WO2017173859A1 - 冷芯盒粘结剂及铸造成型体 - Google Patents

冷芯盒粘结剂及铸造成型体 Download PDF

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Publication number
WO2017173859A1
WO2017173859A1 PCT/CN2016/112931 CN2016112931W WO2017173859A1 WO 2017173859 A1 WO2017173859 A1 WO 2017173859A1 CN 2016112931 W CN2016112931 W CN 2016112931W WO 2017173859 A1 WO2017173859 A1 WO 2017173859A1
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Prior art keywords
component
resin
cold box
benzyl ether
phenolic resin
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PCT/CN2016/112931
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English (en)
French (fr)
Inventor
祝建勋
许增彬
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济南圣泉集团股份有限公司
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Publication of WO2017173859A1 publication Critical patent/WO2017173859A1/zh

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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
    • 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
    • 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
    • B22C1/2273—Polyurethanes; Polyisocyanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C7/00—Patterns; Manufacture thereof so far as not provided for in other classes
    • B22C7/06—Core boxes
    • 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

Definitions

  • the invention relates to the technical field of adhesives, in particular to a cold box adhesive and a cast molded body for colored cast resin sand, which is mixed with a cast aggregate to form a casting mixture and acts on a catalyst.
  • the core mold for forming a cast metal casting is formed, and is particularly suitable for casting a colored alloy member.
  • the existing cold box binder is a two-component resin which is cured under the catalytic action of triethylamine, dimethylethylamine and dimethylisopropylamine.
  • the amount of resin added is generally high, between 1.0 and 2.0%.
  • the resin addition amount is reduced to 0.85-1.2% under the condition that the strength of the resin sand core is satisfied, but the casting temperature is low (like the aluminum alloy casting temperature).
  • the casting temperature is low (like the aluminum alloy casting temperature).
  • the binder in the sand core is not completely decomposed by heat, and the resin sand can not be completely broken, which makes the sand falling very difficult.
  • the resin used now also causes the residual tar on the metal mold after casting to be high, which not only affects The quality of the castings, and the need to continuously clean the residual tar on the mold during production, reducing production efficiency.
  • U.S. Patent No. 4,946,876 discloses the addition of polyester polyol to improve the collapsibility, but has the disadvantage of low core strength and the problem of not completely improving the collapsibility
  • US 5,132,339 discloses the addition of polyethylene glycol (molecular weight 400) to improve the collapsibility, but still has the disadvantage of poor moisture resistance, and the collapsibility is not greatly improved
  • Chinese patent CN101524737A discloses the use of glycol to react to the original resin system.
  • the Chinese patent CN101147953 before the applicant discloses a high performance low smoke flame retardant amine cold box adhesive for
  • the two-component adhesive can increase the strength of the resin and does not completely improve the collapse of the resin sand core. Therefore, it is necessary to further improve the problem of the collapsibility of the resin sand core on the basis of this, and to meet the strength and moisture resistance requirements of the resin sand core while reducing the amount of residual tar.
  • the technical problem to be solved by the present invention is to provide a resin capable of reducing the amount of resin to 0.55-0.75% under the condition of ensuring the strength of the resin sand core. Compared with the prior art, the amount of resin used is greatly reduced, and the collapse of the resin sand core is improved.
  • the invention relates to a cold box adhesive comprising component I, characterized in that said component I consists of the following raw parts by weight:
  • a benzyl ether phenolic resin 40 to 80 parts, preferably 50 to 70 parts;
  • the benzyl ether phenolic resin has a methylol content of 32% to 50% and more than 27%.
  • the benzyl ether phenolic resin has a methylol content of from 32% to 50%.
  • the cold box adhesive further comprises a component II consisting of the following raw materials by weight:
  • Additive additives 0 to 10 parts.
  • the affinity/comparison of the functional groups in the benzyl ether phenolic resin is greater than 1; more preferably, the benzyl ether phenolic resin is a benzyl ether phenolic resin having a weight average molecular weight of 500 to 2000 or higher; further preferably The benzyl ether phenolic resin is a benzyl ether phenolic resin having a molecular weight of 600 to 1200 or higher.
  • the high-boiling ester and/or hydrocarbon solvent in the component I and the component II are each independently selected from the group consisting of dibutyl phthalate, dioctyl phthalate, and diphthalic acid.
  • liquid petroleum aromatic fractions and kerosene having a distillation range of 150 to 290 ° C; wherein the liquid petroleum aromatic fraction of the distillation range of 150 to 290 ° C is one of solves 100, solves 150 or solves 200 Kind or several.
  • Solvents which may be used include liquid high boiling esters, vegetable oils, lower alcohols and hydrocarbons such as aromatic hydrocarbons.
  • the high boiling ester means that the boiling point is between 100400 ° C, Especially for carboxylic acid esters between 150 and 400 ° C, especially between 200 and 400 ° C, examples include dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate , diisooctyl phthalate, dioctyl adipate, dimethyl succinate, dimethyl glutarate, dimethyl adipate;
  • examples of lower alcohols include methanol, ethanol, butanol, Isopropanol;
  • aromatic hydrocarbons include benzene, toluene, xylene, and ethylbenzene, and liquid petroleum aromatic fractions having a distillation range of 150 to 290 ° C;
  • the tackifiers in the component I and the component II are each independently selected from a silane coupling agent, which is A-187 silane, A-171 silane, A-172 silane, One or more of A-174 silane, A-151 silane.
  • a silane coupling agent which is A-187 silane, A-171 silane, A-172 silane, One or more of A-174 silane, A-151 silane.
  • the above-mentioned thickening aid is added in an amount of 0.1 to 10 parts by weight.
  • the high ortho benzyl ether phenolic resin is obtained by the following method:
  • the molar ratio of the phenolic substance to the aldehyde substance is from 1:1.0 to 1:3.0, preferably from 1:1.2 to 1:2.5;
  • the catalyst is a catalyst system comprising a metal salt.
  • the phenolic substance is a mixed phenol; more preferably, the phenolic mixture is selected from one or a combination of two of phenol and alkylphenol; further preferably, the alkylphenol is selected from 2 ,6-dimethylphenol, o-cresol, m-cresol, p-cresol, 3,5-dimethylphenol, 3,4-dimethylphenol, 3-ethylphenol, 3,5-diethyl A combination of one or more of a phenol and a p-butyl phenol.
  • the catalyst system containing a metal salt comprises a zinc salt and a lead salt; preferably, the catalyst system containing the metal salt comprises a zinc salt; more preferably, the zinc salt is zinc acetate, sulfuric acid.
  • the zinc salt is zinc acetate, sulfuric acid.
  • zinc, zinc chloride, and zinc naphthenate is zinc acetate, sulfuric acid.
  • the polyisocyanate in the component II is selected from the group consisting of diphenylmethane-4,4'-diisocyanate, crude diphenylmethane-4,4'-diisocyanate or polymethylene polyphenyl polyiso One or more of cyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
  • the polyisocyanate used in the present invention may be an aliphatic polyisocyanate or an aromatic polyisocyanate, and examples of the aliphatic polyisocyanate are isophorone diisocyanate and hexamethylene diisocyanate.
  • aromatic polyisocyanates are diphenylmethane-4,4'-diisocyanate (abbreviated as "MDI”), crude diphenylmethane-4,4'-diisocyanate (abbreviated as crude “MDI”) or more. Methylene polyphenyl polyisocyanate (abbreviated as "PAPI”), or a combination thereof.
  • MDI diphenylmethane-4,4'-diisocyanate
  • crude MDI crude diphenylmethane-4,4'-diisocyanate
  • PAPI Methylene polyphenyl polyisocyanate
  • the components of the above component I and component II may be separate components or mixed with other components described, since the benzyl ether resin can react with polyisocyanate and cure, generally in casting production. Mixing is carried out and a cast body is prepared.
  • a high ortho-benzyl ether phenolic resin is preferably used.
  • the so-called high-ortho benzyl ether phenolic resin means a phenolic resin having an adjacent/contrast ratio of 1, or a phenolic resin which is mostly ortho. Faster cure rates can be achieved with high ortho-benzyl ether phenolic resins.
  • Step 1 The molten phenol, bisphenol A, paraformaldehyde, calcium oxide, zinc acetate are put into the reaction kettle and stirred uniformly, and the pH value of the mixed solution is adjusted to 4-7 by using a pH adjuster at 30-40 ° C;
  • Step 2 The reactor condenser is adjusted to a reflux state, the temperature is raised under stirring, the temperature is raised to 95 ° C in 60 minutes, and the reaction is kept at 95 to 105 ° C for 90 minutes;
  • Step 3 The reaction kettle is adjusted to a normal pressure fractionation state, the temperature in the autoclave is raised to 115 ° C in 60 minutes, and the reaction is kept at 115 to 120 ° C for 60 minutes;
  • Step 4 After the heat preservation is completed, the temperature is cooled to below 100 ° C, and then vacuum is applied to make the degree of vacuum reach 300 mmHg to 600 mmHg, and vacuuming for 25 to 35 minutes yields a high ortho-benzyl ether phenolic resin.
  • the above preparation method is not the only method for preparing a high hydroxyl content high ortho benzyl ether phenolic resin, by adjusting the content of each component, or replacing the similar raw materials, or adjusting the reaction conditions.
  • a high ortho-benzyl ether phenolic resin having a correspondingly high methylol content can be prepared.
  • the alkylphenol can also be used to replace the bisphenol A to obtain a high ortho-benzyl ether phenolic resin having a high methylol content, and the alkylphenol can be used as a 2,6-dimethylphenol, o-cresol or m-cresol. , p-cresol, 3,5-dimethylphenol, 3,4-dimethylphenol, 3-ethylphenol, 3,5-diethylphenol, p-butylphenol, and the like.
