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WO2011097818A1 - Composition de liant à base de résine phénolique - Google Patents

Composition de liant à base de résine phénolique Download PDF

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Publication number
WO2011097818A1
WO2011097818A1 PCT/CN2010/070672 CN2010070672W WO2011097818A1 WO 2011097818 A1 WO2011097818 A1 WO 2011097818A1 CN 2010070672 W CN2010070672 W CN 2010070672W WO 2011097818 A1 WO2011097818 A1 WO 2011097818A1
Authority
WO
WIPO (PCT)
Prior art keywords
phenol
potassium hydroxide
composition according
molar ratio
phenolic resin
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/CN2010/070672
Other languages
English (en)
Chinese (zh)
Inventor
祝建勋
李培强
马彩霞
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.)
Jinan Shengquan Group Share Holding Co Ltd
Original Assignee
Jinan Shengquan Group Share Holding Co Ltd
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 Jinan Shengquan Group Share Holding Co Ltd filed Critical Jinan Shengquan Group Share Holding Co Ltd
Priority to RU2011134668/04A priority Critical patent/RU2480308C1/ru
Priority to TR2011/08926T priority patent/TR201108926T1/xx
Priority to CN201080063717.0A priority patent/CN102753619B/zh
Priority to PCT/CN2010/070672 priority patent/WO2011097818A1/fr
Priority to AU2010345651A priority patent/AU2010345651B2/en
Publication of WO2011097818A1 publication Critical patent/WO2011097818A1/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
    • 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
    • C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols

