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WO1988007567A1 - Compositions de liants pour fonderie comprenant du resorcinol, et applications desdites compositions - Google Patents

Compositions de liants pour fonderie comprenant du resorcinol, et applications desdites compositions Download PDF

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Publication number
WO1988007567A1
WO1988007567A1 PCT/US1988/000873 US8800873W WO8807567A1 WO 1988007567 A1 WO1988007567 A1 WO 1988007567A1 US 8800873 W US8800873 W US 8800873W WO 8807567 A1 WO8807567 A1 WO 8807567A1
Authority
WO
WIPO (PCT)
Prior art keywords
foundry
moldable
mix
metal article
weight
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.)
Ceased
Application number
PCT/US1988/000873
Other languages
English (en)
Inventor
William R. Dunnavant
Heimo J. Langer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ashland LLC
Original Assignee
Ashland Oil Inc
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 Ashland Oil Inc filed Critical Ashland Oil Inc
Publication of WO1988007567A1 publication Critical patent/WO1988007567A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • 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
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates

Definitions

  • the foundry binding compositions comprise a resorcinol component, an amino resin, and a solvent.
  • An aggregate and an acid are mixed with the foundry binding • compositions to form a moldable foundry mix which is shaped and cured with acetaldehyde. The cured shapes are then used for making metal castings.
  • U.S. Patent 3,525,379 relates to a method of making shaped articles such as foundry cores which comprises;
  • the patent indicates at column 3, lines 38-57 that the resorcinol resins used are resorcinol-formaldehyde resins and that the phenolic-resorcinol resins are phenolic-resorcinol- formaldehyde resins. It also indicates that the preferred aldehyde is acetaldehyde and the catalysts used are strong organic or inorganic catalysts.
  • the invention relates to a foundry binding composition
  • a foundry binding composition comprising: (a) a resorcinol component;
  • Moldable foundry mixes are prepared by uniformly distributi the foundry binding composition and an acid on a foundry aggregate.
  • the invention also relates to a process of forming foundry shapes and metal castings, and to articles of manu ⁇ facture comprising a foundry binding composition and acetaldehyde.
  • the binding materials provide moldable foundry mixes which do not require a benchlife extender. They cure rapidly, have no free formaldehyde, and are resistant to humidity.
  • the resorcinol component usually is resorcinol, but for economic reasons i has been found that a mixture of resorcinol and resorcinol pitch .can be used. The more resorcinol pitch that is used, the more economically the invention can be practiced. However, it has been found that at least 30 percent by weig and generally at least 50 percent by weight of resorcinol must be used to obtain the desired properties of moldable foundry mixes and molds, said weight percent being based up the total weight of resorcinol and resorcinol pitch.
  • resorcinol pitch is defined as a by-product recovered from the manufacture of resorcinol. I generally contains a mixture of resorcinol, dihydroxy diphenyl, trihydroxy diphenyl, and high molecular weight polymers.
  • Resorcinol pitch does not contain any amount of the resorcinol-formaldehyde resins as described in U.S. Paten 3,525,379 mentioned previously.
  • Resorcinol pitch is solu in water, alcohol, acetone and other similar polar solven
  • Another component of the foundry binding composition an amino resin, preferably a liquid amino resin.
  • melamine resins such as melamine formaldehyde resins, alkylated melamine-formaldehyde resins, and urea-formaldehyde resins which are all known the art.
  • Useful amino resins are those which are compati with the other components of the binding composition and reactive under acidic conditions. They should also be soluble in the binding composition.
  • Preferably used are alkylated melamine-formaldehyde resins.
  • the weight ratio of the mixture of resorcinol compone to amino resin is from 1:1 to 13:1, preferably from 1:1 to 6:1.
  • the third component of the binding composition is a solvent, preferably water.
  • solvents include polar solvents such as alcohol and acetone.
  • the solvent is used an amount sufficient to dissolve the resorcinol, resorcino pitch, and amino resin and obtain a viscosity of 600 cps o less.
  • a strong organic or inorganic acid is used to catalyz the reaction between the resorcinol component and amino resin.
  • examples of such acids include sulfuric acid, hydrochloric acid, benzene sulfonic acid, p-toluenesulfon acid, perchloric acid, phosphoric acid, polyphosphoric ac boron trifluoride, trifluoracetic acid, hydrobromic acid, furous acid, and the like.
  • sulfuric a Different concentrations of acid may be used. Using lowe concentrations, however, will require that more acid be u
  • the acid is preferably mixed with the aggregate befo the binding composition is mixed with the aggregate.
  • the acid is used in an amount sufficient to catalyze the reac between the resorcinol component and the acetaldehyde.
  • the acid is used in amount of about 0.1 to 5.0, usually about 0.3 to 0.8 weight percent based upon the to weight of the aggregate.