  • a high ortho-benzyl ether phenolic resin having a high methylol content can be obtained by using calcium oxide and zinc acetate as a composite catalyst.
  • Some of the divalent metal oxides include bismuth oxide, magnesium oxide, etc., which can replace calcium oxide for the purpose of the invention.
  • Zinc sulfate, zinc chloride, zinc naphthenate and the like zinc salts with zinc ions can also replace zinc acetate for the purpose of the invention. It should be noted that the single zinc salt catalyst is also helpful for obtaining a high ortho-benzyl ether phenolic resin having a high methylol content.
  • the present invention relates to a cast molded body characterized in that it is prepared by casting a aggregate and an effective amount of the cold box binder according to any one of claims 3-9-8, and then preparing under the action of a catalyst. Obtained; wherein the component I and the component II of the cold box adhesive are sequentially added or simultaneously mixed with the cast aggregate.
  • the cold box adhesive is mixed with the cast aggregate in a weight ratio of 0.55% to 0.75%.
  • Different types of aggregates and varying amounts of binder are used to prepare the foundry mix by methods known in the art.
  • Conventional molded bodies, precision cast molded bodies, and colored cast molded bodies can be prepared by using the binder system and appropriate aggregates, and are particularly suitable for preparing colored cast molded bodies.
  • the amount of binder used and the type of aggregate are well known to those skilled in the art.
  • Excellent The aggregate selected for use in preparing the foundry mix is sand wherein at least about 70% by weight, preferably at least about 85% by weight, of the sand is silica.
  • Other suitable aggregate materials for conventional cast molded bodies include zircon, olivine, aluminosilicate, chromite ore, and the like.
  • the amount of cold box binder is typically no greater than 2 wt%, and often in the range of 0.85-1.2 wt%, based on the weight of the aggregate.
  • the cold box adhesive has a weight ratio of 0.55% to 0.75%.
  • the cast aggregate is mixed.
  • the catalyst for preparing the cast shaped body is a gaseous amine
  • the gaseous amine may be triethylamine, dimethylethylamine or dimethylisopropylamine, preferably triethylamine.
  • the invention further optimizes the preparation process of the high ortho-benzyl ether phenolic resin, and prepares a high ortho-benzyl ether phenolic resin with a high methylol content and a high ortho-benzyl group by using a composite catalyst (calcium oxide and zinc acetate).
  • the high content of methylol of the ether phenolic resin can be rapidly reacted and solidified with the isocyanate of the isocyanate, thereby greatly improving the normal temperature performance of the binder resin, and on the other hand, the normal temperature strength of the prepared resin sand is greatly improved;
  • the amount of binder resin is also greatly reduced, so that the collapsibility of the resin sand core during the casting process is improved, and the amount of tar remaining on the metal mold after casting is also greatly reduced, so that the production efficiency is greatly improved.
  • the cold box binder of the present invention improves the normal temperature strength of the binder resin by a rapid curing reaction of a high ortho-benzyl ether phenolic resin having a high methylol content with an isocyanate resin, thereby bonding
  • the content of the resin is greatly reduced, the collapsibility of the resin sand core in the casting process is improved, the tar content on the metal mold is lowered, the room temperature strength of the prepared resin sand is improved, and the production efficiency is greatly improved;
  • the cold box binder of the present invention is prepared by using a composite catalyst technology of calcium oxide and zinc acetate to obtain a high hydroxyl content high ortho benzyl ether phenolic resin, which improves the reactivity with the isocyanate resin. ;
  • the cold box adhesive of the present invention can be used in non-ferrous casting, can reduce the amount of use, reduce the production cost, improve the production efficiency, and can be widely promoted and used.
  • the methylol content of the high-ortho benzyl ether phenolic resin was determined by the method of GB/T14074-2006 to characterize the effect of its methylol content on the strength of the resin sand.
  • component I In a mixing kettle equipped with a stirrer, 586 kg of high ortho-benzyl ether phenolic resin with high methylol content, 206 kg of dioctyl adipate, 199 kg of Solvesso 150 aromatics, A -187 silane 9 kg, start stirring, mix for about 2 hours to make the material mix evenly.
  • the high ortho-benzyl ether phenol resin has a methylol content of 32.99% and a weight average molecular weight of 1,000.
  • component II In a mixing kettle equipped with a stirrer, 800 kg of diphenylmethane-4,4'-diisocyanate, 173 kg of dioctyl phthalate, 18 kg of Solvesso 150 aromatics, A- 187 silane 9 kg, start stirring, mix for about 2 hours, so that the material is mixed evenly.
  • the liquid component I and the liquid component II are separately packaged by a container to obtain the cold box adhesive of the present invention.
  • the cold box binder of the present invention can be applied to a colored casting by mixing with a sand at a weight ratio of 0.55% to 0.75% to obtain a colored cast molded body.
  • the high ortho-benzyl ether phenolic resin having a high methylol content can be prepared by the following method:
  • Step 1 420 kg of melted phenol, 60 kg of bisphenol A, 312 kg of paraformaldehyde, 4 kg of calcium oxide, and 0.6 kg of zinc acetate were put into the reaction vessel and stirred uniformly, and mixed with a pH adjuster at 30-40 ° C.
  • the pH of the liquid is 4-7;
  • Step 2 The reactor condenser is adjusted to a reflux state, the temperature is raised under stirring, the temperature is raised to 95 ° C in 60 minutes, and the reaction is kept at 95 to 105 ° C for 90 minutes;
  • Step 3 The reaction kettle is adjusted to a normal pressure fractionation state, the temperature in the autoclave is raised to 115 ° C in 60 minutes, and the reaction is kept at 115 to 120 ° C for 60 minutes;
  • Step 4 After the heat preservation is completed, the temperature is cooled to below 100 ° C, and then vacuum is applied to make the vacuum degree reach 300 mmHg, and vacuum is applied for 30 minutes to obtain a high ortho-benzyl ether phenolic resin having a high methylol content.
  • component I same as in example 1, except that the hydroxymethyl group of the high ortho-benzyl ether phenolic resin added The amount is 25.38%.
  • Component II was prepared in the same manner as in Example 1.
  • the liquid component I and the liquid component II are separately packaged by a container to obtain a cold box adhesive.
  • the above high ortho-benzyl ether phenolic resin can be prepared by the following method:
  • Step 1 420 kg of melted phenol, 60 kg of bisphenol A, 312 kg of paraformaldehyde, and 4.6 kg of calcium oxide were put into the reaction vessel and stirred uniformly.
  • the pH of the mixture was adjusted at 30-40 ° C with a pH adjuster of 4 ⁇ 7;
  • Step 2 The reactor condenser is adjusted to a reflux state, the temperature is raised under stirring, the temperature is raised to 95 ° C in 60 minutes, and the reaction is kept at 95 to 105 ° C for 90 minutes;
  • Step 3 The reaction kettle is adjusted to a normal pressure fractionation state, the temperature in the autoclave is raised to 115 ° C in 60 minutes, and the reaction is kept at 115 to 120 ° C for 60 minutes;
  • Step 4 After the heat preservation is completed, the temperature is cooled to below 100 ° C, and then vacuum is applied to make the vacuum degree reach 300 mmHg, and vacuum is applied for 30 minutes to obtain a high ortho-benzyl ether phenolic resin.
  • component I 400 kg of high- ortho-benzyl ether phenolic resin with high hydroxyl content, 313 kg of dibutyl phthalate, 187 kg of Solvesso 150 aromatic hydrocarbon, A- in a mixing kettle equipped with a stirrer 187 silane 100 kg, start stirring, mix for about 2 hours to make the material mix evenly.
  • the high ortho benzyl ether phenol resin has a methylol content of 39.30% and a weight average molecular weight of 600.
  • component II In a mixing kettle equipped with a stirrer, 800 kg of diphenylmethane-4,4'-diisocyanate, 163 kg of dibutyl phthalate, 10 kg of ethanol, Solvesso 200 aromatics 18 were added. Kilograms, 9 kg of A-174 silane, start stirring, mix for about 2 hours, and mix the materials evenly.
  • the liquid component I and the liquid component II are separately packaged by a container to obtain the cold box adhesive of the present invention.
  • the cold box binder of the present invention can be applied to a colored casting by mixing with a sand at a weight ratio of 0.55% to 0.75% to obtain a colored cast molded body.
  • the high ortho-benzyl ether phenolic resin having a high methylol content can be prepared by the following method:
  • Step 1 420 kg of melted phenol, 60 kg of bisphenol A, 398 kg of paraformaldehyde, 4 kg of calcium oxide, and 1 kg of zinc acetate were put into the reaction vessel and stirred uniformly, and mixed with a pH adjuster at 30-40 ° C.
  • the pH of the liquid is 5-6;
  • Step 2 The reactor condenser is adjusted to a reflux state, the temperature is raised under stirring, the temperature is raised to 95 ° C in 60 minutes, and the reaction is kept at 95 to 105 ° C for 90 minutes;
  • Step 3 The reaction kettle is adjusted to a normal pressure fractionation state, the temperature in the autoclave is raised to 115 ° C in 60 minutes, and the reaction is kept at 115 to 120 ° C for 60 minutes;
  • Step 4 After the heat preservation is completed, the temperature is cooled to below 100 ° C, and then vacuum is applied to make the degree of vacuum reach 600 mmHg, and vacuum is applied for 25 minutes to obtain a high ortho-benzyl ether phenolic resin having a high methylol content.
  • component II is the same as in the second embodiment.
  • the liquid component I and the liquid component II are separately packaged by a container to obtain a cold box adhesive.