Definitions

  • PHENOL RESIN Binder Composition FIELD OF THE INVENTION The present invention relates to phenolic binder compositions and their use in the production of bonded particulate material compositions, such as molds, mold core materials. Background technique
  • the CO 2 curing phenolic resin binder is composed of a resole phenolic resin with a high methylol content and a base, a hardening agent and a modifier. Because it is non-toxic and has a good environmental advantage, it is currently used most in the foundry industry.
  • the resol phenolic resin is the main component in the binder, and is obtained by polycondensation reaction of phenol and formaldehyde under the action of a basic catalyst.
  • the base acts as a dispersing agent in the binder, and it is considered that the most preferred base is KOH because the viscosity of the resin solution prepared with KOH is relatively low compared to NaOH and LiOH.
  • the current CO 2 hardening alkaline phenolic resin binder has defects in the application of the mold, for example, the strength of the cast mold and the core, the high wet strength and the high temperature strength are low, and the mold and the core are damaged in use. And castings such as sand washing and thermal cracking and other defects. These shortcomings can affect the application range of the mold and the core.
  • Another object of the invention is to adjust the rate of cure of the resin in the binder and to increase the strength of the binder.
  • the present invention therefore proposes an alkaline phenolic resin binder composition
  • an alkali phenolic resin, a first base and a hardening agent the basic phenolic resin being prepared by substituting bisphenol A for a part of phenol, bisphenol A
  • the molar ratio to phenol is in the range of 1:10 to 25, preferably in the range of 1:15 to 20.
  • the first base is composed of potassium hydroxide and sodium hydroxide
  • hydrogen The ratio of the molar total amount of potassium oxide and sodium hydroxide to the number of moles of phenol is in the range of 1.5:1 to 2.5:1.
  • the molar ratio of potassium hydroxide to phenol of hydrogen is between 0.5:1 and 2.5:1, and the molar ratio of hydrogen to oxygen is between 0.1:1 and 2.0:1.
  • the composition of the present invention may further comprise 1 to 20% by weight of an additive selected from the group consisting of cyclic ethers, phenylethylene glycol methyl ethers, glyceryl ethers, ethylene glycol alkyl ethers, and propylene glycol alkyl ethers.
  • the addition of a polyol or a carbohydrate to the binder increases the amount of the complex reactive groups and increases the bond strength of the binder.
  • These compounds contain active hydroxyl groups which undergo polymerization reaction with each other or cross-link with a resin.
  • the gel produced by such a crosslinking reaction is an irreversible gel, and the bond strength of the binder is greatly improved.
  • Ethylene glycol and propylene glycol polyols are capable of coordination with boric acid or borate ions.
  • Another aspect of the invention relates to an alkaline phenolic resin binder composition comprising an alkali phenolic resin, a first base and a hardening agent, the first base being composed of potassium hydroxide and sodium hydroxide, hydrogen
  • the ratio of the molar total amount of potassium oxide and sodium hydroxide to the number of moles of phenol is in the range of 1.5:1 to 2.5:1.
  • the molar ratio of potassium hydroxide to phenol is between 0.5:1 and 2.5:1, and the molar ratio of sodium hydroxide to phenone is between 0.1:1 and 2.0:1.
  • a hardening agent may be added to the composition selected from the group consisting of borate, stannate and aluminate. Borax in borate is a preferred choice for performance and economy.
  • the use of bisphenol A instead of a part of phenol to synthesize a phenolic resin binder can improve the moisture absorption resistance of the mold and the core after the gas is passed, and is beneficial for storing in a humid environment for a long time and after brushing the water-based paint. Core strength, increase the high temperature strength of the mold and core after storage of the gas.
  • bisphenol A is introduced into a raw material for preparing a phenol resin.
  • the molar ratio of bisphenol A to phenol may be in the range of 1:10 to 25, preferably in the range of 1:15 to 20.
  • the inventors have found that the partial replacement of phenol by bisphenol A can improve the multiple properties of the cast mold compared to the case of phenol alone.
  • the moisture absorption resistance of the mold is improved, the mold can be stored in a humid environment for a long time, and the strength of the core is less affected after the mold is brushed and the water is dried;
  • the compressive strength of the mold at a high temperature for example, between 100 and 200 ° C
  • the raw material for the preparation of the phenol resin includes phenol, an optional bisphenol A, a base (second base), formaldehyde, and water.
  • the molar ratio of formaldehyde to phenol is suitably from 1.75 to 2.3.
  • the second base used may be selected from the group consisting of Na 2 CO 3 , NaOH, KOH and aqueous ammonia, and may be used in a conventional amount in the prior art, and may have a molar ratio to phenol of 0.02 0.15.
  • the other ingredients include a hardening aid, a first base, and an optional additive.
  • the hardeners are mainly oxoacid salts such as borate, stannate, aluminate and titanate.
  • the first base used may be sodium hydroxide, potassium hydroxide or lithium hydroxide.
  • the combination of sodium hydroxide and potassium hydroxide is used as a viscosity modifier in the binder, unlike the prior art, which uses a single species of the first base.
  • the molar ratio of potassium hydroxide to phenol is preferably between 0.5:1 and 2.5:1, and the molar ratio of sodium hydroxide to benzene face is preferably between 0.1:1 and 2.0:1, and hydrogen
