WO1989007626A1 - Liants de fonderie formant du polyurethane a faible teneur en solides, pour procede a boite froide - Google Patents

Liants de fonderie formant du polyurethane a faible teneur en solides, pour procede a boite froide Download PDF

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Publication number
WO1989007626A1
WO1989007626A1 PCT/US1989/000448 US8900448W WO8907626A1 WO 1989007626 A1 WO1989007626 A1 WO 1989007626A1 US 8900448 W US8900448 W US 8900448W WO 8907626 A1 WO8907626 A1 WO 8907626A1
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Prior art keywords
foundry
shape
aggregate
weight
pattern
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Application number
PCT/US1989/000448
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English (en)
Inventor
Colleen M. Henry
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Ashland Oil, Inc.
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Publication date
Application filed by Ashland Oil, Inc. filed Critical Ashland Oil, Inc.
Publication of WO1989007626A1 publication Critical patent/WO1989007626A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/542—Polycondensates of aldehydes with phenols
    • 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

  • This invention relates to low solids polyurethane-formin foundry binders.
  • the binders are used for forming foundry mixes which are used in a cold-box process for preparing foundr shapes.
  • the polyurethane-forming binders utilize specific organic polyisocyanates in conjunction with polymerized linseed
  • sand casting In the foundry industry, one of the procedures used for making metal parts is by sand casting. In sand casting, disposable molds and cores are fabricated with a mixture of sand and an organic or inorganic binder. The binder is usually used to strengthen the cores, which are the most fragile part of the 5 mold assembly.
  • a binder commonly used in the cold-box fabrication process is a polyurethane binder derived from curing a polyurethane- forming binder composition with a gaseous tertiary amine catalyst.
  • the polyurethane-forming binder composition usually consists of a phenolic resin component and polyisocyanate 5 hardener component which may react prior to curing with the gaseous catalyst. If this reaction occurs, it will reduce the flowability of the mixture when it is used for casting, and the resulting molds and cores will have reduced strength.
  • the bench life of the mixture of the sand and polyurethane- forming binder composition is the time period between forming the mixture of the sand and polyurethane-forming binder and the time when the mixture is no longer useful for making and acceptable molds and cores.
  • a measure of mold and core acceptability is tensile strength. If a mixture of sand and 5 polyurethane-forming binder composition is used after the bench life has expired, the resulting molds and cores will hav insufficient tensile strength.
  • This invention relates to polyurethane-forming foundr binders comprising
  • T e polyurethane-forming binders are used to form foundr mixes which are cured by the cold-box process with a gaseous o vaporized tertiary amine, used alone or mixed with an iner carrier gas such as carbon dioxide, to form foundry shapes whic are used to prepare metal castings.
  • SUBSTITUTESHEET Several advantages result when using the subject binders.
  • the major advantage is that foundry mixes prepared with th binders have an extended benchlife.
  • the use of lower solids in the isocyanate component enables the formulato to use a phenolic resin component with lower solids which wil result in lower amounts of free formaldehyde. This i advantageous from an environmental standpoint.
  • the use of lowe solids formulations also results in a reduction of lustrous carbon when castings are prepared. Lustrous carbon causes casting defects.
  • the phenolic resin component comprises a phenolic resin and a solvent.
  • phenolic resins used in the phenolic resin compositions are well known in the foundry art. Suitable phenolic resins are those which are soluble in the solvents employed, such as phenolic resole or phenolic novolak resins formed by reacting phenolic compounds with aldehydes.
  • Resole or A-stage resins, as well as resitol or B-stage resins may be made by reacting a molar excess of aldehyde, such as formaldehyde, with a phenolic material in the presence divalent metal ion catalysts.
  • the novolak resins may be formed by reacting a molar excess of phenolic material with an aldehyde in the presence of an acid catalyst.
  • These 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 1.0:1.0, preferably from 1.1:1.0 to 2.0:1.0 in the presence of a divalent metal ion catalyst, preferably a divalent metal ion such as zinc, lead, manganese, copper, tin, magnesium, cobalt, calcium, and barium.