  • Step 1 420 kg of melted phenol, 60 kg of bisphenol A, 275 kg of paraformaldehyde, and 4.6 kg of zinc acetate are put into the reaction vessel and stirred uniformly. The mixture is adjusted to 4 to 7 with a pH adjuster at 30-40 ° C. ;
  • Step 2 The reactor condenser is adjusted to a reflux state, the temperature is raised under stirring, the temperature is raised to 95 ° C in 60 minutes, and the reaction is kept at 95 to 105 ° C for 90 minutes;
  • Step 3 The reaction kettle is adjusted to a normal pressure fractionation state, the temperature in the autoclave is raised to 115 ° C in 60 minutes, and the reaction is kept at 115 to 120 ° C for 60 minutes;
  • Step 4 After the heat preservation is completed, the temperature is cooled to below 100 ° C, and then vacuum is applied to make the vacuum degree reach 600 mmHg, and vacuum is applied for 25 minutes to obtain a high ortho-benzyl ether phenolic resin.
  • component I In a mixing kettle equipped with a stirrer, 634 kg of a high ortho-benzyl ether phenolic resin with a high methylol content, 245 kg of dioctyl phthalate and 110 kg of a Solvesso 150 aromatic hydrocarbon were added. A-187 silane 11 kg, start stirring, mix for about 2 hours, so that the material is mixed evenly. Among them, the high ortho-benzyl ether phenol resin has a methylol content of 35.69% and a weight average molecular weight of 800.
  • component II In a mixing kettle equipped with a stirrer, 700 kg of polymethylene polyphenyl polyisocyanate, 111 kg of dioctyl phthalate, 180 kg of Solvesso 100 aromatic hydrocarbon, A- 187 silane 9 kg, start stirring, mix for about 2 hours, so that the material is mixed evenly.
  • the liquid component I and the liquid component II are separately packaged by a container to obtain the cold box adhesive of the present invention.
  • the cold box binder of the present invention can be applied to a colored casting by mixing with a sand at a weight ratio of 0.55% to 0.75% to obtain a colored cast molded body.
  • Step 1 420 kg of melted phenol, 60 kg of bisphenol A, 368 kg of paraformaldehyde, 4 kg of calcium oxide, and 1 kg of zinc acetate were put into the reaction vessel and stirred uniformly. The mixture was adjusted and mixed at 30-40 °C with a pH adjuster. The liquid is 5-6;
  • Step 2 The reactor condenser is adjusted to a reflux state, the temperature is raised under stirring, the temperature is raised to 95 ° C in 60 minutes, and the reaction is kept at 95 to 105 ° C for 90 minutes;
  • Step 3 The reaction kettle is adjusted to a normal pressure fractionation state, the temperature in the autoclave is raised to 115 ° C in 60 minutes, and the reaction is kept at 115 to 120 ° C for 60 minutes;
  • Step 4 After the heat preservation is completed, the temperature is cooled to below 100 ° C, and then vacuum is applied to make the vacuum degree reach 400 mmHg, and vacuum is applied for 30 minutes to obtain a high ortho-benzyl ether phenolic resin having a high methylol content.
  • the liquid component I and the liquid component II are separately packaged by a container to obtain a cold box adhesive.
  • Step 1 420 kg of melted phenol, 208 kg of paraformaldehyde, 6 kg of calcium oxide into the reaction kettle and stir well, and adjust the mixture to 5 to 6 with a pH adjuster at 30-40 ° C;
  • Step 2 The reactor condenser is adjusted to a reflux state, the temperature is raised under stirring, the temperature is raised to 95 ° C in 60 minutes, and the reaction is kept at 95 to 105 ° C for 90 minutes;
  • Step 3 The reaction kettle is adjusted to a normal pressure fractionation state, the temperature in the autoclave is raised to 115 ° C in 60 minutes, and the reaction is kept at 115 to 120 ° C for 60 minutes;
  • Step 4 After the heat preservation is completed, the temperature is cooled to below 100 ° C, and then vacuum is applied to make the vacuum degree reach 400 mmHg, and vacuum is applied for 30 minutes to obtain a high ortho-benzyl ether phenolic resin.
  • component I in a mixing kettle equipped with a stirrer, a high ortho-benzyl ether phenolic resin with a high methylol content 700 kg, 291 kg of dimethyl adipate, 9 kg of A-187 silane, stirring and mixing for about 2 hours to mix the materials evenly.
  • the high ortho-benzyl ether phenol resin has a methylol content of 33.42% and a weight average molecular weight of 1200.
  • component II In a mixing kettle equipped with a stirrer, 800 kg of hexamethylene diisocyanate, 141 kg of dioctyl phthalate, 150 kg of Solvesso 100 aromatic hydrocarbon, and 9 kg of A-187 silane were added. Start stirring and mix for about 2 hours to mix the materials evenly.
  • the liquid component I and the liquid component II are separately packaged by a container to obtain the cold box adhesive of the present invention.
  • the cold box binder of the present invention can be colored and mixed with sand at a weight ratio of 0.55% to 0.75% to obtain a colored cast molded body.
  • Step 1 420 kg of melted phenol, 60 kg of bisphenol A, 348 kg of paraformaldehyde, 5 kg of calcium oxide, and 0.8 kg of zinc acetate were put into the reaction vessel and stirred uniformly, and mixed with a pH adjuster at 30-40 ° C.
  • the liquid is 5-6;
  • Steps 2 to 4 Refer to steps 2 to 4 of the preparation method of the first embodiment.
  • the liquid component I and the liquid component II are separately packaged by a container to obtain a cold box adhesive.
  • Step 1 420 kg of melted phenol, 60 kg of bisphenol A, 258 kg of paraformaldehyde, and 5 kg of sodium hydroxide are put into the reaction vessel and stirred uniformly. The mixture is adjusted to be 8 to 30 °C at 30-40 °C with a pH adjuster. 10;
  • Steps 2 to 4 Refer to Comparative Example 2, Preparation Method Steps 2 to 4.
  • component I In a mixing kettle equipped with a stirrer, 850 kg of high ortho-benzyl ether phenolic resin with high methylol content, 35 kg of dibutyl phthalate, dimethyl adipate 6 kg, Solvesso 100 aromatics 25 kg, Solvesso 100 aromatics 75 kg, A-187 silane 9 kg, start stirring, mixing for about 2 hours to make the material mix evenly.
  • the high ortho-benzyl ether phenolic resin has a methylol content of 27.62% and a weight average molecular weight of 1800.
  • component II In a mixing kettle equipped with a stirrer, 700 kg of hexamethylene diisocyanate was added, Solvesso 100 aromatics 281 kg, butanol 10 kg, A-174 silane 9 kg, start stirring, mixing for about 2 hours to make the material mix evenly.
  • the liquid component I and the liquid component II are separately packaged by a container to obtain the cold box adhesive of the present invention.
  • the cold box binder of the present invention can be applied to a colored casting by mixing with a sand at a weight ratio of 0.55% to 0.75% to obtain a colored cast molded body.
  • Step 1 420 kg of melted phenol, 80 kg of bisphenol A, 372 kg of paraformaldehyde, 3 kg of calcium oxide, and 0.1 kg of zinc acetate were put into the reaction vessel and stirred uniformly, and mixed with a pH adjuster at 30-40 ° C.
  • the liquid is 5-6;
  • Steps 2 to 4 Refer to steps 2 to 4 of the preparation method of the second embodiment.
  • Component II was prepared in the same manner as in Example 5.
  • the liquid component I and the liquid component II are separately packaged by a container to obtain a cold box adhesive.
  • Step 1 420 kg of melted phenol, 60 kg of bisphenol A, 312 kg of paraformaldehyde and 4 kg of zinc acetate are put into the reaction vessel and stirred uniformly. The mixture is adjusted to 5-6 by using a pH adjuster at 30-40 °C. ;
  • Step 2 Refer to Comparative Example 3 Preparation Method Steps 2 to 4.
  • component I 500 kg of high ortho-benzyl ether phenolic resin with high methylol content, 268 kg of dimethyl adipate, 223 kg of Solvesso 100 aromatic hydrocarbon, A in a mixing kettle equipped with a stirrer -187 silane 9 kg, start stirring, mix for about 2 hours to make the material mix evenly.
  • the high ortho-benzyl ether phenol resin has a methylol content of 36.39% and a weight average molecular weight of 500.
  • component II In a mixing kettle equipped with a stirrer, 800 kg of polymethylene polyphenyl polyisocyanate, 151 kg of dioctyl adipate, 40 kg of Solvesso 150 aromatic hydrocarbon, A-151 9 kg of silane, start stirring, mix for about 2 hours, and mix the materials evenly.
  • the liquid component I and the liquid component II are separately packaged by a container to obtain the cold box adhesive of the present invention.
  • the cold box binder of the present invention can be applied to a colored casting by mixing with a sand at a weight ratio of 0.55% to 0.75% to obtain a colored cast molded body.
  • Step 1 420 kg of melted phenol, 80 kg of bisphenol A, 368 kg of paraformaldehyde, 4 kg of calcium oxide, and 0.6 kg of zinc acetate were put into the reaction vessel and stirred uniformly, and mixed with a pH adjuster at 30-40 ° C.
  • the liquid is 5-6;
  • Step 2 Refer to Example 3, Preparation Steps 2 to 4.
  • the thickening aids in the first to sixth embodiments of the present invention including A187 silane and the like, may be omitted, and after the thickening aid is omitted, compared with the cold box adhesive of the present invention in which the tackifier is not omitted, after casting
  • the room temperature of the resin sand hardly changes (the strength is reduced to within 2%).
  • the present invention employs a composite catalyst (calcium oxide and zinc acetate) technology to greatly increase the methylol content of the high ortho benzyl ether phenolic resin, and to make the high ortho benzyl ether in the cold box binder of the present invention.
