18 1999-11-09 Borden Chemical, Inc. Foundry binder of polyurethane, phenolic resin, polyisocyanate and epoxy resin
US20040051078A1 (en) * 2002-09-12 2004-03-18 Gernon Michael David Reactive amine catalysts for use in PUCB foundry binder

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3429848A (en) * 1966-08-01 1969-02-25 Ashland Oil Inc Foundry binder composition comprising benzylic ether resin,polyisocyanate,and tertiary amine
US3432457A (en) * 1967-07-12 1969-03-11 Ashland Oil Inc Resinous composition comprising benzylic ether resin,polyisocyanate,and tertiary amine
EP0177871B1 (de) * 1984-10-12 1990-06-06 Acme Resin Corporation Polyurethan-Binder-Zusammensetzungen
US5981622A (en) * 1995-10-18 1999-11-09 Borden Chemical, Inc. Foundry binder of polyurethane, phenolic resin, polyisocyanate and epoxy resin
EP0854159A1 (de) * 1997-01-21 1998-07-22 Sumitomo Bayer Urethane Co., Ltd. Verfahren zur Herstellung von Polyrethanhartschaum mit geringer Rauchentwicklung
WO1999043455A1 (en) * 1998-02-28 1999-09-02 Ashland Inc. Polyurethane forming no-bake foundry binders
US20040051078A1 (en) * 2002-09-12 2004-03-18 Gernon Michael David Reactive amine catalysts for use in PUCB foundry binder

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BURDITT M F ET AL: "MOLD & CORE BINDERS KEEP PACE WITH INDUSTRY DEMANDS", MODERN CASTING, AMERICAN FOUNDRY SOCIETY, SCHAUMBURG, IL, US, vol. 78, no. 6, 1 June 1988 (1988-06-01), pages 20 - 24, XP000020514, ISSN: 0026-7562 *

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