EP2454036A1 - Liant de fonderie comprenant un ou plusieurs cycloalcanes comme solvant - Google Patents

Liant de fonderie comprenant un ou plusieurs cycloalcanes comme solvant

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Publication number
EP2454036A1
EP2454036A1 EP10800213A EP10800213A EP2454036A1 EP 2454036 A1 EP2454036 A1 EP 2454036A1 EP 10800213 A EP10800213 A EP 10800213A EP 10800213 A EP10800213 A EP 10800213A EP 2454036 A1 EP2454036 A1 EP 2454036A1
Authority
EP
European Patent Office
Prior art keywords
foundry
binder
shape
cycloalkanes
component
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Withdrawn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
EP10800213A
Other languages
German (de)
English (en)
Inventor
Mark R. Stancliffe
Joerg Kroker
Xianping Wang
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.)
ASK Chemicals LLC
Original Assignee
ASK Chemicals LLC
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 ASK Chemicals LLC filed Critical ASK Chemicals LLC
Publication of EP2454036A1 publication Critical patent/EP2454036A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16Compositions 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
    • B22C1/20Compositions 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
    • B22C1/22Compositions 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
    • B22C1/2233Compositions 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
    • B22C1/2246Condensation polymers of aldehydes and ketones
    • B22C1/2253Condensation polymers of aldehydes and ketones with phenols
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16Compositions 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
    • B22C1/20Compositions 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
    • B22C1/22Compositions 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22CFOUNDRY MOULDING
    • B22C1/00Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16Compositions 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
    • B22C1/20Compositions 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
    • B22C1/22Compositions 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
    • B22C1/2206Compositions 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 by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/2213Polyalkenes