  • the phenols may be represented by the following structural formula:
  • A, B, and C are hydrogen atoms, or hydroxyl radicals, or hydrocarbon radicals or oxyhydrocarbon radicals, or halogen atoms, or combinations of these.
  • the phenol may be a multiple ring phenol such as bisphenol A.
  • the phenolic resin is preferably non-aqueous.
  • non- aqueous is meant a phenolic resin which contains water in amounts of no more than about 10%, preferably no more than about 1% based on the weight of the resin.
  • the phenolic resin component preferably includes benzylic ether resins.
  • the aldehyde has the formula R'CHO wherein R' is a hydrogen or hydrocarbon radical of 1 to 8 carbon atoms.
  • phenolic resin is meant the reaction product of a phenol with an aldehyde in which the final mixture of molecules in the reaction products is dependent upon the specific reactants selected, the starting ratio of these reactants, and the conditions of the reaction _ (for example, the type of catalyst, the time and temperature of the reaction, the solvents, and/or other ingredients present, and so forth).
  • the reaction products, that is the phenolic resin will be a mixture of different molecules and may contain in widely varying ratios addition products, condensation products, and unreacted reactants such as unreacted phenol and/or unreacted aldehyde.
  • addition product is meant reaction products in which n organic group has been substituted for at least one hydrogen of a previously unreacted phenol or of a condensation product.
  • condensation product is meant reaction products that link two or more aromatic rings.
  • the phenolic resins are preferably substantially free of water and are organic solvent soluble.
  • the phenolic component includes any one or more of the phenols which have heretofore been employed in the formation of phenolic resins and which are not substituted at both ortho-positions or at one ortho-position and the para-position. It has been found that substitution in these positions interfere with the polymerization reaction. Any one, all, or none of the remaining carbon atoms of the phenol ring can be substituted.
  • the nature of the sub ⁇ tituent can vary widely and it is only necessary that the substituent not interfere in the polymerization of the aldehyde with the phenol at the ortho-position and/or para-position.
  • Substituted phenols employed in the formation of the phenolic resins include alkyl-substituted phenols, aryl-substituted phenols, cyclo-alkyl-substituted phenols, aryloxy-substituted phenols, and halogen-substituted phenols, the foregoing substituents containing from 1 to 26 carbon atoms and preferably from 1 to 12 carbon atoms.
  • Suitable phenols include phenol, 2,6-xylenol, o-cresol, p-cresol, 3,5-xylenol, 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.
  • the phenol reactant is preferably reacted with an aldehyde to form phenolic resins and more preferably benzylic ether resins.
  • 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, and benzaldehyde.
  • the aldehydes employed have the formula R'CHO wherein R' is a hydrogen or a hydrocarbon radical of 1 to 8 carbon atoms. The most preferred aldehyde is formaldehyde.
  • the phenolic resin used must be liquid or organic solvent- suitable. Solubility in an organic solvent is desirable to achieve uniform distribution of the binder on the aggregate.
  • the substantial absence of water in the phenolic resin is desirable in view of the reactivity of the binder composition of the present invention with isocyanates.
  • Mixtures of phenolic resins can be used. It is also possible to use phenolic resins as described herein which are modified with lower alkyl alcohols having from 1 to 8 carbon atoms such as methanol, n-butanol, ethanol, and the like. By methods well known in the art it is possible to modify the phenolic resin by adding the alcohol to the phenol and formaldehyde during the reaction, or reacting the alcohol with the phenolic resin after the resin has formed.
  • the liquid organic polyisocyanate used in the isocyanate component has a functionality of 2.0 to 2.4, preferably 2.2 to 2.4 and is used in conjunction with from 1 weight percent to 5 weight percent of polymerized linseed oil, preferably from 2 weight to 4 weight percent, based upon the total weight of the isocyanate component.
  • Polymerized linseed oil is a type of blown oil prepared by oxidizing linseed according to well known methods.
  • the polymerized linseed oils particularly useful are known as heat bodied medium acid oils, preferably having a viscosity of Z to
