CN104162625A - Adhesive for casting and preparation method thereof - Google Patents
Adhesive for casting and preparation method thereof Download PDFInfo
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- CN104162625A CN104162625A CN201410401065.7A CN201410401065A CN104162625A CN 104162625 A CN104162625 A CN 104162625A CN 201410401065 A CN201410401065 A CN 201410401065A CN 104162625 A CN104162625 A CN 104162625A
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Abstract
The invention provides an adhesive for casting. The adhesive is prepared from benzyl ether phenolic resin, polyisocyanate, epoxy resin, acrylic ester, an organic compound and graphene through reaction, wherein the organic compound comprises one or several of a diacid diol ester type compound, an alcohol type compound and a hydrocarbon compound. The invention provides a preparation method for the adhesive for casting. The preparation method comprises the steps of performing reaction on benzyl ether phenolic resin, polyisocyanate, epoxy resin, acrylic ester, an organic compound and graphene to obtain the adhesive for casting; and the organic compound comprises one or several of the diacid diol ester type compound, the alcohol type compound and the hydrocarbon compound. A casting mold or a casting core prepared by the adhesive for casting, which is provided by the invention, is relatively long in high-temperature heat resistance time and relatively high in high-temperature heat resistance strength.
Description
Technical field
The present invention relates to adhesive techniques field, relate in particular to a kind of binder for casting and preparation method thereof.
Background technology
In foundary industry, conventionally adopt cold-box process to prepare core, cold-box process refer to gas or aerosol catalyst at room temperature catalytic resin sand to reach quick-setting process.Cold-box process is pressed the difference of binding agent in gas, aerosol catalyst and resin sand, can be divided into amine method, SO
2-epoxy resin method, CO
2resin method and methyl formate method.Wherein, SO
2the core sand up time that-epoxy resin method prepares is longer, and has solved the production problems such as core box fouling and sticking to mould, is applicable to producing in enormous quantities.
Application number is that 201010176020.6 Chinese patent discloses a kind of binding agent for casting core, the 10g benzylic ether phenolic resins having melted is dropped in reactor, add thermal agitation, dehydration (vacuum is 15mm mercury column) under vacuum, reaches 120 DEG C without till bubble to temperature.Be cooled to 60 DEG C, add the PIC of 7.5g; Reactor condenser is adjusted into reflux state, and under agitation logical steam heats up, and makes temperature rise to 70 DEG C in 30 minutes, and at 70 DEG C～90 DEG C insulation reaction 180 minutes; After insulation finishes, material is cooled to 60 DEG C, adds the epoxy resin of 750g, in 60 minutes, make temperature in the kettle rise to 110 DEG C, and 110 DEG C～150 DEG C insulation reaction 180 minutes; Cool to 60 DEG C, the hydrocarbon diluent of the high boiling ester of the acrylate of 200g, 22.5g, 10g is added in mixing kettle, start stirring, mix 2 hours, make mixing of materials even, obtain the binding agent for casting core.
Although the core strength that this core binder for casting that prior art provides prepares is higher, high-temperature heat-resistance time and the high temperature compression strength of the core that this binding agent prepares are poor, have limited the application of this binding agent.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of binder for casting and preparation method thereof, adopt mold or the casting core that binder for casting provided by the invention prepares to there is longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.
The invention provides a kind of binder for casting, prepared through reaction by benzylic ether phenolic resins, PIC, epoxy resin and acrylate, organic compound and Graphene; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.
Preferably, the parts by weight of described benzylic ether phenolic resins are 1 part～30 parts, and the parts by weight of described PIC are 0.1 part～10 parts; The parts by weight of described epoxy resin are 40 parts～70 parts; The parts by weight of described acrylate are 20 parts～30 parts; The parts by weight of described organic compound are 1 part～30 parts; The parts by weight of described Graphene are 0.1 part～10 parts.
Preferably, the parts by weight of described Graphene are 0.5 part～8 parts.
Preferably, the mass ratio of described benzylic ether phenolic resins and epoxy resin is (1～50): 100.
Preferably, the mass ratio of described PIC and benzylic ether phenolic resins is (1～30): 100.
Preferably, the weight average molecular weight of described benzylic ether phenolic resins is 500～2000.
Preferably, described PIC comprises one or more in aliphatic polymeric isocyanate and aromatic poly-isocyanate.