  • a moldable foundry mix is prepared by uniformly distributing the foundry binding composition on an aggreg which preferably contains the acid. Generally sand will the primary constituent of the aggregate.
  • the amount of binding composition required is an amo sufficient to produce a core or mold which can be handled. Generally this is less than 10% by weight based upon the amount of the aggregate, usually from 0.5 to 5.0 percent weight.
  • moldable mixes are generally used in foundry applications, they can also be used in preparing refractory.
  • moldable mixes for different applications, see U.S. Paten 4,540,724 which is hereby incorporated by reference into disclosure.
  • Foundry shapes are then prepared by shaping the foun mixture and contacting the shaped foundry mixture with acetaldehyde according to conventional methods such as th described in U.S. Patents 3,409,579 and 3,525,379 which a hereby incorporated by reference into this disclosure.
  • the acetaldehyde is used in amount sufficient to for shape which can be handled. Gassing times are generally from 1 second to 30 seconds. In ⁇ eneral the amount of acetaldehyde needed to cure the shaped foundry mix is fro
  • the acetaldehyde can be effectively dispers by means of an inert gas such as nitrogen, argon, and the
  • An additional componenet used in the binding composi is a silane such as those having the general formula:
  • R 1 is a hydrocarbo radical and preferably an alk radical of 1 to 6 carbon atoms and R is an alkyl radical, alkoxy-substituted alkyl radical, or an alkylamine- substituted alkyl radical in which the alkyl groups have
  • silane when employed in
  • ⁇ - ⁇ concentrations of 0.1 to 2% based on the phenolic binder hardener improves the humidity resistance of the system.
  • silanes examples include Corning Z6040 and Union Carbide A-187 (gamma glycidoxy propyltrimethoxy silane) ; Union Carbide A-1100 (gamma
  • accelerators Other optional components include accelerators,
  • Component _1 2 Resorcinol 60 55 • j c Cymel 303 (an amino resin sold 10 15 by American Cyanamid) H 2 0 30 30 Silane A-1100 0. 2 0 . 2
  • the 6 pbw of the binding composition was mixed with 2 pbw cone. HdonSO.. Afterwards 1.2 pbw acetaldehyde was adde with rapid stirring. The mixture reacted instantaneously form a brittle gel.
  • Example 4 was repeated using 5 pbw binding compositio 0.5 pbw cone. HdonS0 4 and 1.0 pbw acetaldehyde. A brittle g was formed within seconds.
  • Examples 6-9 illustrate the preparation of foundry shapes with resorcinol and an amino resin.
  • the binding compositions were as follows:
  • Foundry core shapes were prepared by adding 10 pbw of 50% H ⁇ SO. (0.5% B.O.S.) on 2000 pbw Wedron silica sand and mixing for 1 minute. Then 30 pbw (1.5% B.O.S.) of the binding composition were added to the sand and again mixed for 1 minute. Each sand mix was blown into a dog bone shaped core cavity. After a certain dwell time, the sand mix was gasse with acetaldehyde vapor obtained by placing acetaldehyde i 1 liter autoclave and compressing it with N_ (40 psi) into the core cavity thereby forming AFS tensile strength dogbo shaped samples using the standard procedures. The tensile strength was measured immediately after curing at a relati humidity of 26% and temperature of 23°C. The specific conditions and results are summarized in Table I.
  • Examples 6-9 show that acceptable foundry shapes can prepared with the binding compositions containing resorcin and amino resin which have acceptable tensile strengths ev though no benchlife extender is used. TABLE I
  • Examples 10-15 illustrate the preparation of foundry shapes with a binding compositions containing resorcinol pitch.
  • Foundry core shapes were prepared as in Examples 6-11 except 10 pbw of concentrated H 2 S0. was used.
  • the curing gas was obtained by heating acetaldehyde in a 1 liter autoclave at 40-50°C and compressing with responsibly (40 psi) into core cavity.
  • the specific conditions are set forth in Tab II.
  • the tensile strengths were measured immediately after curing at 75% relative humidity and 24°C. They were also measured at 1 hour, 3 hours, and 24 hours after curing.
  • Examples 10-15 show that a binding composition containing resorcinol pitch is also effective in preparing moldable foundry mixes.
  • Examples 8 and 11 also illustrate the effective benchlife of the moldable foundry mixes. Th mixes are effective even 24 hours after mixing.
  • Component A B Resorcinol 60 50.2 Cymel 303 10 8. 3 H 2 0 30 41.5 Silane 0 . 2 (A-1506) 0. 16 (A
  • a binding composition was used in a penetration test casting. Using the following binder formulation, standard AF 2 compressive a test core was prepared using the autocla generate acetaldehyde gas.
  • the binding composition used the following:
  • the sand mix was heated to about 65°C before acetal ⁇ dehyde gas was introduced.
  • the core was allowed to age 2 days before casting tests were performed.
  • a test casting was poured with a medium carbon equivalent to inoculated gray iron. Composition of the i poured was: 3.5% C, 2.5% Si, 0.4% Mn and 0.0020% S.
  • Pou temperature was: 2700°F. The test casting showed no veining.
  • Example 18 illustrates that acceptable castings can made with cores prepared from binding compositions within scope of this invention.