Definitions

  • sand casting In the foundry industry, one of the procedures used for making metal parts is "sand casting". In sand casting, disposable foundry shapes, e.g. molds, cores, sleeves, pouring cups, coverings, etc. are fabricated with a foundry mix that comprises a mixture of a refractory (typically sand) and an organic or inorganic binder.
  • a refractory typically sand
  • Foundry shapes are typically made by the so-called no-bake, cold-box processes, and/or heat cured processes.
  • a liquid curing catalyst is mixed with a refractory and binder to form a foundry mix before shaping the mixture in a pattern.
  • the foundry sand mix is shaped by compacting it in a pattern, and allowing it to cure until it is self-supporting.
  • a vaporous curing catalyst is passed through a shaped mixture (usually in a corebox) of the aggregate and binder to form a cured foundry shape.
  • the shape mixture is exposed to heat which activates the curing catalyst to form the cured foundry shape.
  • the binder typically has a low viscosity, must be gel-free, and remain stable under storage and use conditions. In order to obtain high productivity in the
  • binders are needed that cure efficiently, so the foundry shapes become self-supporting and handleable as soon as possible.
  • no-bake and heat cured processes there must be adequate worktime to allow for the fabrication of larger cores and molds.
  • cold-box processes the shaped foundry mix must cure nearly instantaneously upon contact with the vaporous curing catalyst.
  • the foundry shapes made with the foundry mixes using either no-bake, coid-box or heat cured binders have adequate mechanical strengths, particularly immediate tensile and transverse strengths, scratch hardness, and exhibit resistance to ambient humidity.
  • the flowability of a foundry mix made from a refractory and an organic binder can pose greater problems with respect to cold-box applications. This is because, in some cases, the components of the binder, particularly the components of phenolic urethane binders, may prematurely react after mixing with the refractory sand, while they are waiting to be used. If this premature reaction occurs, it will reduce the flowability of the foundry mix and the molds and cores made from the binder will have reduced mechanical strengths. This reduced flowability and decrease in strength with time indicates that the "benchlife" of the foundry mix is inadequate. If a binder results in a foundry mix without adequate benchlife, the binder is of limited commercial value.
  • Acyclic aliphatic solvents for instance kerosene and tetradecene have been used in small additions in polyol-polyisocya ⁇ ate binders, particularly phenolic urethane cold-box and no-bake binders, but their strong non-polar solvency properties have resulted in significantly limiting their amount in the binder formulation to less than five weight percent in the total binder, i.e. the combined weight of the Part I (polyol component) and the Part II (polyisocyanate component).
  • This disclosure relates to foundry binders comprising (a) a polyol
  • component selected from the group consisting of phenolic resins, polyether polyols, polyester polyols, aminopolyols, and mixtures thereof, and (b) a polyisocyanate component, wherein component (a) and/or (b) further comprise, as a solvent, one or more cycloalkanes.
  • foundry mixes prepared with the foundry binders, the cold-box, no-bake and heat cured processes for making foundry shapes using the foundry mixes, and processes for making cast metal parts using the foundry shapes and the processes for metal casting.
  • cycloalkanes as solvents in the defined foundry binders, as a complete or partial replacement for aromatic hydrocarbon solvents may: (1) reduce the amount of photochemically active species that may have a deleterious effect on the ozone layer and which are liberated when foundry shapes are made with the binders and when the foundry shapes are used to make metal parts in the course of the metal casting process; (2) reduce the formation of tar-like materials in the venting system of semi-permanent molds, a technology commonly used to make automotive cylinder heads; (3) provide improvements in quality of the cast metal parts made from the foundry shapes; (4) improve mold and core quality by eliminating or reducing solvent build-up in attrition reclaimed sand and green sand molding systems; and (5) reduce dense smoke formation during pouring, cooling and shake-out.
  • the polyol component of the foundry binder comprises a polyol selected from the group consisting of phenolic resins, polyether polyols, polyester polyols, amine polyols, and mixtures thereof.
  • phenolic resins Preferably used as the polyol are phenolic resole resins.
  • the polyisocyanate component of the binder comprises a polyisocyanate selected from the group consisting of aliphatic polyisocyanates and aromatic polyisocyanates and mixtures thereof.
  • a polyisocyanate selected from the group consisting of aliphatic polyisocyanates and aromatic polyisocyanates and mixtures thereof.
  • the preferred polyol is a phenolic resin, which is liquid or organic solvent-soluble.
  • the phenolic resin component of the binder composition is generally employed as a solution in an organic solvent.
  • the amount of solvent used should be sufficient to result in a binder composition with adequate viscosity permitting uniform coating thereof on the aggregate and uniform reaction with the polyisocyanate component in the foundry sand mix.
  • the specific solvent should be sufficient to result in a binder composition with adequate viscosity permitting uniform coating thereof on the aggregate and uniform reaction with the polyisocyanate component in the foundry sand mix.
  • concentration for the phenolic resin will vary depending on the type of phenolic resin employed and its molecular weight. In general, the solvent concentration will be in the range of up to 80% by weight of the polyol component, typically in the range of 20% to 80% by weight of the polyol component.
  • a phenolic resole resin is preferably prepared by reacting a molar excess of aldehyde with a phenol in the presence of either an alkaline catalyst or a metal catalyst.