  • the ratio of the molar total amount of potassium oxide and sodium hydroxide to the number of moles of phenol is in the range of 1.5:1 to 2.5:1. This ratio can be flexibly 4 bar grips depending on the specific requirements of the product.
  • the resin using potassium hydroxide alone has a faster curing speed and a higher initial strength, but the final strength after 24 hours is lower; after adding a part of sodium hydroxide instead of potassium hydroxide, the curing speed is slow, and the initial strength is somewhat Lower, but the final strength after 24 hours is significantly improved. If the product is expected to have a high initial strength and no requirement for ultimate strength, then sodium hydroxide may not be used. If it is desired to increase the final strength of the product, it is possible to use sodium hydroxide which does not exceed 2 times the molar amount of phenol. The inventors have found that as the amount of sodium hydroxide used increases, the ultimate strength of the product increases accordingly.
  • the desired initial strength and final strength can be flexibly adjusted by the combination of sodium hydroxide and potassium hydroxide.
  • Both the first base and the second base used in the present invention are used in the form of an aqueous solution, and the base is usually formulated to a concentration of 20 to 50% by weight.
  • Additives may also be incorporated into the compositions of the present invention to improve the properties of the resin sand, such as strength, surface stability, moisture resistance, and the like. The amount of the additive is usually not more than 20% by weight of the composition.
  • an ether compound is often used to improve the strength and surface stability of the sand core (core), improve the fluidity of the resin, and reduce the porosity defects.
  • These ether compounds are mainly cyclic ethers, phenylethylene glycol methyl ether, glyceryl ether, ethylene glycol alkyl ethers, propylene glycol alkyl ethers and the like.
  • a water-soluble polymer compound such as a carbohydrate, a binary or ternary fatty acid, a divalent or ternary fatty amine, a binary or a ternary fatty amide.
  • a silane coupling agent can also be used in the binder composition, and the silane coupling agent can effectively increase the adhesion strength of the binder to the sand particles and reduce the adhesion and cracking of the resin sand.
  • Silanes commonly used in the prior art include triaminopropyltrimethoxysilane, N-(2-aminoethane)-3-aminopropyltrimethoxysilane, phenyltrimethylsilane or triglycidyl ether. Propyltrimethoxysilane.
  • the above preferred features of the invention may also be used alone.
  • Example 1 An alkaline phenolic resin was synthesized using the following components:
  • Formaldehyde double face A molar ratio 40 : 1
  • the above resin contains 1.0% of its own total N-(2-aminoethane)-3-aminopropyltrimethoxysilane.
  • Formaldehyde phenol molar ratio 2.0 : 1
  • Example 3-6 Following the procedure of Example 1, the following components were used to synthesize an alkaline phenolic resin: table 3
  • Example 3 173.58 69.27 0 33.84 37.44 60
  • Example 4 173.58 69.27 0 33.84 37.44 60
  • Example 5 173.58 69.27 0 33.84 37.44 60
  • Example 6 173.58 69.27 0 33.84 37.44 60
  • Example 7 The binder in the above examples was mixed with Dalin silica sand (50 100 mesh), and the amount of the binder was 3% less than that of Dalinwa. The mixture was used to prepare a standard AFS 50 mm x 50 mm cylindrical core. The temperature of the sand is 18.6 ° C.
  • Example 1 modified with bisphenol A was used in high humidity and high temperature strength compared to phenol alone.
  • Example 2 has a big improvement. Table 6
  • the degree of polymerization is low, so that the curing speed of the resin and the final strength of 24H become lower; the lower addition amount of bisphenol A in Example 4 makes the effect less obvious, and the high humidity and high temperature strength of the resin are less increased;
  • the addition of bisphenol A to 6 will increase the high humidity and high temperature strength of the resin within a desirable range.
  • bisphenol A is used instead of partial phenol synthesis, the moisture absorption resistance of the mold and the core after storage of the gas can be improved, which is advantageous for storing the core strength after drying for a long time in a humid environment and brushing the water-based paint.
  • the addition of water reduces the viscosity of the resin and facilitates uniform sand mixing.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mold Materials And Core Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de liant à base de résine phénolique contenant une résine phénolique alcaline, une première base et un accélérateur de durcissement. Ladite composition est caractérisée en ce que la résine phénolique alcaline est produite au moyen de bisphénol A plutôt que de fractions de phénol, et en ce que le rapport molaire entre le bisphénol A et le phénol se situe dans un intervalle de 1/10-25. Cette composition de liant peut être utilisée en tant que matériau constitutif des boîtes à noyaux pour procédé boîte froide dans l'industrie du moulage. La présente composition de liant peut améliorer la résistance à l'humidité et la résistance aux hautes températures des moules et des noyaux lors de leur stockage après exposition à des gaz.
PCT/CN2010/070672 2010-02-11 2010-02-11 Composition de liant à base de résine phénolique Ceased WO2011097818A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
RU2011134668/04A RU2480308C1 (ru) 2010-02-11 2010-02-11 Клеевая композиция на основе фенольной смолы
TR2011/08926T TR201108926T1 (tr) 2010-02-11 2010-02-11 Fenolik reçineli yapıştırıcı bileşimi.
CN201080063717.0A CN102753619B (zh) 2010-02-11 2010-02-11 酚醛树脂粘结剂组合物
PCT/CN2010/070672 WO2011097818A1 (fr) 2010-02-11 2010-02-11 Composition de liant à base de résine phénolique
AU2010345651A AU2010345651B2 (en) 2010-02-11 2010-02-11 Phenolic Resin Adhesive Composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2010/070672 WO2011097818A1 (fr) 2010-02-11 2010-02-11 Composition de liant à base de résine phénolique

