WO2005009647A2 - Compositions stabilisees de resine phenolique de type resol, et leur utilisation - Google Patents

Compositions stabilisees de resine phenolique de type resol, et leur utilisation Download PDF

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Publication number
WO2005009647A2
WO2005009647A2 PCT/US2004/023910 US2004023910W WO2005009647A2 WO 2005009647 A2 WO2005009647 A2 WO 2005009647A2 US 2004023910 W US2004023910 W US 2004023910W WO 2005009647 A2 WO2005009647 A2 WO 2005009647A2
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WO
WIPO (PCT)
Prior art keywords
resole resin
phenolic resole
resin composition
phenolic
foundry
Prior art date
Application number
PCT/US2004/023910
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English (en)
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WO2005009647A3 (fr
Inventor
Chia-Hung Chen
Xianping Wang
Jorg Kroker
Original Assignee
Ashland Inc.
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Filing date
Publication date
Application filed by Ashland Inc. filed Critical Ashland Inc.
Publication of WO2005009647A2 publication Critical patent/WO2005009647A2/fr
Publication of WO2005009647A3 publication Critical patent/WO2005009647A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • 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
    • B22C1/2246—Condensation polymers of aldehydes and ketones
    • B22C1/2253—Condensation polymers of aldehydes and ketones 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
    • B22C1/2266—Polyesters; Polycarbonates