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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)
  • General Chemical & Material Sciences (AREA)
  • Mold Materials And Core Materials (AREA)

Abstract

L'invention concerne des compositions de liants pour fonderie et leurs applications. Lesdites compositions comprennent du résorcinol, une résine aminée et un solvant. Les compositions sont mélangées avec un agrégat et un acide pour produire un mélange moulable pour fonderie, qui est façonné et durci par l'action de l'éthanal. Les formes sont appliquées ensuite à la production de pièces coulées.
PCT/US1988/000873 1987-03-23 1988-03-21 Compositions de liants pour fonderie comprenant du resorcinol, et applications desdites compositions Ceased WO1988007567A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US2925587A 1987-03-23 1987-03-23
US029,255 1987-03-23

Publications (1)

Publication Number Publication Date
WO1988007567A1 true WO1988007567A1 (fr) 1988-10-06

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1988/000873 Ceased WO1988007567A1 (fr) 1987-03-23 1988-03-21 Compositions de liants pour fonderie comprenant du resorcinol, et applications desdites compositions

Country Status (2)

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AU (1) AU1547388A (fr)
WO (1) WO1988007567A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018118311A (ja) * 2017-01-23 2018-08-02 花王株式会社 鋳型用添加剤
JP2018140438A (ja) * 2017-02-24 2018-09-13 花王株式会社 鋳型造型用粘結剤組成物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA455354A (fr) * 1949-03-22 Pennsylvania Coal Products Company Complex resineux de resorcinol-aldehyde et d'amine aromatique-aldehyde
US2521614A (en) * 1946-01-30 1950-09-05 Emerik Imre Valyi Investment compositions and method of producing refractory molds therefrom
US3036028A (en) * 1958-10-20 1962-05-22 Formica Corp Phenol-melamine-formaldehyde resin and process of preparing same
US3525379A (en) * 1968-04-18 1970-08-25 Cpc International Inc Foundry compositions,cores and method of making same
US4387173A (en) * 1981-04-16 1983-06-07 General Refractories Company Use of resorcinal polymer blend as a binder for carbon-containing refractory brick and shape

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA455354A (fr) * 1949-03-22 Pennsylvania Coal Products Company Complex resineux de resorcinol-aldehyde et d'amine aromatique-aldehyde
US2521614A (en) * 1946-01-30 1950-09-05 Emerik Imre Valyi Investment compositions and method of producing refractory molds therefrom
US3036028A (en) * 1958-10-20 1962-05-22 Formica Corp Phenol-melamine-formaldehyde resin and process of preparing same
US3525379A (en) * 1968-04-18 1970-08-25 Cpc International Inc Foundry compositions,cores and method of making same
US4387173A (en) * 1981-04-16 1983-06-07 General Refractories Company Use of resorcinal polymer blend as a binder for carbon-containing refractory brick and shape

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018118311A (ja) * 2017-01-23 2018-08-02 花王株式会社 鋳型用添加剤
JP2018140438A (ja) * 2017-02-24 2018-09-13 花王株式会社 鋳型造型用粘結剤組成物

Also Published As

Publication number Publication date
AU1547388A (en) 1988-11-02

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