Preferably, described aliphatic polymeric isocyanate comprises one or both in vulcabond and hexamethylene diisocyanate.
Preferably, described aromatic poly-isocyanate comprises diphenyl methane-4, one or both in 4-vulcabond and polymethylene polyphenyl polyisocyanates.
Preferably, described epoxy resin comprises one or more in novolac epoxy resin, amino polyfunctional epoxy resin and cycloaliphatic epoxy resin.
Preferably, described diacid diol-lipid compound comprises one or more in dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate, diisooctyl phthalate, adipic acid dibutyl ester, dimethyl succinate, dimethyl glutarate and dimethyl adipate.
Preferably, described alcohol compound comprises one or more in methyl alcohol, ethanol, butanols and isopropyl alcohol.
Preferably, described hydrocarbon compound comprises one or both in aromatic hydrocarbon and kerosene.
The preparation method who the invention provides a kind of binder for casting, comprising:
Benzylic ether phenolic resins, PIC, epoxy resin, acrylate, organic compound and Graphene are reacted, obtain binder for casting; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.
Preferably, the raw materials of described Graphene is living beings carbon source.
Preferably, the preparation method of described Graphene comprises the following steps:
1), under the effect of catalyst, living beings carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyst comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), under the condition of protective gas, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 DEG C～40 DEG C, described the second temperature is 300 DEG C～400 DEG C;
3), under the condition of protective gas, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 DEG C～900 DEG C;
4), under the condition of protective gas, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 DEG C～1300 DEG C;
5), under the condition of protective gas, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain Graphene, described the 5th temperature is 900 DEG C～1000 DEG C.
Preferably, the preparation method of described binder for casting comprises the following steps:
Benzylic ether phenolic resins and PIC are carried out to the first reaction, obtain the first product;
Described the first product and epoxy resin are carried out to the second reaction, obtain the second product;
Described the second product, acrylate, organic compound and Graphene are carried out to the 3rd reaction, obtain binder for casting.
Preferably, the temperature of described the first reaction is 70 DEG C～90 DEG C.
Preferably, the temperature of described the second reaction is 110 DEG C～150 DEG C.
Preferably, 60 DEG C of the described the 3rd temperature < reacting.
The invention provides a kind of binder for casting, prepared through reaction by benzylic ether phenolic resins, PIC, epoxy resin, acrylate, organic compound and Graphene; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.The mold that binder for casting provided by the invention prepares or casting core have longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.Experimental result shows, adopting the casting core that binder for casting provided by the invention prepares is 107 seconds～128 seconds at the heat-resistant time of 1100 DEG C, is 0.28MPa～0.5MPa the compression strength of 1100 DEG C.
The preparation method who the invention provides a kind of binder for casting, comprising: benzylic ether phenolic resins, PIC, epoxy resin, acrylate, organic compound and Graphene are reacted, obtain binder for casting; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.The mold that the binder for casting that method provided by the invention prepares prepares or casting core have longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of binder for casting, prepared through reaction by benzylic ether phenolic resins, PIC, epoxy resin and acrylate, organic compound and Graphene; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.
The mold that binder for casting provided by the invention prepares or casting core have longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.
In the present invention, the parts by weight of described benzylic ether phenolic resins are preferably 1 part～30 parts, more preferably 5 parts～25 parts, most preferably are 10 parts～20 parts.In the present invention, described benzylic ether phenolic resins is preferably high ortho position benzylic ether phenolic resins.In the present invention, the weight average molecular weight of described benzylic ether phenolic resins is preferably 500～2000, and more preferably 1000～1500.The present invention does not have special restriction to the source of described benzylic ether phenolic resins, can be bought and be obtained by market, can prepare according to preparation method well known to those skilled in the art yet.The preparation method of the disclosed high ortho position of the Chinese patent benzylic ether phenolic resins that in the present invention, described high ortho position benzylic ether phenolic resins is preferably 200710188114.3 according to application number prepares.