Definitions

  • This invention relates to a stabilized phenolic resole resin composition comprising a phenolic resole resin and an effective stabilizing amount of an ortho ester.
  • the invention also relates to phenolic urethane binders prepared with the phenolic resole resin compositions, and the use of the binders to make foundry mixes, foundry shapes, and metal castings.
  • sand casting h sand casting
  • disposable foundry shapes are made by shaping and curing a foundry binder system that is a mixture of sand and an organic or inorganic binder.
  • the binder is used to strengthen the molds and cores.
  • Two of the major processes used in sand casting for making molds and cores are the no- bake process and the cold-box process.
  • a liquid curing agent is mixed with an aggregate and shaped to produce a cured mold and/or core.
  • a gaseous curing agent is passed through a compacted shaped mix to produce a cured mold and/or core.
  • Phenolic urethane binder, cured with a gaseous tertiary amine catalyst are often used in the cold-box process to hold shaped foundry aggregate together as a mold or core. See for example U.S. Patent 3,409,579.
  • the phenolic urethane binder system usually consists of a phenolic resin component and polyisocyanate component, which are mixed with sand prior to compacting and curing to form a foundry binder system.
  • the binder must have a low viscosity, be gel-free, remain stable under use conditions, and cure efficiently.
  • the foundry binder system made by mixing sand with the binder must have adequate benchlife or the mix will not shape and cure properly.
  • the cores and molds made with the binders must have adequate tensile strengths under normal and humid conditions, and release effectively from the pattern. Binders that meet all of these requirements are not easy to develop.
  • phenolic resole resins used in phenolic urethane binders are heat sensitive, and thus are not stable when stored at or exposed to elevated temperature for a prolonged period of time. This causes the viscosity of the resin to increase, or in extreme cases, the resin will gel. This seriously adversely affects the quality and performance of the binder.
  • Ortho esters are known in the prior art to stabilize organic isocyanates.
  • U. S. Patent 3,535,359 discloses that certain ortho-esters are capable of stabilizing a polyisocyanate against several different kinds of degradation, for instance moisture, and viscosity increases, even when only small amounts of ortho esters are used.
  • the stabilized isocyanates are useful in the preparation of polyurethane foam, nonporous plastics including polyurethane castings such as gear wheels and the like, and coating compositions. Chadwick does not disclose the use of such polyisocyanates in foundry binders, foundry mixes, or the preparation of foundry shapes and metal castings.
  • U.S. Patent 6,288,139 discloses phenolic urethane binders wherein the polyisocyanate component contains an ortho ester.
  • the patent indicates that, when added to a polyisocyanate component that contains a non reactive organic solvent, the ortho ester improves the tensile strength of foundry shapes. It also indicates that polyisocyanate components containing the ortho ester have lower turbidity, which indicates that it is more stable or homogeneous. As a result the polyisocyanate component will not be subjected to settling of particulate matter, and will be easier to pump.
  • This patent does not teach or suggest the use of ortho esters in the phenolic resole resin component of the phenolic urethane binder.
  • This invention relates to stabilized phenolic resole resin compositions comprising a phenolic resole resin and an effective stabilizing amount of an ortho ester.
  • the invention also relates to phenolic urethane binders prepared with the phenolic resole resin compositions, and the use of the binders to make foundry mixes, foundry shapes, and metal castings.
  • the addition of the ortho ester was found to be an effective stabilizing agent to improve the shelf stability of the phenolic resole resin composition.
  • the advantages of using the ortho ester in the phenolic resole resin composition are: (1) the phenolic resole resin composition has better shelf storage stability if it contains the ortho ester, and (2) the phenolic resole resin composition has improved heat stability at elevated temperatures if it contains the ortho ester.
  • shelf stability and heat stability are demonstrated because the phenolic resole resin composition does not undergo viscosity increase or gelation, even when subjected to increased temperatures. This advantage is particular important when the phenolic resole resin composition is stored and exposed at elevated temperatures during summer time.
  • the phenolic resole resin used in the phenolic resole resin composition is preferably prepared by reacting an 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. Alkoxy-modified benzylic ether phenolic resole resins can also be used.
  • the resins are prepared by reacting an excess of 'aldehyde with a phenol and an alcohol in the presence of a metal ion catalyst according to methods well known in the art. Alternatively, they can be prepared by preparing a benzylic ether phenolic resole resin and post-capping with the alcohol. See, for example, U.S. Patent 4,546,124 for a discussion of how these resins are prepared.
  • the phenols use to prepare the phenolic resole resins include 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 ortho-position and the para-position. These unsubstituted positions are necessary for the polymerization reaction. Any 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 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.
  • Multiple ring phenols such as bisphenol A and bisphenol F are also suitable.
  • the aldehyde used to react with the phenol has the formula RCHO wherein R is a hydrogen or 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, and benzaldehyde.
  • the most preferred aldehyde is formaldehyde.
  • the phenolic resin used must be liquid or organic solvent-soluble.
  • the phenolic resin composition generally contains an organic solvent.
  • the amount of solvent used should be sufficient to result in a binder composition permitting uniform coating thereof on the aggregate and uniform reaction of the mixture.
  • the specific solvent concentration for the phenolic resin composition 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 resin solution and preferably in the range of 20% to 80%.
  • the phenolic resole resin composition contains an ortho ester.
  • the ortho esters used have the formula R'C(OR) 3 , where R' is hydrogen, alkyl, alkenyl, aryl, haloalkyl and R is alky or alkenyl of 1 to 18 carbon atoms, chloroethyl, or phenyl.
  • R' is hydrogen, alkyl, alkenyl, aryl, haloalkyl and R is alky or alkenyl of 1 to 18 carbon atoms, chloroethyl, or phenyl.
  • the ortho esters are disclosed in U.S. Patent 3,535,359, which is incorporated by reference into this specification.
  • Preferably used are triethyl orthoformate, trimethyl orthoformate, and mixtures thereof.
  • the amount of ortho ester used is from 0.1 to 5.0 weight percent based upon the weight of the phenolic resole resin, preferably from 0.1 to 1.5 weight percent, most preferably from 0.1 to 0.4 weight percent
  • the phenolic resole resin compositions are used in the phenolic urethane binders. These binders contain a phenolic resin component and a polyisocyanate component, and are typically cured with a tertiary amine curing catalyst.