  • the hydroxymethyl content of the phenolic resin is greater than 27%.
  • the high ortho-benzyl ether phenolic resin prepared by using a single catalyst in the comparative example had a methylol content of less than 26%.
  • the cold box binder prepared by the invention can improve the normal temperature performance of the resin sand, the strength of the resin sand is measured, and the specific method refers to GB2684 "Testing method for raw sand and mixture for casting":
  • Resin sand is formulated in a ratio of 100 parts by weight of Dalin standard sand, 0.3 parts by weight of component I, and 0.25 parts by weight of component II.
  • the weight ratio of the cold box adhesive in the resin sand was 0.55%.
  • Resin sand is formulated in a ratio of 100 parts by weight of Dalin standard sand, 0.34 parts by weight of component I, and 0.32 parts by weight of component II.
  • the weight ratio of the cold box adhesive in the resin sand was 0.66%.
  • Resin sand is formulated in a ratio of 100 parts by weight of Dalin standard sand, 0.39 parts by weight of component I, and 0.37 parts by weight of component II.
  • the weight ratio of the cold box adhesive in the resin sand was 0.75%.
  • Resin sand is formulated in a ratio of 100 parts by weight of Dalin standard sand, 0.45 parts by weight of component I, and 0.43 parts by weight of component II.
  • the weight ratio of the cold box adhesive in the resin sand is 0.87%
  • the preparation method of the resin sand firstly, the component I is mixed with the standard sand for 1 minute, and then the component II is mixed for 2 minutes, and then the resin sand is blown by the MLA1 core making machine to form a bending resistant test piece.
  • the core making process parameters are: sand injection pressure 0.3 MPa, amine blowing pressure 0.2 Mpa, washing pressure 0.2 Mpa, amine blowing time 3.0 seconds, washing time 5.0 seconds.
  • the initial bending strength of the bending test piece, the 24-hour bending strength, and the 24-hour high-humidity strength (humidity ⁇ 95%) were measured.
  • the cold box adhesive of the present invention can significantly improve the bending resistance of the resin sand by separately measuring the initial bending strength of 5 seconds, the bending strength of 24 hours, and the high humidity strength (humidity ⁇ 95%) of the bending test piece. (Pressure) strength, high humidity bending strength (moisture resistance). As shown in Table 1, the resin core sand bending test piece for the cold core box binder of the first to sixth embodiments of the present invention was tested, and it was found that the cold core box adhesive of the present invention was added in an amount of 0.87%.
  • the initial bending strength of the bending test piece prepared in the first to sixth embodiments is 2.38 MPa to 2.85 MPa, the bending strength at 24 hours is 3.98 to 4.42 MPa, and the bending strength at 24 hours ( ⁇ 95%) is 3.48 MPa.
  • the initial bending strength of the flexural test piece prepared by the comparative example of the cold box adhesive of 0.87% is 1.35 MPa to 2.07 MPa, and the bending strength of the 24 hour is 2.29 MPa to 3.39 MPa.
  • the 24-hour high-humidity bending strength ( ⁇ 95%) is 1.93 MPa to 2.89 MPa.
  • the cold box adhesive of the present invention can significantly improve the flexural strength thereof in the case of the same addition amount, for example, 0.87% of the cold core box binder of the first embodiment is added to the bending test block.
  • the 24-hour bending strength is 4.26 ⁇ 0.05 MPa
  • the 24-hour bending strength of Comparative Example 1 is 3.20 ⁇ 0.06 MPa.
  • Explain its 24-hour bending strength that is, the normal temperature bending (pressure) strength is increased by about 30%; in Example 1, the 24-hour high-humidity bending strength ( ⁇ 95%) is 3.60 ⁇ 0.05 MPa, and the comparison ratio is 24 hours high humidity.
  • the flexural strength ( ⁇ 95%) is 2.75 ⁇ 0.06MPa, indicating that its 24-hour high-humidity bending strength ( ⁇ 95%), that is, the resistance to moisture (pressure) is increased by about 25%; Comparative Example 1 is only the high ortho-benzyl ether phenolic resin has different methylol content (32.99% in the first example and 25.38% in the first example), indicating that the high hydroxyl content of the ortho-benzyl ether phenolic resin can be greatly improved.
  • the flexural strength of the flexural test piece according to the addition amount of the 0.66%, 0.75%, and 0.87% cold box adhesives was measured, as shown in Table 1. It has been found that the cold box adhesive of the present invention can meet the casting production requirement only by the addition amount of 0.55%, and the bending strength of the first embodiment to the sixth embodiment can reach 2.79 MPa to 3.13 MPa; 0.66% cold box
  • the 24-hour bending strength (normal temperature bending strength) of the flexural test piece of the binder added amount is 3.01 MPa to 3.57 MPa, and the bending strength of the amount of the addition of 0.87% of the cold box adhesive is 24 hours.
  • 2.29MPa ⁇ 3.39MPa is close to each other, for example, 0.66% of the cold core box binder of the first embodiment has a 24 hour bending strength of 3.28 ⁇ 0.06 MPa, and a heating core of 0.87% of the comparative one.
  • the 24-hour bending strength of the bending test piece of the amount of the box binder is 3.20 ⁇ 0.05 MPa (see Table 1.2), indicating that the same resin sand bending strength is to be achieved, and the cold box adhesive of the present invention is The addition amount can be reduced by about 22% compared with the comparative example; at the same time, the hydroxymethyl content of the high ortho-benzyl ether phenolic resin in the component I is compared with the cold core box binder of the fifth embodiment.
  • the cold core box adhesive of the present invention was used for casting of non-ferrous metals, the amount of use is greatly reduced, the fluidity of the resin sand core at the pouring temperature is increased, the problem of the collapsibility of the resin sand core is greatly improved, and the problem is reduced.
  • the amount of residual tar on the metal mold increases production efficiency.
  • the amount of tar remaining on the metal mold is reduced during sand core casting.
  • Casting a complex shape casting can continuously cast 80 molds or more, even 90 molds or more, and the preferred state is 90 molds or more.
  • the traditional cold core box adhesive needs to clean the tar on the metal mold after continuously casting the 10-30 mold.
  • the resin of this embodiment is industrially produced on the casting mold of the aluminum cylinder head.
  • the sand mixing system of the workshop has a sand mixing capacity of 200 kg per time, and the resin is added in an amount of 0.65%, wherein the ratio of the component I to the component II is 55:45.
  • the component I was added in an amount of 0.715 kg, and the component II was added in an amount of 0.585 kg.
  • the workshop sand mixing system has a sand mixing capacity of 200 kg per time, the resin addition amount is 0.90%, and the ratio of component I to component II is 55:45.
  • the component I was added in an amount of 0.99 kg, and the component II was added in an amount of 0.81 kg.
  • the sand sample block which was placed at room temperature for 24 hours was weighed (160 ⁇ 1 g), sealed with tin foil paper, and baked in a muffle furnace with a constant temperature of 450 °C for 15 minutes, taken out and cooled to room temperature, and then placed in a 70-mesh vibration. Shake for 2 minutes in the sieve and weigh the remaining sample weight.
  • the weight of the sample before calcination is subtracted from the weight of the sample after calcination, and the weight before calcination is expressed.
  • the collapsibility is expressed as a percentage.
  • the high ortho-benzyl ether phenolic resin of the high methylol group prepared by the composite catalyst technology has a methylol content of more than 27% and a methylol content of 32% to 50% of a high ortho-benzyl group.
  • the ether phenolic resin makes the cold box adhesive of the invention more effective, improves the curing reaction efficiency of the cold box adhesive, greatly improves the room temperature performance of the resin, and increases the room temperature strength of the resin sand by about 30%.
  • the moisture-resistant bending strength is increased by about 25%, and the amount of the cold-core box binder is reduced to 0.55-0.75% under the condition of ensuring the strength of the resin sand core, compared with the prior art 0.85-1.2% resin addition.
  • the amount of resin used is greatly reduced, so that the fluidity of the resin sand core at the pouring temperature is increased, the problem of the collapsibility of the resin sand core is greatly improved, the tar residue on the metal mold is reduced, and the production efficiency is improved.

