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WO2006010777A1 - Utilisation de resines phenoliques modifiees dans des procedes de moulage en coquille - Google Patents

Utilisation de resines phenoliques modifiees dans des procedes de moulage en coquille Download PDF

Info

Publication number
WO2006010777A1
WO2006010777A1 PCT/ES2004/000300 ES2004000300W WO2006010777A1 WO 2006010777 A1 WO2006010777 A1 WO 2006010777A1 ES 2004000300 W ES2004000300 W ES 2004000300W WO 2006010777 A1 WO2006010777 A1 WO 2006010777A1
Authority
WO
WIPO (PCT)
Prior art keywords
phenolic resin
modified
fraction
modified phenolic
cashew nut
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/ES2004/000300
Other languages
English (en)
Spanish (es)
Inventor
Antonio Oller Riera
Armando Felis Prior
Luis Iglesias Hernandez
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.)
Sumitomo Bakelite Europe Barcelona SL
Original Assignee
Sumitomo Bakelite Europe Barcelona SL
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 Sumitomo Bakelite Europe Barcelona SL filed Critical Sumitomo Bakelite Europe Barcelona SL
Priority to PCT/ES2004/000300 priority Critical patent/WO2006010777A1/fr
Publication of WO2006010777A1 publication Critical patent/WO2006010777A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • B22C1/24—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 oily or fatty substances; of distillation residues therefrom
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/32—Chemically modified polycondensates by organic acids or derivatives thereof, e.g. fatty oils