  • the phenolic resins are preferably substantially free of water and are organic solvent soluble.
  • the preferred phenolic resins used in the subject binder compositions are well known in the art, and are specifically described in U.S. Patent 3,485,797, which is hereby incorporated by reference. These resins, known as benzylic ether phenolic resole resins, are the reaction products of an aldehyde with a phenol.
  • They contain a preponderance of bridges joining the phenolic nuclei of the polymer, which are ortho- ortho benzylic ether bridges. They are prepared by reacting an aldehyde and a phenol in a mole ratio of aldehyde to phenol of at least 1 :1 in the presence of a metal ion catalyst, preferably a divalent metal ion such as zinc, lead, manganese, copper, tin, magnesium, cobalt, calcium, and barium.
  • a metal ion catalyst preferably a divalent metal ion such as zinc, lead, manganese, copper, tin, magnesium, cobalt, calcium, and barium.
  • the phenol used to prepare the phenolic resole resins include phenol itself and/or any one or more of the phenols which have heretofore been employed in the formation of phenolic resins and which are not substituted at either the two ortho- positions or at one orf ⁇ o-position and the para-position. Such unsubstituted positions are necessary for the polymerization reaction. Any one, all, or none of the remaining carbon atoms of the phenol ring can be substituted.
  • the nature of the substituent can vary widely and it is only necessary that the substituent not interfere in the
  • Substituted phenols employed in the formation of the phenolic resins include alkyl-substituted phenols, aryl-substituted phenols, cycloalkyl-substituted phenols, aryloxy-substituted phenols, and halogen-substituted phenols, the foregoing
  • novolak resins may be used.
  • Bisphenol F is the simplest novolak and is prepared by reacting a large molar excess of phenol with formaldehyde under acidic conditions, which results in an isomer mixture comprising o,p' isomers, p,p' isomers and o,o' isomers.
  • a typical acid catalyst is oxalic acid.
  • Suitable phenols include phenol, o-cresol, p-cresol, 3,5-xyienol, 3,4-xylenol, 2,3,4-trimethyl phenol, 3-ethyl phenol, 3,5-diethyl phenol, p- butyl phenol, 3,5-dibutyl phenol, p-amyl phenol, p-cyclohexyl phenol, p-octyl phenol, 3,5-dicyclohexyl phenol, p-phenyl phenol, p-crotyl phenol, 3,5-dimethoxy phenol, 3,4,5- trimethoxy phenol, p-ethoxy phenol, p-butoxy phenol, 3-methyl-4-methoxy phenol, and p-phenoxy phenol.
  • Multiple ring phenols such as 4,4'-diphenol and bisphenol A are also suitable.
  • the aldehyde used to react with the phenol has the formula RCHO wherein R is a hydrogen or a hydrocarbon radical of 1 to 8 carbon atoms.
  • the aldehydes reacted with the phenol can include any of the aldehydes heretofore employed in the formation of phenolic resins such as formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde, benzaldehyde and the like, and mixtures thereof.
  • the most preferred aldehyde is formaldehyde.
  • Polyether polyols are commercially available and their method of preparation and determining their hydroxyl value is well known.
  • the polyether polyols are prepared by reacting an alkylene oxide with a polyhydric alcohol in the presence of an appropriate catalyst such as sodium methoxide according to methods well known in the art. Any suitable alkylene oxide or mixtures of alkylene oxides may be reacted with the polyhydric alcohol to prepare the poiyether polyols.
  • the alkyiene oxides used to prepare the polyether polyols typically have from two to six carbon atoms.
  • Representative examples include ethylene oxide, propylene oxide, butylene oxide, amylone oxide, styrene oxide, or mixtures thereof.
  • the polyhydric alcohols typically used to prepare the polyether polyols generally have a hydroxy functionality greater than 2.0, preferably from 2.5 to 5.0, most preferably from 2.5 to 4.5. Examples include ethylene glycol, diethylene glycol, propylene glycol, trimethylol propane, glycerine, and tetramethylol methane.
  • Aminopolyols are also well known and are described in U.S. Pat. No. 4,448,907, and are normally produced as the reaction product of an alkylene oxide and an amine compound. In general, any polyol containing at least one or more tertiary amine groups are considered to be within the scope of the definition of "aminopolyol".
  • the alkylene oxides which are used to prepare the amine polyols are preferably ethylene oxide and propylene oxide. However, it appears feasible to use other alkylene oxides as well.
  • the amine compounds which react with an alkylene oxide to yield the aminopolyol useful in the binder composition constituting this invention include ammonia and mono and polyamino compounds with primary or secondary amine groups.
  • aliphatic amines such as primary alkyl amines, ethylene diamine, diethylene triamine and triethylene tetramine
  • cycloaliphatic amines such as cyclohexyl amine, pyrrolidine, morpholine and N,N'-diethylene diamine
  • aromatic amines such as aniline, ortho-, meta-, and para-phenylene diamines, aniline-formaldehyde resins and the like.
  • the aminopolyols typically have a hydroxyl number of from about 200 to 1000 mg/g KOH, preferably from about 600 to 800 mg/g KOH.
  • Polyester polyols that can be used are aliphatic and/or aromatic polyester polyols.
  • Preferred polyester polyols are blends of liquid aromatic polyester polyols, which typically have a hydroxyl number from about 200 to 2,000 mg/g KOH, preferably from 200 to 1200 mg/g KOH, and most preferably from 250 to 800 mg/g KOH; a functionality equal to or greater than 2.0, preferably from 2 to 4; and a viscosity of 500 to 50,000 centipoise at 25 0 C, preferably 1 ,000 to 35,000 centipoise, and most preferably 1 ,500 to 25,000 centipoise.
  • Aromatic polyester polyols are typically prepared by ester interchange of aromatic ester and alcohols or glycols by an acidic catalyst. Phthalates are typically used as aromatic esters to make aromatic polyester polyols. Examples of alcohols used to prepare the aromatic polyester polyols are ethylene glycol, diethylene glycol, triethylene glycol, 1 ,3-propane diol, 1 ,4-butane diol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, trimethylol propane, tetramethylol methane, glycerin, and mixtures thereof. Aliphatic polyester polyols are typically made by direct condensation of the acid with the alcohol.