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Abstract

涉及一种冷芯盒粘结剂及铸造成型体，属于粘结剂技术领域。冷芯盒粘结剂包括组分I，组分I由以下重量份的原料组成：苄基醚酚醛树脂40～80份、高沸点酯和/或烃溶剂1～50份、增粘助剂0.1～10份，其中，苄基醚酚醛树脂的羟甲基含量为32％～50％。所述冷芯盒粘结剂在保证树脂砂型芯强度的条件下树脂使用量降低至0.55-0.75％，与现有技术相比，树脂使用量大大降低，极大改善了树脂砂型芯的溃散性问题，同时减少了金属模具上的焦油残留量，提高了生产效率。

Description

冷芯盒粘结剂及铸造成型体
本申请要求中国发明专利申请201610207257.3(申请日：2016年04月05日；发明名称：高苄基醚酚醛树脂、制备方法及其应用于冷芯盒粘结剂的方法)的优先权，其全部内容通过援引并入本说明书。
技术领域
本发明涉及粘结剂技术领域，特别是指一种用于有色铸造树脂砂的冷芯盒粘结剂及铸造成型体，该粘结剂与铸造骨料混合而成铸造混合物，并在催化剂作用下形成制造铸造金属铸件的型芯模，尤其适于铸造有色合金件。
背景技术
铸造工业中，现有冷芯盒粘结剂为双组分树脂，在三乙胺、二甲基乙胺、二甲基异丙胺等催化作用下固化。为了确保树脂砂型芯有足够的强度，便于取模、搬运与储存，树脂加入量一般较高，在1.0-2.0％之间。该粘结剂应用于铸铁或铸钢生产时，由于浇注温度较高(一般在1400℃以上)，粘结剂能够完全受热分解，砂型芯很容易溃散。
现有冷芯盒粘结剂应用于有色铸造时，在保证树脂砂型芯强度满足使用性能的条件下，树脂加入量尽管降至0.85-1.2％，但由于浇注温度较低(像铝合金浇注温度为700-800℃)，砂型芯中粘结剂受热没有完全分解，树脂砂不能完全溃散，造成落砂非常困难；现用的树脂也造成浇注后金属模具上残留焦油量较高，不仅影响了铸件质量，而且生产时需不断清理模具上的残留焦油，降低了生产效率。
目前有很多研究者在试图解决这一问题，像美国专利US4946876公开了添加聚酯多元醇改善溃散性的措施，但存在砂芯强度低的缺点，同时存在没有完全改善溃散性的问题；美国专利US5132339公开了添加聚乙二醇(分子量400)改善溃散性的措施，但仍然存在抗湿性差的缺点，而且溃散性没有得到大幅改善；中国专利CN101524737A公开了采用二元醇对原树脂体系进行反应性改性，提高树脂的热分解性能，解决较低的浇注温度下砂芯溃散性问题，但存在浇注后金属模具上残留焦油量高，影响铸件质量，生产时仍需不断清理模具上的残留焦油，带来生产效率低的缺点。
申请人之前的中国专利CN101147953公开了一种高性能低烟阻燃胺法冷芯盒粘结剂，为 双组分粘结剂，可以提高树脂的强度，也没有完全改善树脂砂型芯的溃散性问题。因此，有必要在此基础上，进一步改善树脂砂型芯的溃散性问题，并在降低残留焦油量的同时满足树脂砂型芯的强度和抗湿性要求。
发明内容
本发明要解决的技术问题是提供一种能够在保证树脂砂型芯强度的条件下树脂使用量降低至0.55-0.75％，与现有技术相比，树脂使用量大大降低，改善树脂砂型芯的溃散性问题，并在降低残留焦油量的同时满足树脂砂型芯的强度和抗湿性要求的冷芯盒粘结剂及铸造成型体。本发明涉及一种冷芯盒粘结剂，包括组分I，其特征在于，所述组分I由以下重量份的原料组成：
苄基醚酚醛树脂         40～80份，优选50-70份；
高沸点酯和/或烃溶剂    1～45份
增粘助剂               0～10份；
其中，所述苄基醚酚醛树脂的羟甲基含量为32％～50％大于27％。
优选的，所述苄基醚酚醛树脂的羟甲基含量为32％～50％。
优选的，所述冷芯盒粘结剂还包括组分II，所述组分II由以下重量份的原料组成：
聚异氰酸酯           40～90份
高沸点酯和/或烃溶剂  5～45份
增粘助剂             0～10份。
优选的，所述苄基醚酚醛树脂中官能团的邻/对比大于1；更优选地，所述苄基醚酚醛树脂是重均分子量在500～2000高邻位苄基醚酚醛树脂；进一步优选地，所述苄基醚酚醛树脂是分子量在600～1200高邻位苄基醚酚醛树脂。
优选的，所述组分I和组分II中的高沸点酯和/或烃溶剂各自独立地选自为邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、邻苯二甲酸二异丁酯、邻苯二甲酸二异辛酯、己二酸二辛脂、丁二酸二甲酯、戊二酸二甲酯、己二酸二甲酯、甲醇、乙醇、丁醇、异丙醇、馏程150～290℃的液态石油芳烃分馏物、煤油中的一种或几种；其中，所述馏程150～290℃的液态石油芳烃分馏物为solvesso 100、solvesso 150或solvesso 200的一种或几种。
在大多数情况下，需要向粘结剂中引入溶剂(稀释剂)。可以使用的溶剂包括液体高沸点酯、植物油、低级醇和烃类，例如芳烃。在本发明中，高沸点酯是指沸点在100400℃之间， 尤其是在150～400℃之间，特别是在200～400℃之间的羧酸酯，例子包括邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、邻苯二甲酸二异丁酯、邻苯二甲酸二异辛酯、己二酸二辛脂、丁二酸二甲酯、戊二酸二甲酯、己二酸二甲酯；低级醇的例子包括甲醇、乙醇、丁醇、异丙醇；芳烃的例子包括苯、甲苯、二甲苯和乙苯、以及馏程为150～290℃的液态石油芳烃分馏物；优选地，馏程150～290℃的液态石油芳烃分馏物为solvesso 100、solvesso 150、solvesso200中的一种或几种。
优选的，所述组分I和组分II中的增粘助剂各自独立地选自硅烷偶联剂，所述硅烷偶联剂为A-187硅烷、A-171硅烷、A-172硅烷、A-174硅烷、A-151硅烷中的一种或多种。优选地，上述增粘助剂的加入量为0.1～10重量份。优选的，所述高邻位苄基醚酚醛树脂通过以下方法制得：
将酚类物质、醛类物质、催化剂混合加入反应釜中，反应制得所述酚醛树脂；
所述酚类物质和醛类物质的摩尔比为1∶1.0～1∶3.0，优选为1∶1.2-1∶2.5；
催化剂为包含有金属盐的催化剂体系。
优选的，所述酚类物质为混合酚；更优选的，所述酚类混合物选自苯酚、烷基酚中的一种或两种的组合；进一步优选的，所述烷基酚选自2，6-二甲基苯酚、邻甲酚、间甲酚、对甲酚、3，5-二甲基苯酚、3，4-二甲基苯酚、3-乙基酚、3，5-二乙基酚和对丁基酚的一种或多种的组合。
优选的，所述包含有金属盐的催化剂体系为包含锌盐和铅盐；优选的，所述包含有金属盐的催化剂体系为包含锌盐；更优选的，所述锌盐为醋酸锌、硫酸锌、氯化锌、环烷酸锌中的一种或多种。
优选的，所述组分II中的聚异氰酸酯选自二苯基甲烷-4，4’-二异氰酸酯、粗二苯基甲烷-4，4’-二异氰酸酯或多亚甲基多苯基多异氰酸脂、1，6-己二异氰酸酯、异佛尔酮二异氰酸酯中的一种或几种。本发明使用的聚异氰酸酯可以是脂肪族聚异氰酸酯或芳香族聚异氰酸酯，脂肪族聚异氰酸酯的例子有异佛乐酮二异氰酸酯、六亚甲基二异氰酸酯。芳香族聚异氰酸酯的例子有二苯基甲烷-4，4’-二异氰酸酯(简称为“MDI”)、粗二苯基甲烷-4，4’-二异氰酸酯(简称为粗“MDI”)或多亚甲基多苯基多异氰酸酯(简称为“PAPI”)，或它们的组合物。上述组分I和组分II的各组分可以是单独的组分，或者与其它所述的组分进行混合，由于苄基醚树脂可与聚异氰酸发生反应并固化，一般在铸造生产时进行混合并制备铸造体。
通过选用该特定的苄基醚酚醛树脂，可以降低粘结剂的粘度，使得混合有粘结剂的铸造 砂具有较高的流散性和更高的砂型砂芯强度。本发明中优选使用高邻位苄基醚酚醛树脂，所谓高邻位苄基醚酚醛树脂是指邻/对比大于1的酚醛树脂，或者说大部分为邻位的酚醛树脂。使用高邻位苄基醚酚醛树脂可以获得较快的固化速度。
为了制备上述高羟甲基含量的高邻位苄基醚酚醛树脂，可以通过以下方法制得：
步骤1：将熔化好的苯酚、双酚A、多聚甲醛、氧化钙、醋酸锌投入反应釜中搅拌均匀，用PH调节剂在30～40℃下调混合液PH值4～7；
步骤2：将反应釜冷凝器调整为回流状态，在搅拌下升温，在60分钟内使温度升至95℃，并在95～105℃保温反应90分钟；
步骤3：将反应釜调整为常压分馏状态，在60分钟内使釜内温度升至115℃，并在115～120℃保温反应60分钟；
步骤4：保温完毕，冷却降温至100℃以下，然后抽真空，使真空度达300mmHg～600mmHg，抽真空25～35分钟即得高邻位苄基醚酚醛树脂。
本领域技术人员应当理解，上述制备方法不是唯一制备高羟基含量的高邻位苄基醚酚醛树脂的方法，通过调整各组分的含量，或者更换相近似的原料，或者对反应条件进行调整都可以制备得到相应地高羟甲基含量的高邻位苄基醚酚醛树脂。