Definitions

  • the present invention relates to the field of the manufacture of molds and dies for foundry and, in particular, to the field of modified phenolic resins used in the manufacture thereof by means of shell molding processes.
  • sand grains are used, generally of silica coated with a thermosetting resin film. Said particles are brought into contact with a hot metallic model whereby the resin softens and flows around the grains of sand to form a slightly adherent shell on the model. Once the desired shell thickness is obtained (depending on the contact time and the temperature of the model), the excess of non-adhered sand is removed. The model with the bonded shell is then cooked in order to finish the resin cure, thus forming a mold in thermosetting, self-supporting and rigid shell that adapts to The shape of the metal model. After curing, the hardened shell mold is demolished, this, the mold is separated from the model by, for example, the classic ejectors. A mold or male of sufficient three-dimensional precision is thus produced.
  • thermosetting resins of phenolic type such as Novolaca resins are used, for example, to coat the grains of silica sand. Molds or males are thus obtained that have good thermal stability and that withstand the casting temperature. However, they can also exhibit excessive rigidity against the thermal shock of the liquid metal during casting.
  • modified phenolic resins are used so that greater flexibility is achieved in the face of the thermal shock of the molten metal, thus avoiding the "cracking" effect by dilating the silica and getting the castings to have a perfect finish.
  • phenolic resins for shell molding processes have been modified by adding a series of additives.
  • a natural resin commercially called "Vinsol” whose availability is limited given its origin and, therefore, high price, and which also presents other inconveniences such as the production of fumes and odors.
  • the modification of the phenolic resins by adding other products such as rosins, high molecular weight resins, petroleum-derived resins, etc.
  • these additives have never become a real alternative due to deficiencies in thermal behavior.
  • phenolic resins by modifying said phenolic resins by adding cashew nut shell oil, in English called cashew nut shell liquid (CNSL), or a fraction thereof, such as cardanol , so good or better results are obtained than with the phenolic resin modified with Vinsol in terms of the properties of plasticity and hot deformation of the foundry molds and males.
  • CNSL cashew nut shell liquid
  • Said phenolic resins modified with CNSL or fraction thereof also have a series of additional advantages in terms of the availability and cost of this very common natural product.
  • phenolic resins modified with CNSL is known in the industry for various applications such as, for example, the preparation of brake linings and clutches, in the manufacture of photosensitive resins for microlithography (see international patent application WO 02 / 102867), in the preparation of refractory masses (see Spanish patent ES 2151262), etc.
  • phenolic resins modified with CNSL for sand coating used to obtain molds and cast iron by means of shell molding procedures.
  • the invention provides a new use of said phenolic resins modified with CNSL, or some of its components, specifically their use in shell molding processes.
  • the present invention provides the use of a phenolic resin modified with cashew nut shell oil or faction thereof in a shell molding process.
  • Another object of the present invention is a shell molding process in which said phenolic resin modified with cashew nut oil or fraction thereof is used in the step of coating the silica sand grains.
  • Another object of the present invention is a mold or male for melting metals based on sand grains, generally of silica coated with a phenolic resin modified with cashew nut oil or fraction thereof.
  • the present invention provides the use of a phenolic resin modified with cashew nut oil or fraction thereof in a shell molding process.
  • cashew nut shell oil is refers to the oil extracted from the cashew nut shell or fraction thereof.
  • the modified phenolic resin is a novolac resin.
  • the percentage of CNSL in the modified phenolic resin is 1-50% by weight, preferably 5-20% by weight, by weight.
  • the invention provides a process comprising a step of coating the silica sand grains with a modified phenolic resin, characterized in that said modified phenolic resin is a modified phenolic resin with nut shell oil of the cashew nut or fraction thereof.
  • Said procedure basically comprises three stages:
  • CNSL modified novolac resin As starting products, for example, a 100% phenol solution, a 37% formaldehyde solution and CNSL, which are commercial products, are used. For example, to obtain 100 kg of CNSL modified novolac resin, one can start from:
  • Phenol and CNSL or derivatives are charged at a temperature of the order of 40-50 ° C.
  • An acid catalyst organic, such as oxalic acid, or inorganic acid, such as sulfuric acid
  • the formaldehyde is then gradually charged for 1 hour in a phenol / formaldehyde ratio of 1 to 80% by weight, preferably 5 to 15% by weight.
  • the reaction is allowed to proceed for another hour at that temperature and, subsequently, evaporation is carried out at a temperature of the order of 130-140 0 C and a vacuum pressure of 700-760 mm in order to eliminate volatiles.
  • the degree of polymerization can be controlled by controlling the refractive index, the softening point or the amount of free phenol or free formaldehyde.
  • reaction conditions it is possible to work at different temperatures depending on the pressure conditions used.
  • pressure conditions for example, at atmospheric pressure one works at 80-110 ° C, at depression at 80-100 ° C and at overpressure at 110-140 ° C.
  • the resin thus prepared can be a solid resin (chopped, flaked, pearl or granulated), or a resin in liquid solution with organic solvents of the alcohol, acetone, etc. type, with a softening point of 70-100 ° C (typical values of 88-92 0 C) and with a free phenol amount of 0-6% by weight (typical values of 2-4% by weight).
  • Hot coating The sand is heated at a sufficient temperature to melt the solid resin.
  • Tempered coating The dissolved solid resin is added on the grains of sand at room temperature.
  • a crosslinker such as hexamine (hexamethylenetetramine) is added, which catalyzes and fixes the novolac to the grain.
  • hexamine hexamethylenetetramine
  • novolac resins behave by themselves as thermoplastics, that is, they do not react in the presence of heat and require the extra contribution of formaldehyde to polymerize, the most widespread form being the addition of hexamine which, at temperatures of the order of 100 0 C, decomposes into ammonia and formaldehyde, thus facilitating the formation of diethylene amine and methylene bridges.
  • the hot process is the most common of the three previously reviewed.
  • the sand is heated, generally of silica, alone or with additives, up to temperature of 125-175 ° C and then introduced into a mixer.
  • the novolac type resin is added until it is completely fused.
  • water the mixture below 100 0 C.
  • an amount of hexamine solution is introduced and the whole is subjected to depression with entrainment of water from the medium.
  • the mixture is then dried and a release agent introduced, such as a metal stearate, preferably calcium, or a polyethylene wax.
  • the mixture is broken down, cooled and sieved to be packaged or for immediate use.
  • molds or taps are obtained for the smelting of metals for the production of parts for the automotive, railway, aeronautics, chemical, etc. industries.
  • the invention provides a shell molding process characterized in that the modified phenolic resin employed is a novolac resin.
  • the percentage of CNSL in the modified phenolic resin is 1-50% by weight. More specifically, it is 5-20% by weight.
  • the invention provides a mold or male for casting. of metals based on sand grains coated with a phenolic resin modified with cashew nut oil.
  • said mold or male is characterized in that the modified phenolic resin used in the coating of the sand grains thereof is a novolac resin.
  • said mold or male is characterized in that the percentage of cashew nut oil in the modified phenolic resin is 1-50% by weight. More particularly, it is 5-20% by weight. 5