  • Examples of acids used to prepare the aliphatic polyester polyols are succinic acid, glutaric acid, adipic acid, citric acid, tertrahydrophthalic acid, and mixtures thereof.
  • Examples of alcohols used to prepare the aliphatic polyester polyols are ethylene glycol, diethylene glycol, Methylene glycol, 1 ,3-propane diol, 1 ,4-butane diol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, trimethylol propane, tetramethylol methane, glycerin, and mixtures thereof.
  • any organic polyisocyanate can be used in the Part II, the polyisocyanate component.
  • the polyisocyanate component of the binder composition is generally employed as a solution in an organic solvent, but binders can be used in which the Part Il consists of 100% polyisocyanate.
  • polyisocyanate component will vary depending on the type of phenolic resins employed in the Part I and its molecular weight. In general, the solvent concentration will be in the range of up to 80% by weight of the polyisocyanate component, typically in the range of up to 50%.
  • organic polyisocyanates used include polyisocyanates having a functionality of two or more, preferably 2 to 5. It may be aliphatic, cycloaliphattc, aromatic, or a hybrid polyisocyanate, or mixtures thereof.
  • polyisocyanates are aliphatic polyisocyanates such as hexamethylene d ⁇ socyanate and 1 ,12-diisocyanatododecane, alicyclic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate, and aromatic polyisocyanates such as methylene diphenylisocyanate and its isomers and polymeric varieties, 2,6-toluene diisocyanate, and derivatives thereof.
  • suitable organic solvent such as hexamethylene d ⁇ socyanate and 1 ,12-diisocyanatododecane
  • alicyclic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate
  • aromatic polyisocyanates such as methylene diphenylisocyanate and its isomers and polymeric varieties, 2,6-tolu
  • polyisocyanates are 1 ,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, and derivatives thereof, and the like. Also, it is contemplated that chemically modified polyisocyanates, prepolymers of polyisocyanates, and quasi prepolymers of polyisocyanates can be used. Solid or viscous polyisocyanates must be used in the form of organic solvent solutions, the solvent generally being present in a range of up to 80 percent by weight of the solution, typically in the range of up to 50%.
  • the polyisocyanates are used in sufficient concentrations to cause the curing of the phenolic resin when catalyzed with a tertiary amine curing catalyst.
  • the isocyanato group ratio of the polyisocyanate component to the hydroxyl groups of the polyol component is from 1.25:1 to 1 :1.25, preferably about 1 :1.
  • the Part I and/or the Part Il of the binder contain one or more
  • cycloalkanes as a solvent.
  • the cycloalkanes are selected from the group consisting of unsubstituted cycloalkanes, substituted cycloalkanes, and mixtures thereof.
  • the number of carbon atoms in the cycloalkane is from 5 to 24, the number of rings, including individual fused, bridged, and spiro-connected ring arrangements in the cycloalkanes is from 1 to 4, and the number of carbon atoms in the individual rings of bi- , tri-, and tetracyclic cycloalkanes is from 3 to 10, preferably from 5 to 8.
  • cycloalkanes that can be used as solvents in the Part I and/or Part Il of the binder include, but are not limited to, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, norcarane, norpinane, norbornane, decahydroazulene, tricycle[2.2.1.OJhexane, tetracyclo[5,2,2,0,0]undecane, spiro[4.5]decane,
  • dispiro[5.1.7.2]heptadecane decahydronaphthalene, bicyclohexyl, tercyclodecane, 1- cyclobutyi-2-cyclopentylethane, perhydroantharacene, perhydrofluorene, their partially unsaturated congeners, alkyl, alkenyl and alkynyl derivatives, and mixtures thereof.
  • the cycloalkane that will be used is decahydronaphthalene because it is the most readily and abundantly available cycloalkane.
  • the foundry binder may contain other solvents.
  • the foundry binder may further comprise one or more solvents selected from the group consisting of aromatic hydrocarbon solvents, dibasic ester solvents, fatty acid ester solvents, and mixtures thereof, which may be formulated in the Part I, Part II, or both the Part 1 and Part Il of the foundry binder.
  • the total amount of solvents in the binder typically ranges from 1 to 80 parts by weight based upon 100 parts by weight of the binder, preferably from 5 to 60 parts by weight based upon 100 parts by weight of the binder, and most preferably from 15 to 50 parts by weight based upon 100 parts by weight of the binder.
  • the total amount of cycloalkane in the binder typically ranges from 5 to 40 parts by weight based upon 100 parts by weight of the binder, preferably from 5 to 30 parts by weight based upon 100 parts by weight of the binder, and most preferably from 5 to 20 parts by weight based upon 100 parts by weight of the binder.
  • the total amount of cycloalkane used in the Part I ranges from 0 to 30 parts by weight based upon 100 parts by weight of the Part I 1 preferably from 5 to 25 parts by weight based upon 100 parts by weight of the Part I 1 and most preferably from 5 to 20 parts by weight based upon 100 parts by weight of the Part I.
  • the total amount of cycloalkane used in the Part Il typically ranges from 0 to 60 parts by weight based upon 100 parts by weight of the Part II, preferably from 5 to 40 parts by weight based upon 100 parts by weight of the Part II, and most preferably from 5 to 30 parts by weight based upon 100 parts by weight of the Part II.
  • Foundry mixes are prepared by mixing a foundry refractory with the foundry binder.
  • Various types of refractories and amounts of binder are used to prepare foundry sand mixes by methods well known in the art.
  • Ordinary shapes, shapes for precision casting, and refractory shapes can be prepared by using the binder systems and proper refractory.