  • the manner in which the polymerized linseed oil is added to the organic polyisocyanate is not of particular significance. Usually, it is added as a final ingredient to the polyisocyanate component.
  • the polyisocyanates are used in sufficient concentrations to cause the curing of the phenolic resin when reacted with the curing catalyst.
  • the ratio of the isocyanate groups of the polyisocyanate to the hydroxyl of the phenolic resin is from 0.9:1.1 to 1.1:0.9, most preferably about 0.94 1.0 to 1.0:0.94.
  • the resin component contains at least one aromatic hydrocarbon solvent and one ester solvent, while the isocyanate component contains at least one aromatic hydrocarbon solvent.
  • Suitable aromatic solvents are benzene, toluene, xylene, ethylbenzene, and mixtures thereof.
  • Preferred aromatic solvents are mixed solvents that have an aromatic content of at least 90% and a boiling point range of 138°C to 232°C.
  • the polar solvents should not be extremely polar such as to become incompatible with the aromatic solvent.
  • Suitable polar solvents are generally those which have been classified in the art as coupling solvents and include furfural, furfuryl alcohol, Cellosolve acetate, butyl Cellosolve, butyl Carbitol, diacetone alcohol, and Texanol.
  • esters which are used in the phenolic resin component are liquid dialkyl esters such as dialkyl phthalate of the type disclosed in U.S. Patent No. 3,905,934, the entire contents of which are incorporated herein by reference.
  • Such esters preferably have the structure: where R-. and R 2 are alkyl radicals of 1 to 12 carbon atoms and the total number of carbon atoms in the R groups does not exceed 16.
  • R, and R 2 are alkyl radicals of 3 to 6 carbon atoms and the total number of carbon atoms in 1 and R_ is 0 between 6 and 12.
  • R group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, and other isomers of the foregoing.
  • dialkyl esters include dimethyl glutarate such as 5 available from DuPont under the trade designation DBE-5; dimethyl adipate available from DuPont under the trade designation DBE-6, dimethyl succinate; and mixtures of such esters which are available from DuPont under the trade designation DBE, and dialkyl adipates and succinates with 0 alcohols up to 12 carbon atoms.
  • the solids level of the isocyanate component is from 68 weight percent to 75 weight percent, based upon the weight of the isocyanate component, preferably from 70 weight percent to 74 weight percent. Furthermore, since an isocyanate 5 to hydroxyl ratio of 0.9:1.1 to 1.1:0.9, preferably from 0.94:1.0 to 1.0:0.94 is used, the phenolic resin will have a solids level 45 weight percent to 55 weight percent based upon the total weight of the resin component, preferably from 49 weight percent to 54 weight percent. °
  • the amount of aromatic hydrocarbon solvent used in the phenolic resin component is from 10 to 30 weight percent, preferably 15 to 25 weight percent, said weight percent based upon the total weight percent of the phenolic resin component.
  • the amount of ester solvent used in the phenolic resin component 5 is generally from 10 weight percent to 20 weight percent based upon the weight percent of the phenolic resin component.
  • the weight ratio of aromatic hydrocarbon solvent to ester solvent in the phenolic resin component is generally from 1:2 to 2:1.
  • the binder compositions are preferably made available as a two-package system with the phenolic resin in one package and the isocyanate component in the other package.
  • the binder components are combined and then admixed with sand or a similar aggregate to form a foundry mix or the mix can also be formed by sequentially admixing the components with the aggregate. Methods of distributing the binder on the aggregate particles are well-known to those skilled in the art.
  • the mix can, optionally, contain other ingredients such as iron oxide, ground flax fibers, wood cereals, pitch, refractory flours, and the like.
  • benchlife extender In many formulations it is preferred to use a benchlife extender.
  • the benchlife extender is added to the isocyanate component in an effective amount to extend the benchlife of the foundry mix.
  • the amount used varies depending upon the benchlife desired but generally is from 0.1 weight percent to 2.0 weight percent based upon the weight of the isocyanate component.
  • benchlife extenders are such as those disclosed in U.S. Patent 4,540,724 and 4,683,252 which are hereby incorporated by reference.
  • the aggregate employed has a particle size large enough to provide sufficient porosity in the foundry shape to permit escape of volatiles from the shape during the casting operation.
  • ordinary sand-type foundry shapes refers to foundry shapes which have sufficient porosity to permit escape of volatiles from it during the casting operation.