其中，烷基酚替换双酚A也可以获得高羟甲基含量的高邻位苄基醚酚醛树脂，烷基酚可以使用的有2，6-二甲基苯酚、邻甲酚、间甲酚、对甲酚、3，5-二甲基苯酚、3，4-二甲基苯酚、3-乙基酚、3，5-二乙基酚和对丁基酚等。
通过氧化钙和醋酸锌作为复合催化剂，可以获得高羟甲基含量的高邻位苄基醚酚醛树脂。其中一些二价金属氧化物包括化钡、氧化镁等可以替换氧化钙达到发明目的，带有锌离子的硫酸锌、氯化锌、环烷酸锌等锌盐也可以替换醋酸锌达到发明目的，需要说明的是，单独的锌盐催化剂对获得较高的羟甲基含量的高邻位苄基醚酚醛树脂也有帮助。
另一方面，本发明涉及一种铸造成型体，其特征在于，由铸造骨料和有效量的权利要求3-9-8任一所述的冷芯盒粘结剂混合后在催化剂作用下制备得到；其中，将所述冷芯盒粘结剂的所述组分I和组分II依次加入，或者同时加入与所述铸造骨料进行混合。
优选的，所述冷芯盒粘结剂按0.55％～0.75％的重量比与所述铸造骨料混合。
通过本领域已知的方法，不同类型的骨料和不同量的粘结剂被用于制备铸造混合物。使用该粘结剂系统和适当的骨料可制备普通成型体、精密铸造成型体、有色铸造成型体，尤其适合制备有色铸造成型体。所用粘结剂的量和骨料的类型对于本领域技术人员是公知的。优 选用于制备铸造混合物的骨料为砂，其中至少约70wt％、优选至少约85wt％的砂为硅石。其他适合的用于普通铸造成型体的骨料材料包括锆石、橄榄石、铝硅酸盐、铬铁矿砂等。
本领域技术人员应明了可以向骨料或铸造混合物中加入其他添加剂如硅氧烷、脱模剂、消泡剂、润湿剂等。特定添加剂的选择取决于设计者的具体目的。
冷芯盒粘结剂在有色铸造应用中，以骨料的重量为基准，冷芯盒粘结剂的量通常不大于2wt％，并且常常在0.85-1.2wt％的范围内。
为了改善铸造成型体在浇注过程中的溃散性，并在降低残留焦油含量的同时满足树脂砂型芯的强度要求，优选地，所述冷芯盒粘结剂按0.55％～0.75％的重量比与所述铸造骨料混合。
进一步优选地，制备铸造成型体的催化剂为气态胺，气态胺可以是三乙胺、二甲基乙胺或二甲基异丙胺，优选为三乙胺。
本发明通过对高邻位苄基醚酚醛树脂的制备工艺进一步优化，采用复合催化剂(氧化钙和醋酸锌)制备了高羟甲基含量的高邻位苄基醚酚醛树脂，高邻位苄基醚酚醛树脂的高含量的羟甲基可与异氰酸酯的异氰酸根快速反应固化，从而大幅度提高粘结剂树脂的常温性能，一方面使制备出的树脂砂常温强度得到大幅度提高；另一方面粘结剂树脂的用量也有大幅度下降，使得树脂砂型芯在浇注过程中的溃散性得到提高，浇注后残留在金属模具上的焦油量也大幅度减少，使生产效率得到大幅提高。
综上所述，本发明的有益效果表现为：
1)本发明的冷芯盒粘结剂，通过高羟甲基含量的高邻位苄基醚酚醛树脂与异氰酸树脂的快速固化反应提高了粘结剂树脂的常温强度，从而使粘结剂树脂的含量大幅降低，提高了浇注过程中树脂砂型芯的溃散性，降低了金属模具上的焦油含量，并提高了所制备的树脂砂的常温强度，大大提高了生产效率；
2)本发明的的冷芯盒粘结剂，通过采用氧化钙和醋酸锌的复合催化剂技术制备得到了高羟基含量的高邻位苄基醚酚醛树脂，提高了与异氰酸树脂的反应活性；
3)本发明的冷芯盒粘结剂，应用于有色铸造时，可以降低使用量，降低了生产成本，提高了生产效率，可以广泛推广和使用。
具体实施方式
为使本发明的实施例要解决的技术问题、技术方案和优点更加清楚，下面将结合具体实施例进行详细描述。但本发明绝非限于这些例子。以下所述仅为本发明较好的实施例，仅仅 用以解释本发明，并不能因此而理解为本发明专利范围的限制。应当指出的是，凡在本发明的精神和原则之内所做的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。因此，本发明专利的保护范围应以所附权利要求为准。
对高邻位苄基醚酚醛树脂的羟甲基含量进行测定，测定方法参照GB/T14074-2006，以表征其羟甲基含量对树脂砂强度的影响。
实施例一
冷芯盒粘结剂：
组分I的制备：在装有搅拌器的混合釜中，加入高羟甲基含量的高邻位苄基醚酚醛树脂586千克，己二酸二辛脂206千克，Solvesso 150芳烃199千克，A-187硅烷9千克，开动搅拌，混合约2小时，使物料混合均匀。其中，高邻位苄基醚酚醛树脂的羟甲基含量为32.99％，重均分子量为1000。
组分II的制备：在装有搅拌器的混合釜中，加入二苯基甲烷-4，4’-二异氰酸酯800千克，邻苯二甲酸二辛酯173千克，Solvesso 150芳烃18千克，A-187硅烷9千克，开动搅拌，混合约2小时，使物料混合均匀。
用容器对上述液体组分I和液体组分II分别包装，即得到本发明的冷芯盒粘结剂。
可以将本发明的冷芯盒粘结剂按0.55％～0.75％的重量比与砂混合应用于有色铸造，得到有色铸造成型体。
其中，上述高羟甲基含量的高邻位苄基醚酚醛树脂可以参考以下方法制备：
步骤1：将熔化好的苯酚420千克、双酚A 60千克、多聚甲醛312千克、氧化钙4千克、醋酸锌0.6千克投入反应釜中搅拌均匀，用PH调节剂在30～40℃下调混合液PH值为4～7；
步骤2：将反应釜冷凝器调整为回流状态，在搅拌下升温，在60分钟内使温度升至95℃，并在95～105℃保温反应90分钟；
步骤3：将反应釜调整为常压分馏状态，在60分钟内使釜内温度升至115℃，并在115～120℃保温反应60分钟；
步骤4：保温完毕，冷却降温至100℃以下，然后抽真空，使真空度达300mmHg，抽真空30分钟即得高羟甲基含量的高邻位苄基醚酚醛树脂。
对比例一
冷芯盒粘结剂：
组分I的制备：与实施例一相同，不同的是所加入的高邻位苄基醚酚醛树脂的羟甲基含 量为25.38％。
组分II的制备同实施例一。
用容器对上述液体组分I和液体组分II分别包装，即得到冷芯盒粘结剂。
其中，上述高邻位苄基醚酚醛树脂可以通过以下方法制备：
步骤1：将熔化好的苯酚420千克、双酚A 60千克、多聚甲醛312千克、氧化钙4.6千克投入反应釜中搅拌均匀，用PH调节剂在30～40℃下调混合液PH值为4～7；
步骤2：将反应釜冷凝器调整为回流状态，在搅拌下升温，在60分钟内使温度升至95℃，并在95～105℃保温反应90分钟；
步骤3：将反应釜调整为常压分馏状态，在60分钟内使釜内温度升至115℃，并在115～120℃保温反应60分钟；
步骤4：保温完毕，冷却降温至100℃以下，然后抽真空，使真空度达300mmHg，抽真空30分钟即得高邻位苄基醚酚醛树脂。
实施例二
冷芯盒粘结剂：
组分I的制备：在装有搅拌器的混合釜中，加入高羟基含量的高邻位苄基醚酚醛树脂400千克，邻苯二甲酸二丁酯313千克，Solvesso 150芳烃187千克，A-187硅烷100千克，开动搅拌，混合约2小时，使物料混合均匀。其中，高邻位苄基醚酚醛树脂的羟甲基含量为39.30％，重均分子量为600。
组分II的制备：在装有搅拌器的混合釜中，加入二苯基甲烷-4，4’-二异氰酸酯800千克，邻苯二甲酸二丁酯163千克，乙醇10千克，Solvesso 200芳烃18千克，A-174硅烷9千克，开动搅拌，混合约2小时，使物料混合均匀。
用容器对上述液体组分I和液体组分II分别包装，即得到本发明的冷芯盒粘结剂。
可以将本发明的冷芯盒粘结剂按0.55％～0.75％的重量比与砂混合应用于有色铸造，得到有色铸造成型体。
其中，上述高羟甲基含量的高邻位苄基醚酚醛树脂可以参考以下方法制备：
步骤1：将熔化好的苯酚420千克、双酚A 60千克、多聚甲醛398千克、氧化钙4千克、醋酸锌1千克投入反应釜中搅拌均匀，用PH调节剂在30～40℃下调混合液PH值为5～6；
步骤2：将反应釜冷凝器调整为回流状态，在搅拌下升温，在60分钟内使温度升至95℃，并在95～105℃保温反应90分钟；
步骤3：将反应釜调整为常压分馏状态，在60分钟内使釜内温度升至115℃，并在115～120℃保温反应60分钟；
步骤4：保温完毕，冷却降温至100℃以下，然后抽真空，使真空度达600mmHg，抽真空25分钟即得高羟甲基含量的高邻位苄基醚酚醛树脂。
对比例二
冷芯盒粘结剂：
组分I的制备：与实施例二相同，不同的是所加入的高邻位苄基醚酚醛树脂的羟甲基含量为22.69％。
组分II的制备同实施例二。
用容器对上述液体组分I和液体组分II分别包装，即得到冷芯盒粘结剂。
上述高邻位苄基醚酚醛树脂的制备方法可参考：
步骤1：将熔化好的苯酚420千克、双酚A 60千克、多聚甲醛275千克、醋酸锌4.6千克投入反应釜中搅拌均匀，用PH调节剂在30～40℃下调混合液为4～7；
步骤2：将反应釜冷凝器调整为回流状态，在搅拌下升温，在60分钟内使温度升至95℃，并在95～105℃保温反应90分钟；
步骤3：将反应釜调整为常压分馏状态，在60分钟内使釜内温度升至115℃，并在115～120℃保温反应60分钟；
步骤4：保温完毕，冷却降温至100℃以下，然后抽真空，使真空度达600mmHg，抽真空25分钟即得高邻位苄基醚酚醛树脂。