  • the polyisocyanate component of the binder typically comprises a polyisocyanate and organic solvent.
  • the polyisocyanate has a functionality of two or more, preferably 2 to 5. It may be aliphatic, cycloaliphatic, aromatic, or a hybrid polyisocyanate. Mixtures of such polyisocyanates may be used. Also, it is contemplated that capped polyisocyanates, prepolymers of polyisocyanates, and quasi prepolymers of polyisocyanates can be used. Optional ingredients such as release agents may also be used in the polyisocyanate hardener component.
  • polyisocyanates which can be used are aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate, and aromatic polyisocyanates such as 2,4-, 2,4-, 2,6-toluene diisocyanate and 2,2'-, 2,4'-, 4,4'-diphenylmethane diisocyanate, and dimethyl derivates thereof.
  • aliphatic polyisocyanates such as hexamethylene diisocyanate
  • alicyclic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate
  • aromatic polyisocyanates such as 2,4-, 2,4-, 2,6-toluene diisocyanate and 2,2'-, 2,4'-, 4,4'-diphenylmethane diisocyanate, and dimethyl derivates thereof.
  • polyisocyanates are 1,5- naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, and the methyl derivates thereof, polymethylenepolyphenyl isocyanates, chlorophenylene- 2,4- diisocyanate, and the like.
  • the polyisocyanates are used in sufficient concentrations to cause the curing of the phenolic resin in the presence of the curing catalyst.
  • the polyisocyanate ratio of the polyisocyanate to the hydroxyl of the phenolic resin is from 1.25:1 to 1:1.25, preferably about 1:1.
  • the amount of polyisocyanate used is from 10 to 500 weight percent, preferably 20 to 300 weight percent, based on the weight of the phenolic resin.
  • the polyisocyanate is used in a liquid form. Solid or viscous polyisocyanate must be used in the form of organic solvent solutions. In general, the solvent concentration will be in the range of up to 80% by weight of the resin solution and preferably in the range of 20% to 80%.
  • aromatic solvents examples include xylene and ethylbenzene.
  • the aromatic solvents are preferably a mixture of aromatic solvents that have a boiling point range of 125° C to 250° 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".
  • the binder may also contain a silane (typically added to the phenolic resin component) having the following general formula:
  • R' is a hydrocarbon radical and preferably an alkyl radical of 1 to 6 carbon atoms and R is an alkyl radical, an alkoxy-substituted alkyl radical, or an alkyl-amine- substituted alkyl radical in which the alkyl groups have from 1 to 6 carbon atoms.
  • the silane is preferably added to the phenolic resin component in amounts of 0.01 to 2 weight percent, preferably 0.1 to 0.5 weight percent based on the weight of the phenolic resin component.
  • 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.
  • the preferred aggregate employed for preparing ordinary foundry shapes is silica wherein at least about 70 weight percent and preferably at least about 85 weight percent of the sand is silica.
  • Other suitable aggregate materials include zircon, olivine, aluminosilicate sand, chromite sand, and the like. Although the aggregate employed is preferably dry, it can contain minor amounts of moisture.
  • the aggregate constitutes the major constituent and the binder constitutes a relatively minor amount.
  • 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 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 binder compositions are preferably made available as a two-package system with the phenolic resin component in one package and the polyisocyanate component in the other package.
  • the phenolic resin component is first mixed with sand and then the polyisocyanate component is added.
  • Methods of distributing the binder on the aggregate particles are well known to those skilled in the art.
  • the foundry binder system is molded into the desired shape, such as a mold or core, and cured.
  • Curing by the cold-box process is carried out by passing a volatile tertiary amine, preferably triethyl amine, through the shaped mix as described in U.S. Patent 3,409,579.
  • Curing by the no-bake process takes place by mixing a liquid amine curing catalyst into the foundry binder system, shaping it, and allowing it to cure.
  • Useful liquid amines have a pK value generally in the range of about 7 to about 11. Specific examples of such amines include 4-alkyl pyridines, isoquinoline, arylpyridines, 1-methylbenzimidazole, and 1,4-thiazine.
  • Preferably used as the liquid tertiary amine catalyst is an aliphatic tertiary amine, particularly tris (3-dimethylamino) propylamine.
  • the concentration of the liquid amine catalyst will range from about 0.2 to about 5.0 percent by weight of the phenolic resin, preferably 1.0 percent by weight to 4.0 percent by weight, most preferably 2.0 percent by weight to 3.5 percent by weight based upon the weight of the phenolic resin.
  • PEP SET® 1670/2670 a phenolic urethane no-bake foundry binder, manufactured by Ashland Specialty Chemical Company.
  • PEP SET 1670 is the phenolic component and comprises about 50-60 weight percent PR, 20-30 weight percent aromatic solvent, and 10-20 weight percent ester solvent.
  • PEP SET 2670 is the isocyanate component and comprises about 60-80 weight percent isocyanate, and 30- 40 weight percent aromatic solvents.
  • ST striptime is the time interval for a foundry mix to reach a green hardness of 90.
  • T w ⁇ rktime' is the time interval for a foundry mix to reach a green hardness of 60.
  • Table I shows that the incorporation of TMOF as stabilizing agent at levels of 0.7 and 1.4% by weight into the phenolic component (PEP SET 1670) greatly improved the
  • Test cores were made with PEP SET® 1670/2670 using Wedron 540 sand at a binder level of 1.2%, based upon the weight of the sand, a Part I/Partll mix ratio of 55/45 mix ratio, and PEP SET 3502 catalyst (4-phenyl propyl pyridine in an aromatic solvent) in an amount of about 3 weight percent based upon the Part I.
  • Tensile strengths of test dog bone shapes were measured according to the AFS standard tensile strength test. Determining the tensile strengths of the dog bone test shapes enables one to predict how the mixture of sand and binder will work in actual foundry facilities.
  • the dog bones were stored for 1.0 hour, 3 hours and 24 hours in a constant temperature room at relative humidity of 50% and a temperature of 25°C before measuring their tensile strengths. Unless otherwise specified, the tensile strengths were also measured on dog bone specimens stored 24 hours at a relative humidity (RH) of 90%. The results of these tests are shown in Table II.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention se rapporte à une composition stabilisée de résine phénolique de type résol comprenant une résine phénolique de type résol ainsi qu'une quantité, efficace en termes de stabilisation, d'un orthoester. Cette invention concerne également des liants d'uréthane phénolique préparés au moyen des compositions de résine phénolique de type résol, ainsi que l'utilisation de ces liants pour produire des mélanges de fonderie, des moules de fonderie, ainsi que des pièces de fonte métalliques.
PCT/US2004/023910 2003-07-24 2004-07-23 Compositions stabilisees de resine phenolique de type resol, et leur utilisation WO2005009647A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/626,189 US20050020723A1 (en) 2003-07-24 2003-07-24 Stabilized phenolic resole resin compositions and their use
US10/626,189 2003-07-24