  • at least about 80% and preferably about 90% by weight of aggregate employed for foundry shapes has an average particle size no smaller than about 0.1mm.
  • the aggregate for foundry shapes preferably has an average particle size between about 0.1mm and about 0.25mm.
  • the preferred aggregate employed for ordinary foundry shapes is sand wherein at least about 70 weight percent and preferably at least about 85 weight percent of the sand is silica.
  • Suitable aggregate materials in ⁇ clude zircon, olivine, aluminosilicate, chromite, and the like.
  • the predominant portion and generally at least about 80% of the aggregate has an average particle size no larger than 0.1mm and preferably between about 0.04mm and 0.075mm.
  • Preferably at least about 90% by weight of the aggregate for precision casting applications has a particle size no larger than 0.1mm and preferably between 0.04mm and 0.075mm.
  • the preferred aggregates employed for precision casting applications are fused quartz, zircon, magnesium silicate, olivine, and aluminosilicate.
  • the predominant portion and at least 80 weight percent of the aggregate employed has an average particle size under 0.075mm and preferably no smaller than 0.04mm.
  • Preferably at least about 90% by weight of the aggregate for a refractory has an average particle size under 0.075mm and preferably no smaller than 0.04mm.
  • the aggregate employed in the preparation of refractories must be capable of withstanding the curing temperatures such as above about 815°C which are needed to cause sintering for utilization.
  • Suitable aggregate employed for preparing refractories include the ceramics such as refractory oxides, carbides, nitrides, and suicides such as aluminum oxide, lead oxide, chromic oxide, zirconium oxide, silica, silicon carbide, titanium nitride, boron nitride, molybdenum disilicide, and carbonaceous material such as graphite. Mixtures of the aggregate can also be used, when desired, including mixtures of metals and ceramic.
  • abrasive grains for preparing abrasive articles examples include aluminum oxide, silicon carbide, boron carbide, corundum, garnet, emery, and mixtures thereof. These abrasive materials and their uses for particular jobs are understood by persons skilled in the art and are not altered in the abrasive articles contemplated by the present invention.
  • inorganic filler can be employed along with the abrasive grit in preparing abrasive articles. It is preferred that at least about 85% of the inorganic fillers has an average particle size no greater than 0.075mm. It is most preferred that at least about 95% of the inorganic filler has an average particle size no greater than 0.075mm.
  • Some inorganic fillers include cryolite, fluorospar, silica, and the like. When an inorganic filler is employed along with the abrasive grit, it is generally present in amounts from about 1% to about 30% by weight based upon the combined weight of the abrasive grit and inorganic filler.
  • the aggregate employed is preferably dry, it can contain small amounts of moisture, such as up to about 0.3% by weight or even higher based on the weight of the aggregate.
  • the aggregate constitutes the major constituent and the binder constitutes a relatively minor amount of the foundry mix.
  • 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 15 the weight of the aggregate. Most often, the binder content ranges from about 0.6% to about 5% by weight based upon the weight of the aggregate in ordinary sand-type foundry shapes.
  • the amount of binder is generally no greater than about 40% by
  • the amount of binder is generally no greater than about 40% by weight and frequently within the range of about 5% to about 20% by weight based upon the weight of the
  • the amount of binder is generally no greater than about 25% by weight and frequently within the range of about 5% to about 15% by weight based upon the weight of the abrasive material or grit.
  • the aggregate employed is preferably dry, moisture of up to about 1 weight percent based on the weight of the sand can be tolerated. This is particularly true if the solvent employed is non-water-miscible or if an excess of the polyiso ⁇ cyanate necessary for curing is employed since such excess
  • SUBSTITUTE SHEET release agents, solvents, etc. can be added to the phenolic resin composition, polyisocyanate composition, binder composi ⁇ tion, aggregate, or foundry mix.
  • the particular additives chosen will depend upon the specific purposes of the formulator.
  • the molding mix is molded into the desired shape, whereupon it is cured by the so called cold box process at ambient temper ⁇ ature. Curing can be affected by passing a gaseous or vaporized tertiary amine, used alone or mixed with an inert carrier gas such as carbon dioxide, through the molded mix such as described in U.S. Patent 3,409,579 which is hereby incorporated by reference.