Publications (1)

Publication Number Publication Date
WO2011097818A1 true WO2011097818A1 (fr) 2011-08-18

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PCT/CN2010/070672 Ceased WO2011097818A1 (fr) 2010-02-11 2010-02-11 Composition de liant à base de résine phénolique

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CN (1) CN102753619B (fr)
AU (1) AU2010345651B2 (fr)
RU (1) RU2480308C1 (fr)
TR (1) TR201108926T1 (fr)
WO (1) WO2011097818A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104338892A (zh) * 2013-07-31 2015-02-11 见得行股份有限公司 用于添加湿砂模的安定剂

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1110199A (zh) * 1994-04-11 1995-10-18 花王株式会社 铸模用粘合剂组合物和生产铸模的方法
CN1150070A (zh) * 1995-11-08 1997-05-21 花王株式会社 铸型用粘结剂组合物、铸型组合物和铸型的制造方法
CN1158769A (zh) * 1995-11-08 1997-09-10 花王株式会社 铸型的制造方法、铸型组合物及铸型用粘结剂组合物
CN1171991A (zh) * 1996-01-31 1998-02-04 花王株式会社 二氧化碳气体硬化用粘结剂组合物
WO1999011686A1 (fr) * 1997-09-04 1999-03-11 Ashland-Südchemie-Kernfest GmbH Resine phenolique et liant pour la production de moules et de noyaux selon le procede polyurethanne-resine phenolique
CN101348549A (zh) * 2008-08-22 2009-01-21 辽宁福鞍铸业集团有限公司 端羟基碱性酚醛树脂及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2044589C1 (ru) * 1992-04-01 1995-09-27 Акционерное общество "Уралхимпласт" Синтетическое смоляное связующее, отверждаемое кислотными катализаторами, для изготовления литейных стержней и форм в холодной оснастке
US5639806A (en) * 1995-03-28 1997-06-17 Borden Chemical, Inc. Bisphenol-containing resin coating articles and methods of using same
CN1410466A (zh) * 2001-09-29 2003-04-16 济南圣泉集团股份有限公司 一种有机酯硬化碱性酚醛树脂及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1110199A (zh) * 1994-04-11 1995-10-18 花王株式会社 铸模用粘合剂组合物和生产铸模的方法
CN1150070A (zh) * 1995-11-08 1997-05-21 花王株式会社 铸型用粘结剂组合物、铸型组合物和铸型的制造方法
CN1158769A (zh) * 1995-11-08 1997-09-10 花王株式会社 铸型的制造方法、铸型组合物及铸型用粘结剂组合物
CN1171991A (zh) * 1996-01-31 1998-02-04 花王株式会社 二氧化碳气体硬化用粘结剂组合物
WO1999011686A1 (fr) * 1997-09-04 1999-03-11 Ashland-Südchemie-Kernfest GmbH Resine phenolique et liant pour la production de moules et de noyaux selon le procede polyurethanne-resine phenolique
CN101348549A (zh) * 2008-08-22 2009-01-21 辽宁福鞍铸业集团有限公司 端羟基碱性酚醛树脂及其制备方法

Also Published As

Publication number Publication date
CN102753619A (zh) 2012-10-24
TR201108926T1 (tr) 2012-04-24
AU2010345651B2 (en) 2013-11-28
AU2010345651A1 (en) 2011-10-06
CN102753619B (zh) 2014-10-01
RU2011134668A (ru) 2013-02-27
RU2480308C1 (ru) 2013-04-27

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