实施例三
冷芯盒粘结剂：
组分I的制备：在装有搅拌器的混合釜中，加入高羟甲基含量的高邻位苄基醚酚醛树脂634千克，邻苯二甲酸二辛酯245千克，Solvesso 150芳烃110千克，A-187硅烷11千克，开动搅拌，混合约2小时，使物料混合均匀。其中，高邻位苄基醚酚醛树脂的羟甲基含量为35.69％，重均分子量为800。
组分II的制备：在装有搅拌器的混合釜中，加入多亚甲基多苯基多异氰酸脂700千克，邻苯二甲酸二辛酯111千克，Solvesso 100芳烃180千克，A-187硅烷9千克，开动搅拌，混合约2小时，使物料混合均匀。
用容器对上述液体组分I和液体组分II分别包装，即得到本发明的冷芯盒粘结剂。
可以将本发明的冷芯盒粘结剂按0.55％～0.75％的重量比与砂混合应用于有色铸造，得到有色铸造成型体。
上述高羟甲基含量的高邻位苄基醚酚醛树脂的制备方法可参考：
步骤1：将熔化好的苯酚420千克、双酚A 60千克、多聚甲醛368千克、氧化钙4千克、醋酸锌1千克投入反应釜中搅拌均匀，用PH调节剂在30～40℃下调混合液为5～6；
步骤2：将反应釜冷凝器调整为回流状态，在搅拌下升温，在60分钟内使温度升至95℃，并在95～105℃保温反应90分钟；
步骤3：将反应釜调整为常压分馏状态，在60分钟内使釜内温度升至115℃，并在115～120℃保温反应60分钟；
步骤4：保温完毕，冷却降温至100℃以下，然后抽真空，使真空度达400mmHg，抽真空30分钟即得高羟甲基含量的高邻位苄基醚酚醛树脂。
对比例三
冷芯盒粘结剂：
组分I的制备：与实施例三相同，不同的是所加入的高邻位苄基醚酚醛树脂的羟甲基含量为16.78％。
组分II的制备同实施例三。
用容器对上述液体组分I和液体组分II分别包装，即得到冷芯盒粘结剂。
上述高邻位苄基醚酚醛树脂的制备方法可参考：
步骤1：将熔化好的苯酚420千克、多聚甲醛208千克、氧化钙6千克投入反应釜中搅拌均匀，用PH调节剂在30～40℃下调混合液为5～6；
步骤2：将反应釜冷凝器调整为回流状态，在搅拌下升温，在60分钟内使温度升至95℃，并在95～105℃保温反应90分钟；
步骤3：将反应釜调整为常压分馏状态，在60分钟内使釜内温度升至115℃，并在115～120℃保温反应60分钟；
步骤4：保温完毕，冷却降温至100℃以下，然后抽真空，使真空度达400mmHg，抽真空30分钟即得高邻位苄基醚酚醛树脂。
实施例四
冷芯盒粘结剂：
组分I的制备：在装有搅拌器的混合釜中，加入高羟甲基含量的高邻位苄基醚酚醛树脂 700千克，己二酸二甲酯291千克，A-187硅烷9千克，开动搅拌，混合约2小时，使物料混合均匀。其中，高邻位苄基醚酚醛树脂的羟甲基含量为33.42％，重均分子量为1200。
组分II的制备：在装有搅拌器的混合釜中，加入1，6-己二异氰酸酯800千克，邻苯二甲酸二辛酯141千克，Solvesso 100芳烃150千克，A-187硅烷9千克，开动搅拌，混合约2小时，使物料混合均匀。
用容器对上述液体组分I和液体组分II分别包装，即得到本发明的冷芯盒粘结剂。
可以将本发明的冷芯盒粘结剂按0.55％～0.75％的重量比与砂混合进行有色铸造，得到有色铸造成型体。
上述高羟甲基含量的高邻位苄基醚酚醛树脂的制备方法可参考：
步骤1：将熔化好的苯酚420千克、双酚A 60千克、多聚甲醛348千克、氧化钙5千克、醋酸锌0.8千克投入反应釜中搅拌均匀，用PH调节剂在30～40℃下调混合液为5～6；
步骤2～4：参考实施例一制备方法步骤2～4。
对比例四
冷芯盒粘结剂：
组分I的制备：与实施例四相同，不同的是所加入的高邻位苄基醚酚醛树脂的羟甲基含量为19.32％。
组分II的制备同实施例四。
用容器对上述液体组分I和液体组分II分别包装，即得到冷芯盒粘结剂。
上述高邻位苄基醚酚醛树脂的制备方法可参考：
步骤1：将熔化好的苯酚420千克、双酚A 60千克、多聚甲醛258千克、氢氧化钠5千克投入反应釜中搅拌均匀，用PH调节剂在30～40℃下调混合液为8～10；
步骤2～4：参考对比例二制备方法步骤2～4。
实施例五
冷芯盒粘结剂：
组分I的制备：在装有搅拌器的混合釜中，加入高羟甲基含量的高邻位苄基醚酚醛树脂850千克，邻苯二甲酸二丁酯35千克，己二酸二甲酯6千克，Solvesso 100芳烃25千克，Solvesso 100芳烃75千克，A-187硅烷9千克，开动搅拌，混合约2小时，使物料混合均匀。其中，高邻位苄基醚酚醛树脂的羟甲基含量为27.62％，重均分子量为1800。
组分II的制备：在装有搅拌器的混合釜中，加入1，6-己二异氰酸酯700千克，Solvesso 100芳烃281千克，丁醇10千克，A-174硅烷9千克，开动搅拌，混合约2小时，使物料混合均匀。
用容器对上述液体组分I和液体组分II分别包装，即得到本发明的冷芯盒粘结剂。
可以将本发明的冷芯盒粘结剂按0.55％～0.75％的重量比与砂混合应用于有色铸造，得到有色铸造成型体。
上述高羟甲基含量的高邻位苄基醚酚醛树脂的制备方法可参考：
步骤1：将熔化好的苯酚420千克、双酚A 80千克、多聚甲醛372千克、氧化钙3千克、醋酸锌0.1千克投入反应釜中搅拌均匀，用PH调节剂在30～40℃下调混合液为5～6；
步骤2～4：参考实施例二制备方法步骤2～4。
对比例五
冷芯盒粘结剂：
组分I的制备：与实施例四相同，不同的是所加入的高邻位苄基醚酚醛树脂的羟甲基含量为25.98％。
组分II的制备同实施例五。
用容器对上述液体组分I和液体组分II分别包装，即得到冷芯盒粘结剂。
上述高邻位苄基醚酚醛树脂的制备方法可参考：
步骤1：将熔化好的苯酚420千克、双酚A 60千克，多聚甲醛312千克、醋酸锌4千克投入反应釜中搅拌均匀，用PH调节剂在30～40℃下调混合液为5～6；
步骤2：参考对比例三制备方法步骤2～4。
实施例六
冷芯盒粘结剂：
组分I的制备：在装有搅拌器的混合釜中，加入高羟甲基含量的高邻位苄基醚酚醛树脂500千克，己二酸二甲酯268千克，Solvesso 100芳烃223千克，A-187硅烷9千克，开动搅拌，混合约2小时，使物料混合均匀。其中，高邻位苄基醚酚醛树脂的羟甲基含量为36.39％，重均分子量为500。
组分II的制备：在装有搅拌器的混合釜中，加入多亚甲基多苯基多异氰酸脂800千克，己二酸二辛酯151千克，Solvesso 150芳烃40千克，A-151硅烷9千克，开动搅拌，混合约2小时，使物料混合均匀。
用容器对上述液体组分I和液体组分II分别包装，即得到本发明的冷芯盒粘结剂。
可以将本发明的冷芯盒粘结剂按0.55％～0.75％的重量比与砂混合应用于有色铸造，得到有色铸造成型体。
上述高羟甲基含量的高邻位苄基醚酚醛树脂的制备方法可参考：
步骤1：将熔化好的苯酚420千克、双酚A 80千克、多聚甲醛368千克、氧化钙4千克、醋酸锌0.6千克投入反应釜中搅拌均匀，用PH调节剂在30～40℃下调混合液为5～6；
步骤2：参考实施例三制备方法步骤2～4。
本发明实施例一至实施例六中的增粘助剂包括A187硅烷等可以省略，省略增粘助剂后，与未省略增粘助剂的本发明的冷芯盒粘结剂相比，铸造后的树脂砂的常温强度几乎不发生变化(强度降低在2％以内)。
因此，本发明采用复合催化剂(氧化钙和醋酸锌)技术大大提高了高邻位苄基醚酚醛树脂的羟甲基含量，使本发明的冷芯盒粘结剂中的高邻位苄基醚酚醛树脂的羟甲基含量均大于27％。而对比例采用单催化剂制备的高邻位苄基醚酚醛树脂的羟甲基含量小于26％。
为进一步证明本发明制备的冷芯盒粘结剂能够改善树脂砂的常温性能，对树脂砂强度进行测定，具体方法参照GB2684《铸造用原砂及混合料试验方法》：
1)按照100重量份大林标准砂、0.3重量份组分I、0.25重量份组分II的比例配成树脂砂。冷芯盒粘结剂在树脂砂中的重量比为0.55％。
2)按照100重量份大林标准砂、0.34重量份组分I、0.32重量份组分II的比例配成树脂砂。冷芯盒粘结剂在树脂砂中的重量比为0.66％。
3)按照100重量份大林标准砂、0.39重量份组分I、0.37重量份组分II的比例配成树脂砂。冷芯盒粘结剂在树脂砂中的重量比为0.75％。
4)按照100重量份大林标准砂、0.45重量份组分I、0.43重量份组分II的比例配成树脂砂。冷芯盒粘结剂在树脂砂中的重量比为0.87％
树脂砂的制备方法：首先加入组分I与标准砂混合1分钟，再加入组分II混合2分钟，然后将该树脂砂通过MLA1制芯机吹气压制成抗弯试块。其制芯工艺参数为：射砂压力0.3MPa，吹胺压力0.2Mpa，洗涤压力0.2Mpa，吹胺时间3.0秒，洗涤时间5.0秒。
分别测定抗弯试块的5秒初始抗弯强度、24小时抗弯强度、24小时高湿强度(湿度≥95％)。
表1实施例及对比例冷芯盒粘结剂加入量所制抗弯试块的抗弯强度测试
Figure PCTCN2016112931-appb-000001