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (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

La présente invention concerne l'utilisation d'une résine phénolique modifiée à l'aide d'huile de coquille de noix de cajou ou d'une fraction de celle-ci dans un procédé de moulage en coquille. L'invention concerne également un procédé de moulage en coquille dans lequel ladite résine phénolique moodifiée est utilisée dans l'étape de revêtement des grains de sable de silice. L'invention concerne enfin un moule ou noyau utilisé dans la fusion des métaux à base de grains de sable de silice revêtus de ladite résine phénolique modifiée.
PCT/ES2004/000300 2004-06-25 2004-06-25 Utilisation de resines phenoliques modifiees dans des procedes de moulage en coquille Ceased WO2006010777A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/ES2004/000300 WO2006010777A1 (fr) 2004-06-25 2004-06-25 Utilisation de resines phenoliques modifiees dans des procedes de moulage en coquille

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2004/000300 WO2006010777A1 (fr) 2004-06-25 2004-06-25 Utilisation de resines phenoliques modifiees dans des procedes de moulage en coquille

Publications (1)

Publication Number Publication Date
WO2006010777A1 true WO2006010777A1 (fr) 2006-02-02

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/ES2004/000300 Ceased WO2006010777A1 (fr) 2004-06-25 2004-06-25 Utilisation de resines phenoliques modifiees dans des procedes de moulage en coquille

Country Status (1)

Country Link
WO (1) WO2006010777A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008017476A1 (fr) * 2006-08-09 2008-02-14 Ashland-Südchemie-Kernfest GmbH Utilisation de dérivés de coquille de noix de cajou dans des liants pour fonderie à base de polyuréthanne
WO2018185400A1 (fr) 2017-04-04 2018-10-11 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc a base de resine renforcante et d'un derive d'aminobenzoate
CN110586847A (zh) * 2019-10-08 2019-12-20 赵陆军 一种高温稳定型覆膜砂
US10853502B1 (en) 2015-03-04 2020-12-01 Micro Focus Llc Systems and methods for reducing computational difficulty of cryptographic operations

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES8101944A1 (es) * 1980-06-09 1980-12-16 Borden Inc Un procedimiento para preparar una composicion de moldeo pa-ra fundicion
JPS63117060A (ja) * 1986-11-04 1988-05-21 Asahi Organic Chem Ind Co Ltd 結合剤用粉末状フェノール系樹脂組成物
ES2168147T3 (es) * 1997-05-22 2002-06-01 Hatsunen Co Ltd Procedimiento de produccion de un cuerpo exotermico de fundicion.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES8101944A1 (es) * 1980-06-09 1980-12-16 Borden Inc Un procedimiento para preparar una composicion de moldeo pa-ra fundicion
JPS63117060A (ja) * 1986-11-04 1988-05-21 Asahi Organic Chem Ind Co Ltd 結合剤用粉末状フェノール系樹脂組成物
ES2168147T3 (es) * 1997-05-22 2002-06-01 Hatsunen Co Ltd Procedimiento de produccion de un cuerpo exotermico de fundicion.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 1988-179489 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008017476A1 (fr) * 2006-08-09 2008-02-14 Ashland-Südchemie-Kernfest GmbH Utilisation de dérivés de coquille de noix de cajou dans des liants pour fonderie à base de polyuréthanne
DE102006037288B4 (de) 2006-08-09 2019-06-13 Ask Chemicals Gmbh Formstoffmischung enthaltend Cardol und/oder Cardanol in Gießereibindemitteln auf Polyurethanbasis, Verfahren zur Herstellung eines Formkörpers sowie Verwendung desselben
US10853502B1 (en) 2015-03-04 2020-12-01 Micro Focus Llc Systems and methods for reducing computational difficulty of cryptographic operations
WO2018185400A1 (fr) 2017-04-04 2018-10-11 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc a base de resine renforcante et d'un derive d'aminobenzoate
CN110586847A (zh) * 2019-10-08 2019-12-20 赵陆军 一种高温稳定型覆膜砂
CN110586847B (zh) * 2019-10-08 2020-11-24 青铜峡市瑞通支撑剂有限公司 一种高温稳定型覆膜砂

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