  • the phenolic resin (abbreviated as PR) used in all of the examples was a resin containing a polymeric material having a preponderance of bridges joining its phenolic nuclei which are ortho-ortho benzylic ether bridges.
  • the resins were prepared by reacting a molar excess of paraformaldehyde with phenol at elevated temperatures in the presence of a divalent metal catalyst. The procedures for preparing such resins are set forth in U.S. Patent 3,485,797.
  • organic polyisocyanate used had a functionality of 2.2 and is sold under the tradename MONDUR MRS-5 by Mobay Chemical Company.
  • the IC used contained a medium acid polymerized linseed oil (PLO) having a viscosity of Z-Zl and meets Federal Specifications TT-L-201.
  • PLO medium acid polymerized linseed oil
  • the amount of PLO used is specified in the examples and tables that follow.
  • the resulting foundry mix was formed into standard AFS tensile test samples (dogbones) according to standard procedures by blowing it into a corebox and contacting it with dimethyl- ethylamine according to the cold-box process. Measuring the tensile strength of the dog bone samples enables one to predict how the mixture of sand and polyurethane-forming binder will work in actual foundry operations.
  • dog bone samples were formed from the foundry mix immediately after mixing, (zero bench) 3 hours after mixing, and 5 hours after mixing. Then tensile strengths of the various cured samples were measured immediately (IMM), 1 hour, and 24 hours after curing.
  • Some of the dog bone samples that were formed from freshly prepared (zerobench) foundry mixes were stored for 24 hours at a relative humidity (RH) of 100% and a temperature of 25°C. Tensile strengths of the dog bone samples are given in the tables.
  • AHS an aromatic hydrocarbon solvent such as HI-SOL 15, HI-SOL 10, Getty 400, etc. or mixtures thereof.
  • DBE a dibasic ester solvent blend.
  • DOA dioctyl adipate
  • KER kerosene
  • PMA propylene glycol mono methyl ether acetate.
  • A-187 a silane sold by Union Carbide
  • MPCP a benchlife extender known as onphenylchloro- phosphate.
  • the weights in the examples are parts by weight unless otherwise specified.
  • Examples 1 - 3 illustrate the effect of using varying solids levels in the isocyanate component (IC) and phenolic resin component (PRO when MRS-5 and PLO are used in the isocyanate component.
  • the amount of PLO used in these examples was four weight percent based upon the total weight of the IC.
  • Table I discloses solids level (SL) of the IC and formulations used in the IC and PRC.
  • the calculated isocyanate to hydroxyl ratio in these examples is 0.94.
  • Example A had high tensile strengths at zero bench and after 24 hours benchlife, the tensile strength after 5 hours benchlife was unacceptable.
  • Example 1-3 which used a low solids formulation, had had acceptable tensile strengths at zero bench and after 5 hours benchlife.
  • Extended benchlife also occurs if a benchlife extender is added to the formulation as Examples 4 - 5 show. Moreover, because the tensile measurement are better after extended benchlife with the low solids ' formulation, less benchlife extender can be used.
  • EXAMPLE 4 - 5 The formulations used in these examples were substantially the same as those in Examples 1-3 except 0.99 pbw of MPCP benchlife extender was added to IC (the AHS was adjusted appropriately for the elimination of the silane and addition of
  • Example B is a comparative example.
  • the isocyanate to hydroxyl ratio in these examples was 0.94.
  • the tensile strengths are also given in the table. The data confirms that formulations using the particular isocyanate component with lower solids provide better tensile strengths when the foundry mix has an extended benchlife, ie. 5 hours.
  • Example 6 and Comparative Example C illustrate the signifi ⁇ cance of using the organic polyisocyanate with PLO. Both formu ⁇ lations were similar to those used in Examples 4-5 except Comparison Example C did not contain PLO. The results are shown in Table IV which follows. The data indicate that the PLO is needed to obtain acceptable tensile strengths.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Cette invention concerne un liant formant du polyuréthane à faible teneur en solides, destiné au procédé à boîte froide. Les liants utilisent des polyisocyanates organiques spécifiques conjointement avec de l'huile de lin polymérisée.
PCT/US1989/000448 1988-02-16 1989-02-06 Liants de fonderie formant du polyurethane a faible teneur en solides, pour procede a boite froide WO1989007626A1 (fr)