通过分别测定抗弯试块的5秒初始抗弯强度、24小时抗弯强度、24小时高湿强度(湿度≥95％)发现本发明的冷芯盒粘结剂能够显著提高树脂砂的抗弯(压)强度、高湿抗弯强度(抗湿性)。如表1所示，对本发明实施例一到六的冷芯盒粘结剂制备树脂砂抗弯试块进行测试，结果发现将本发明的冷芯盒粘结剂按0.87％的加入量实施例一至实施例六制备的抗弯试块的5秒初始抗弯强度为2.38MPa～2.85MPa，24小时抗弯强度3.98～4.42MPa，24小时高湿抗弯强度(≥95％)为3.48MPa～3.91MPa；而对比例的冷芯盒粘结剂按0.87％的加入量制备的抗弯试块的5秒初始抗弯强度为1.35MPa～2.07MPa，24小时抗弯强度2.29MPa～3.39MPa，24小时高湿抗弯强度(≥95％)为1.93MPa～2.89MPa。说明本发明的冷芯盒粘结剂相比对比例在相同加入量的情况下可以显著提高其抗弯强度，例如0.87％实施例一的冷芯盒粘结剂的加入量的抗弯试块的24小时抗弯强度为4.26±0.05MPa，对比例一的24小时抗弯强度为3.20±0.06MPa， 说明其24小时抗弯强度，即常温抗弯(压)强度提高了约30％；实施例一24小时高湿抗弯强度(≥95％)为3.60±0.05MPa，对比例一24小时高湿抗弯强度(≥95％)为2.75±0.06MPa，说明其24小时高湿抗弯强度(≥95％)，即抗湿的抗弯(压)强度提高了约25％；而实施例一与对比例一仅仅是高邻位苄基醚酚醛树脂的羟甲基含量不同(实施例一为32.99％，对比例一为25.38％)，说明高羟基含量的邻位苄基醚酚醛树脂可以大大提高树脂砂的常温抗弯(压)强度。
进一步测定按0.66％、0.75％、0.87％冷芯盒粘结剂的加入量的抗弯试块的抗弯(压)强度，见表1。研究发现本发明的冷芯盒粘结剂仅按0.55％的加入量就可以满足铸造生产需要，实施例一至实施例六的24小时抗弯强度可以达到2.79MPa～3.13MPa；0.66％冷芯盒粘结剂的加入量的抗弯试块的24小时抗弯强度(常温抗弯强度)为3.01MPa～3.57MPa，与对比例0.87％冷芯盒粘结剂的加入量的24小时抗弯强度2.29MPa～3.39MPa相接近，例如，0.66％实施例一的冷芯盒粘结剂的加入量的抗弯试块的24小时抗弯强度为3.28±0.06MPa，0.87％对比例一的冷芯盒粘结剂的加入量的抗弯试块的24小时抗弯强度为3.20±0.05MPa(见表1.2)，说明要达到相同的树脂砂抗弯强度，本发明的冷芯盒粘结剂的加入量与对比例相比可以降低22％左右；同时实施例五与对比例五的冷芯盒粘结剂相比，除组分I中的高邻位苄基醚酚醛树脂的羟甲基含量分别为27.62％和25.98％，其他组分均相同，其0.87％的加入量的常温抗弯(压)强度(24小时抗弯强度)分别为4.08±0.05MPa和3.39±0.05MPa，其常温抗压强度也提高了约20％。因而使用本发明的冷芯盒粘结剂进行有色金属铸造时，使用量大大减少，使树脂砂型芯在浇注温度下的流动性增加，极大改善了树脂砂型芯的溃散性问题，同时减少了金属模具上的残留焦油量，提高了生产效率。
采用本发明的方法，在进行砂型芯浇注时减少了金属模具上的焦油残余量。浇注复杂形状的铸件，可连续浇注80模以上，甚至90模以上，较佳的状态是90模以上。而传统的冷芯盒粘结剂连续浇注10-30模后需要清理金属模具上的焦油。
用本实施例的树脂，在铝缸盖铸造金属模上工业化生产，车间混砂系统每次混砂容量200公斤，树脂加入量0.65％，其中组分I与组分II的比例为55∶45，组分I加入量0.715公斤，组分II加入量0.585公斤。
Figure PCTCN2016112931-appb-000002
用对比例的树脂，在铝缸盖铸造金属模上工业化生产，车间混砂系统每次混砂容量200公斤，树脂加入量0.90％，其中组分I与组分II的比例为55∶45，组分I加入量0.99公斤，组分II加入量0.81公斤。
Figure PCTCN2016112931-appb-000003
树脂砂的溃散性测试方法：
取室温放置24小时的砂样试块称重(160±1克)，用锡箔纸包裹密封好，放入恒温450度的马弗炉中焙烧15分钟，取出冷却至室温后放入70目振动筛中震动2分钟，称量剩余的试样重量。
将焙烧前试样的重量减去焙烧后试样重量后除焙烧前重量，溃散性以百分比来表示。
  溃散性％
实施例1 95％
实施例2 90％
实施例3 92％
实施例4 96％
实施例5 88％
实施例6 92％
对比例1 57％
对比例2 52％
对比例3 60％
对比例4 56％
对比例5 66％
因此，本发明通采用复合催化剂技术制备的高羟甲基的高邻位苄基醚酚醛树脂的羟甲基含量均大于27％，而羟甲基含量为32％～50％的高邻位苄基醚酚醛树脂使本发明的冷芯盒粘结剂效果更优，使冷芯盒粘结剂的固化反应效率提高，大幅度提高了树脂的常温性能，使树脂砂的常温强度提高约30％，抗湿抗弯强度提高了约25％，冷芯盒粘结剂在保证树脂砂型芯强度的条件下添加量降低至0.55-0.75％，与现有技术0.85-1.2％的树脂添加量相比，树脂使用量大大降低，使树脂砂型芯在浇注温度下的流动性增加，极大改善了树脂砂型芯的溃散性问题，同时减少了金属模具上的焦油残留量，提高了生产效率。
以上所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明所述原理的前提下，还可以作出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (12)

  1. 一种冷芯盒粘结剂，包括组分I，其特征在于，所述组分I由以下重量份的原料组成：
    苄基醚酚醛树脂        40～80份
    高沸点酯和/或烃溶剂   1～45份
    增粘助剂              0～10份；
    其中，所述苄基醚酚醛树脂的羟甲基含量为32％～50％。
  2. 根据权利要求1所述的冷芯盒粘结剂，其特征在于，还包括组分II，所述组分II由以下重量份的原料组成：
    聚异氰酸酯           40～90份
    高沸点酯和/或烃溶剂  5～45份
    增粘助剂             0～10份。
  3. 根据权利要求1或2所述的冷芯盒粘结剂，其特征在于，所述苄基醚酚醛树脂中官能团的邻/对比大于1。
  4. 根据权利要求3所述的冷芯盒粘结剂，其特征在于，所述苄基醚酚醛树脂是重均分子量在500～2000高邻位苄基醚酚醛树脂。
  5. 根据权利要求1或2所述的冷芯盒粘结剂，其特征在于，所述组分I和组分II中的高沸点酯和/或烃溶剂各自独立地选自为邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、邻苯二甲酸二异丁酯、邻苯二甲酸二异辛酯、己二酸二辛脂、丁二酸二甲酯、戊二酸二甲酯、己二酸二甲酯、甲醇、乙醇、丁醇、异丙醇、馏程150～290℃的液态石油芳烃分馏物、煤油中的一种或几种；其中，所述馏程150～290℃的液态石油芳烃分馏物为solvesso 100、solvesso 150或solvesso 200的一种或几种。
  6. 根据权利要求1或2所述的冷芯盒粘结剂，其特征在于，所述组分I和组分II中的增粘助剂各自独立地选自硅烷偶联剂，所述硅烷偶联剂为A-187硅烷、A-171硅烷、A-172硅烷、A-174硅烷、A-151硅烷中的一种或多种。
  7. 根据权利要求4所述的冷芯盒粘结剂，其特征在于，所述高邻位苄基醚酚醛树脂通过以下方法制得：
    将酚类物质、醛类物质、催化剂混合加入反应釜中，反应制得所述酚醛树脂；
    所述酚类物质和醛类物质的摩尔比为1∶1.0～1∶3.0，优选为1∶1.2-1∶2.5；
    催化剂为包含有金属盐的催化剂体系。
  8. 根据权利要求7所述的冷芯盒粘结剂，其特征在于，所述酚类物质为混合酚。
  9. 根据权利要求7所述的冷芯盒粘结剂，其特征在于，所述包含有金属盐的催化剂体系为包含锌盐和铅盐。
  10. 根据权利要求2所述的冷芯盒粘结剂，其特征在于，所述组分II中的聚异氰酸酯选自二苯基甲烷-4，4’-二异氰酸酯、粗二苯基甲烷-4，4’-二异氰酸酯或多亚甲基多苯基多异氰酸脂、1，6-己二异氰酸酯、异佛尔酮二异氰酸酯中的一种或几种。
  11. 一种铸造成型体，其特征在于，由铸造骨料和有效量的权利要求2-9任一所述的冷芯盒粘结剂混合后在催化剂作用下制备得到；其中，将所述冷芯盒粘结剂的所述组分I和组分II依次加入，或者同时加入与所述铸造骨料进行混合。
  12. 根据权利要求11所述的铸造成型体，其特征在于，所述冷芯盒粘结剂按0.55％～0.75％的重量比与所述铸造骨料混合。
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