In the present invention, taking the parts by weight of described benzylic ether phenolic resins as benchmark, the parts by weight of described PIC are preferably 0.1 part～10 parts, and more preferably 0.5 part～8 parts, most preferably be 1 part～6 parts, be the most preferably 2 parts～4 parts.In the present invention, described PIC is preferably one or more in aliphatic polymeric isocyanate and aromatic poly-isocyanate, more preferably one or more in aromatic poly-isocyanate.In the present invention, described aliphatic polymeric isocyanate is preferably one or both in vulcabond and hexamethylene diisocyanate.In the present invention, described aromatic poly-isocyanate is preferably diphenyl methane-4, one or both in 4-vulcabond and polymethylene polyphenyl polyisocyanates.The present invention does not have special restriction to the source of described PIC, can be bought and be obtained by market.
In the present invention, taking the parts by weight of described benzylic ether phenolic resins as benchmark, the parts by weight of described epoxy resin are preferably 40 parts～70 parts, more preferably 45 parts～60 parts, most preferably are 50 parts～55 parts.In the present invention, described epoxy resin preferably includes one or more in novolac epoxy resin, amino polyfunctional epoxy resin and cycloaliphatic epoxy resin, more preferably novolac epoxy resin.In the present invention, described novolac epoxy resin preferably includes one or both in bisphenol A epoxide resin and bisphenol F epoxy resin.The present invention does not have special restriction to the source of described epoxy resin, can be bought and be obtained by market.
In the present invention, the mass ratio of described benzylic ether phenolic resins and epoxy resin is preferably (1～50): 100, more preferably (5～35): 100, most preferably be (10～30): 100, be the most preferably (15～25): 100.In the present invention, the mass ratio of described PIC and benzylic ether phenolic resins is preferably (1～30): 100, and more preferably (5～25): 100, most preferably be (10～20): 100.
In the present invention, taking the parts by weight of described benzylic ether phenolic resins as benchmark, the parts by weight of described acrylate are preferably 20 parts～30 parts, more preferably 24 parts～28 parts, most preferably are 25 parts.In the present invention, described acrylate preferably includes one or more in tripropylene glycol diacrylate, hexanediyl ester and trimethylolpropane triacrylate, more preferably tripropylene glycol diacrylate, hexanediyl ester or trimethylolpropane triacrylate.The present invention does not have special restriction to the source of described acrylate, can be bought and be obtained by market.
In the present invention, taking the parts by weight of described benzylic ether phenolic resins as benchmark, the parts by weight of described organic compound are preferably 1 part～30 parts, more preferably 5 parts～25 parts, most preferably are 10 parts～20 parts.In the present invention, described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound, is preferably one or more in diacid diol-lipid compound and alcohol compound.In the present invention, described diacid diol-lipid compound is preferably dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate, diisooctyl phthalate, adipic acid dibutyl ester, dimethyl succinate, one or more in dimethyl glutarate and dimethyl adipate, more preferably dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate, adipic acid dibutyl ester, one or more in dimethyl succinate and dimethyl glutarate, most preferably be dibutyl phthalate, dioctyl phthalate, one or more in adipic acid dibutyl ester and dimethyl succinate.
In the present invention, described alcohol compound preferably includes one or more in methyl alcohol, ethanol, butanols and isopropyl alcohol, and more preferably one or more in methyl alcohol, ethanol and butanols, most preferably are methyl alcohol or ethanol.
In the present invention, described hydrocarbon compound is preferably one or more in aromatic hydrocarbon and kerosene, more preferably aromatic hydrocarbon.The present invention does not have special restriction to the source of described organic compound, can be bought and be obtained by market, can prepare according to method well known to those skilled in the art yet.
In the present invention, taking the parts by weight of described benzylic ether phenolic resins as benchmark, the parts by weight of described Graphene are preferably 0.1 part～10 parts, and more preferably 0.5 part～8 parts, most preferably be 1 part～6 parts, be the most preferably 2 parts～4 parts.In the present invention, the raw materials of described Graphene is preferably living beings carbon source.In the present invention, the preparation method of described Graphene preferably includes following steps:
1), under the effect of catalyst, living beings carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyst comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), under the condition of protective gas, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 DEG C～40 DEG C, described the second temperature is 300 DEG C～400 DEG C;
3), under the condition of protective gas, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 DEG C～900 DEG C;
4), under the condition of protective gas, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 DEG C～1300 DEG C;
5), under the condition of protective gas, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain Graphene, described the 5th temperature is 900 DEG C～1000 DEG C.