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US15627588A 1988-02-16 1988-02-16
US156,275 1988-02-16

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WO1989007626A1 true WO1989007626A1 (fr) 1989-08-24

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6214265B1 (en) 1998-12-17 2001-04-10 Bayer Corporation Mixed PMDI/resole resin binders for the production of wood composite products
US6294117B1 (en) 1998-12-17 2001-09-25 Bayer Corporation Mixed PMDI/solid novolac resin binders for the production of wood composite products
US6416696B1 (en) 1999-12-16 2002-07-09 Bayer Corporation Aqueous mixed pMDI/phenolic resin binders for the production of wood composite products
WO2012127299A1 (fr) 2011-03-22 2012-09-27 Rhodia Poliamida E Especialidades Ltda Systèmes liants de fonderie
CN103320080A (zh) * 2013-06-06 2013-09-25 常熟市江南粘合剂有限公司 聚异氰酸酯胶生产工艺
WO2014125313A1 (fr) 2013-02-12 2014-08-21 Rhodia Poliamida E Especialidades Ltda Systèmes de solvants et compositions de revêtement contenant lesdits systèmes

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US3409579A (en) * 1966-08-01 1968-11-05 Ashland Oil Inc Foundry binder composition comprising benzylic ether resin, polyisocyanate, and tertiary amine
US3485797A (en) * 1966-03-14 1969-12-23 Ashland Oil Inc Phenolic resins containing benzylic ether linkages and unsubstituted para positions
US3676392A (en) * 1971-01-26 1972-07-11 Ashland Oil Inc Resin compositions
US4268425A (en) * 1979-05-14 1981-05-19 Ashland Oil, Inc. Phenolic resin-polyisocyanate binder systems containing a drying oil and use thereof
US4698377A (en) * 1986-09-26 1987-10-06 Acme Resin Corporation Binder compositions containing phenolic resins and esters of alkoxy acids
US4760101A (en) * 1986-08-25 1988-07-26 Ashland Oil, Inc. Polyurethane-forming binder compositions containing certain carboxylic acids as bench life extenders

Patent Citations (6)

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Publication number Priority date Publication date Assignee Title
US3485797A (en) * 1966-03-14 1969-12-23 Ashland Oil Inc Phenolic resins containing benzylic ether linkages and unsubstituted para positions
US3409579A (en) * 1966-08-01 1968-11-05 Ashland Oil Inc Foundry binder composition comprising benzylic ether resin, polyisocyanate, and tertiary amine
US3676392A (en) * 1971-01-26 1972-07-11 Ashland Oil Inc Resin compositions
US4268425A (en) * 1979-05-14 1981-05-19 Ashland Oil, Inc. Phenolic resin-polyisocyanate binder systems containing a drying oil and use thereof
US4760101A (en) * 1986-08-25 1988-07-26 Ashland Oil, Inc. Polyurethane-forming binder compositions containing certain carboxylic acids as bench life extenders
US4698377A (en) * 1986-09-26 1987-10-06 Acme Resin Corporation Binder compositions containing phenolic resins and esters of alkoxy acids

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6214265B1 (en) 1998-12-17 2001-04-10 Bayer Corporation Mixed PMDI/resole resin binders for the production of wood composite products
US6294117B1 (en) 1998-12-17 2001-09-25 Bayer Corporation Mixed PMDI/solid novolac resin binders for the production of wood composite products
US6641761B2 (en) 1998-12-17 2003-11-04 Bayer Corporation Mixed PMDI/resole resin binders for the production of wood composite products
US6641762B2 (en) 1998-12-17 2003-11-04 Bayer Corporation Mixed PMDI/solid novolac resin binders for the production of wood composite products
US6416696B1 (en) 1999-12-16 2002-07-09 Bayer Corporation Aqueous mixed pMDI/phenolic resin binders for the production of wood composite products
WO2012127299A1 (fr) 2011-03-22 2012-09-27 Rhodia Poliamida E Especialidades Ltda Systèmes liants de fonderie
WO2014125313A1 (fr) 2013-02-12 2014-08-21 Rhodia Poliamida E Especialidades Ltda Systèmes de solvants et compositions de revêtement contenant lesdits systèmes
WO2014125357A1 (fr) 2013-02-12 2014-08-21 Rhodia Poliamida E Especialidades Ltda Système de solvants et compositions le contenant
US10239116B2 (en) 2013-02-12 2019-03-26 Rhodia Poliamida E Especialidades Ltda Solvent system and compositions therewith
CN103320080A (zh) * 2013-06-06 2013-09-25 常熟市江南粘合剂有限公司 聚异氰酸酯胶生产工艺

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