  • the amount of binder and the type of refractory used are known to those skilled in the art.
  • the preferred refractory employed for preparing foundry mixes is silica sand wherein at least about 70 weight percent, and preferably at least about 85 weight percent, of the sand is silica.
  • Other suitable refractory materials for ordinary foundry shapes include zircon, olivine, aluminosilicate, chromite, and the like.
  • the amount of binder is generally no greater than about 10% by weight and frequently within the range of about 0.5% to about 7% by weight based upon the weight of the refractory. Most often, the binder content for ordinary foundry shapes ranges from about 0.6% to about 5% by weight based upon the weight of the refractory.
  • the binder compositions are preferably made available as a two-part system with the polyol component in one part (Part I) and the polyisocyanate component as the other part (Part II).
  • Part I polyol component
  • Part II polyisocyanate component
  • the polyol is first mixed with the refractory and then the polyisocyanate component is added, but the order of addition can be reversed. Methods of distributing the binder onto the refractory particles are well- known to those skilled in the art.
  • additives such as coupling agents, flow enhancers, benchlife extenders, release agents, drying agents, defoamers, wetting agents, etc. can be added to the binder, refractory, or foundry mix. The particular additives chosen will depend upon the specific purposes of the formulator.
  • metal parts are made by creating a mold assembly with an internal cavity shaped to match the dimensions and profile of the metal part to be cast and a gating system to feed the hot liquid metal into the cavity. Molds and/or cores are inserted are inserted into the mold assembly to produce external and internal casting geometry that will shape the metal part when molten metal is poured into the mold assembly and cools.
  • a refractory coating can be applied to all or select components of the mold assembly that come in contact with the liquid metal.
  • Foundry shapes are prepared by a cold-box process comprising:
  • Curing of polyol-polyisocyanate binders by the cold-box process is carried out by contacting the foundry shape with the vapor of a volatile tertiary amine as described in U.S. Patent 3,409,579, which is hereby incorporated into this disclosure by reference.
  • volatile tertiary amines which can be used, include
  • Foundry shapes are prepared by a no-bake process comprising:
  • the preferred liquid curing catalyst for the polyol-polyisocyanate binders is a tertiary amine and the preferred no-bake curing process is described in U.S. Patent 3,485,797 which is hereby incorporated by reference into this disclosure.
  • liquid curing catalysts are amines which have a pK b value generally in the range from about 5 to about 11 and include 4-alkyl pyridines wherein the alkyl group has from one to four carbon atoms, for instance 4-phenylpropylpyridine, isoquinoline, arylpyridines such as phenyl pyridine, pyridine, acridine, 2-methoxypyridine, pyridazine, 3- chloro pyridine, quinoline, N-methyl imidazole, N-ethyl imidazole, N-vinyl imidazole, 4,4'- dipyridine, 1-methyibenzimidazole, 1,4-thiazine and (3-dimethylamino)propylamine.
  • 4-alkyl pyridines wherein the alkyl group has from one to four carbon atoms
  • arylpyridines such as phenyl pyridine, pyridine, acridine, 2-methoxypyr
  • Foundry shapes are prepared by a heat cured process comprising:
  • Metal parts are prepared by a process for casting a metal part comprising: (k) inserting a foundry shape into a casting assembly having one or more molds and/or cores;
  • the metal parts can be cast from ferrous metals such as grey and white iron, ductile iron, compacted graphite iron and steel, and nonferrous metals such as aluminum, magnesium, copper, zinc, titanium and alloys thereof.
  • ferrous metals such as grey and white iron, ductile iron, compacted graphite iron and steel
  • nonferrous metals such as aluminum, magnesium, copper, zinc, titanium and alloys thereof.
  • the temperature of the molten ferrous metal ranges from about 1100 0 C to about 1700 0 C.
  • the temperature of the molten nonferrous metal ranges from about 400 0 C to about 1700 0 C.
  • Test foundry cores were made with by the cold-box process by first mixing Congleton HST 50 silica sand (from WBB minerals, Sibelco UK Ltd.) with the binder formulations described in Table I in a Kenwood Chef mixer for one minute.
  • the phenolic resole resin (RESIN) used in the Part I of the binder was a polybenzylic ether phenolic resin prepared with zinc acetate dihydrate as the catalyst according to methods well-known in the art.
  • the polyisocyanate used in the Part Il of the binder was poly(methylene diphenylisocyanate) having a functionality of 2.7. Equal amounts of Part I and Part Il were employed and the amount of the total binder used was 1.2 weight percent based on the weight of the sand.
  • test cores having dimensions of 120mm x 22.4mm x 6mm by blowing the foundry sand mix into a metal pattern where they were cured by the cold-box process as described in U.S. Patent 3,409,579.
  • the test cores were contacted with a mixture of triethylamine (0.25 ml) in nitrogen at a pressure of 1.4 bar for 1 second, followed by purging with nitrogen at a pressure of 4 bar for about 18 seconds, thereby forming the test specimen.
  • test cores were made with a freshly prepared foundry sand mix and the transverse strength was measured 30 seconds, 3 minutes, and 6 minutes after the specimen was formed. Measuring the transverse strength of the test cores enables one to predict how the mixture of sand and binder will work in actual foundry operations. Lower transverse strengths for the shapes indicate that the phenolic resin and polyisocyanate reacted more extensively during and after mixing with the sand and prior to curing.
  • Examples A and B are comparison examples and do not contain any cycloalkane, while Example 1 is within the scope of this invention.
  • Table I Binder formulations and transverse strengths of test cores made with binders
  • Aromatic hydrocarbon solvent Aromatic hydrocarbon solvent