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WO2005009647A2 true WO2005009647A2 (fr) 2005-02-03
WO2005009647A3 WO2005009647A3 (fr) 2005-05-12

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DE102015102952A1 (de) 2015-03-02 2016-09-08 Ask Chemicals Gmbh Verfahren zur Aushärtung von Polyurethan-Bindemitteln in Formstoffmischungen durch Einleiten tertiärer Amine und Lösungsmittel und Kit zur Durchführung des Verfahrens
RU2717419C2 (ru) * 2015-05-14 2020-03-23 Аск Кемикалз Ллс Система связующего для уменьшения взаимодействия металла с формой
JP2018160294A (ja) * 2017-03-22 2018-10-11 東芝メモリ株式会社 メモリデバイス

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6288139B1 (en) * 1998-09-24 2001-09-11 Ashland Inc. Foundry binder system containing an ortho ester and their use

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3535359A (en) * 1966-03-22 1970-10-20 Mobay Chemical Corp Stabilization of organic isocyanates
JPS58109534A (ja) * 1981-12-23 1983-06-29 Toagosei Chem Ind Co Ltd 硬化用組成物
US4814363A (en) * 1988-01-15 1989-03-21 Ashland Oil, Inc. Phenolic resin compositions and their use in foundry binders
US6017978A (en) * 1998-02-28 2000-01-25 Ashland Inc. Polyurethane forming no-bake foundry binders

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6288139B1 (en) * 1998-09-24 2001-09-11 Ashland Inc. Foundry binder system containing an ortho ester and their use

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US20060270753A1 (en) 2006-11-30
US20050020723A1 (en) 2005-01-27
WO2005009647A3 (fr) 2005-05-12

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