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention se rapporte à un liant de fonderie comprenant (a) un composant polyol sélectionné dans le groupe de résines phénoliques, de polyols de polyéther, polyester polyols, d’aminopolyols, et de mélanges de ceux-ci, et (b) un composant polyisocyanate, le composant (a) et/ou le composant (b) comprenant en outre, comme solvant, un ou plusieurs cycloalcanes.
EP10800213A 2009-07-16 2010-06-03 Liant de fonderie comprenant un ou plusieurs cycloalcanes comme solvant Withdrawn EP2454036A1 (fr)

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US22603609P 2009-07-16 2009-07-16
PCT/US2010/037212 WO2011008362A1 (fr) 2009-07-16 2010-06-03 Liant de fonderie comprenant un ou plusieurs cycloalcanes comme solvant

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EP2454036A1 true EP2454036A1 (fr) 2012-05-23

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US (1) US20110129387A1 (fr)
EP (1) EP2454036A1 (fr)
JP (1) JP2012533433A (fr)
KR (1) KR20120081070A (fr)
CN (1) CN102481621A (fr)
BR (1) BR112012000928A2 (fr)
CA (1) CA2766997A1 (fr)
EA (1) EA201270141A1 (fr)
MX (1) MX2012000758A (fr)
WO (1) WO2011008362A1 (fr)

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ES2613594T3 (es) * 2011-07-19 2017-05-24 Ask Chemicals L. P. Método para el curado de un perfil de fundición de caja fría con un catalizador gaseoso
AU2013271509A1 (en) * 2012-06-08 2014-12-11 Ask Chemicals L.P. "no-bake" foundry mix with extended work time
JP6233996B2 (ja) 2013-08-16 2017-11-22 ザ エクスワン カンパニー 3次元印刷される金属鋳造用鋳型及び同鋳型の製造方法
CN104785708B (zh) * 2015-04-17 2016-09-07 广西藤县通轩立信化学有限公司 铸造用酚醛树脂的制备方法
WO2017075351A1 (fr) * 2015-10-30 2017-05-04 Ask Chemicals, L.P. Liant polyuréthane contenant un solvant alcoolique
DE102016203896A1 (de) * 2016-03-09 2017-09-14 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Zweikomponenten-Bindemittelsystem für den Polyurethan-Cold-Box-Prozess
CN106391992B (zh) * 2016-10-12 2018-07-13 山东科技大学 聚酯多元醇与酚醛树脂复合型冷芯盒制芯粘结剂体系
CN106424536B (zh) * 2016-10-12 2018-07-27 山东科技大学 无游离醛、游离酚的新型三乙胺冷芯盒铸造用粘结剂
DE102016125702A1 (de) * 2016-12-23 2018-06-28 Ask Chemicals Gmbh Komponentenystem zur Herstellung von Kernen und Formen
DE102020118148A1 (de) 2020-07-09 2022-01-13 Bindur Gmbh Formstoff zur Herstellung von Kernen und Verfahren zu dessen Härtung

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3281378A (en) * 1963-06-06 1966-10-25 Merck & Co Inc Diisocyanato substituted aliphatic carboxylic acid ester urethane reaction products
US3216078A (en) * 1962-08-30 1965-11-09 Magnet Cove Barium Corp Process for casting steel and compositions of matter for use therein
US3404118A (en) * 1964-01-30 1968-10-01 Ashland Oil Inc Reactive modifiers for thermosetting resins
US3485797A (en) * 1966-03-14 1969-12-23 Ashland Oil Inc Phenolic resins containing benzylic ether linkages and unsubstituted para positions
US3429848A (en) * 1966-08-01 1969-02-25 Ashland Oil Inc Foundry binder composition comprising benzylic ether resin,polyisocyanate,and tertiary amine
US4448907A (en) * 1981-03-30 1984-05-15 Ashland Oil, Inc. Process for casting lightweight metals
US4590229A (en) * 1984-06-04 1986-05-20 Ashland Oil, Inc. Phenolic resin-polyisocyanate binder systems
US4568728A (en) * 1984-07-16 1986-02-04 Delta Resins & Refractories Foundry binder with improved breakdown and improved thermal reclamation properties
US4663473A (en) * 1986-08-25 1987-05-05 The United States Of America As Represented By The Secretary Of The Army Isocyanates from oxalyl chloride and amines
JPH07310104A (ja) * 1994-03-23 1995-11-28 Nippon Shokubai Co Ltd 粉体射出成形用バインダー、粉体射出成形用組成物及び焼結部材の製造法
US6342543B1 (en) * 1999-09-24 2002-01-29 Ashland Inc. Amine curable foundry binder system
DE10256953A1 (de) * 2002-12-05 2004-06-24 Ashland-Südchemie-Kernfest GmbH Heißhärtendes Bindemittel auf Polyurethanbasis
WO2004103607A2 (fr) * 2003-05-13 2004-12-02 Ashland Inc. Procede de production de formes pour la fonderie
US20050250874A1 (en) * 2004-05-04 2005-11-10 Ha-International, Llc Phenolic urethane foundry binder
US20060079601A1 (en) * 2004-10-13 2006-04-13 Gullo Mark J Foundry sandcore mold release composition
CN100506426C (zh) * 2006-07-10 2009-07-01 旭有机材工业株式会社 铸型用有机粘结剂、型砂组合物及铸型
DE102006058414A1 (de) * 2006-12-12 2008-06-19 Clariant International Limited Carboxyethyl(alkyl)phosphinsäure-Alkylestersalze

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011008362A1 *

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US20110129387A1 (en) 2011-06-02
JP2012533433A (ja) 2012-12-27
BR112012000928A2 (pt) 2016-03-01
CA2766997A1 (fr) 2011-01-20
MX2012000758A (es) 2012-08-03
KR20120081070A (ko) 2012-07-18
WO2011008362A1 (fr) 2011-01-20
CN102481621A (zh) 2012-05-30

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