The present invention preferably, under the effect of catalyst, carries out catalytic treatment by living beings carbon source, obtains the first intermediate product, and described catalyst comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese.In the present invention, described living beings carbon source is preferably one or both in cellulose and lignin, and more preferably cellulose, most preferably is porous cellulose.In the present invention, the preparation method of described porous cellulose preferably includes following steps:
A), biomass resource is hydrolyzed in acid, obtain lignocellulosic, described biomass resource comprises one or more in plant and agriculture and forestry organic waste material;
B), described lignocellulosic is processed, obtain porous cellulose, described processing comprises that acid treatment, salt processes or organic solvent processing.
The present invention is preferably hydrolyzed biomass resource in acid, obtains lignocellulosic, and described biomass resource comprises one or more in plant and agriculture and forestry organic waste material.In the present invention, more preferably agriculture and forestry organic waste material of described biomass resource, most preferably is one or more in cornstalk, corncob, kaoliang stalk, megasse, bagasse, furfural dregs, xylose residue, wood chip, cotton stalk and reed, is the most preferably corncob.
In the present invention, the acid of described hydrolysis is preferably one or more in sulfuric acid, nitric acid, hydrochloric acid, formic acid, sulfurous acid, phosphoric acid and acetic acid.In the present invention, the sour consumption of described hydrolysis is preferably the 3wt%～20wt% of biomass resource.In the present invention, the temperature of described hydrolysis is preferably 90 DEG C～180 DEG C.In the present invention, the time of described hydrolysis is preferably 10min～10h.
Obtain after lignocellulosic, the present invention preferably processes described wood fibre, obtains porous cellulose, and described processing comprises acid treatment, salt processing or organic solvent processing.In the present invention, process the more preferably salt processing of method of described lignocellulosic, most preferably be acid sulfite process and process or alkali sulfite process processing.In the present invention, the pH of described acid sulfite process processing is preferably 1～7.In the present invention, when described acid sulfite process is processed, the consumption of acid is preferably the 4wt%～30wt% of lignocellulosic.In the present invention, when described acid sulfite process is processed, preferably to make liquid-solid ratio be (2～20) to the concentration expressed in percentage by weight of acid: 1.In the present invention, the temperature of described acid sulfite process processing is preferably 70 DEG C～180 DEG C.In the present invention, the time of described acid sulfite process processing be preferably 1 hour～6 hours.
In the present invention, the pH of described alkali sulfite process processing is preferably 7～14.In the present invention, when described alkali sulfite process is processed, the consumption of alkali is preferably the 4wt%～30wt% of lignocellulosic.In the present invention, when described alkali sulfite process is processed, preferably to make liquid-solid ratio be (2～20) to the concentration expressed in percentage by weight of alkali: 1.In the present invention, the temperature of described alkali sulfite process processing is preferably 70 DEG C～180 DEG C.In the present invention, the time of described alkali sulfite process processing be preferably 1 hour～6 hours.
In the present invention, the catalyst of preparing described Graphene preferably includes the chlorate of cyanide, iron content hydrochlorate, the cobalt of chlorate, the iron of iron, containing the chlorate of cobaltatess, nickel with containing one or more in nickelate; More preferably comprise that iron chloride, frerrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, the potassium ferricyanide, potassium ferrocyanide, three oxalic acid close one or more in potassium ferrite, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickelous sulfate and nickel acetate.
In the present invention, while preparing described Graphene, the mass ratio of catalyst and living beings carbon source is preferably (0.01～2): 1.In the present invention, the temperature of described catalytic treatment is preferably 20 DEG C～180 DEG C.In the present invention, the time of described catalytic treatment be preferably 2 hours～10 hours.
Obtain after the first intermediate product, the present invention preferably, under the condition of protective gas, is incubated described the first intermediate product from the first temperature is warming up to the second temperature, obtains the second intermediate product; Described the first temperature is 20 DEG C～40 DEG C, and described the second temperature is 300 DEG C～400 DEG C.In the present invention, the heating rate that described the first intermediate product is warming up to the second temperature from the first temperature is preferably 5 DEG C/min～20 DEG C/min.In the present invention, the temperature retention time of described the first intermediate product from the first temperature is warming up to the second temperature be preferably 4 hours～8 hours.In the present invention, described protective gas is preferably one or more in nitrogen and inert gas, more preferably nitrogen.
Obtain after the second intermediate product, the present invention preferably, under the condition of protective gas, is incubated described the second intermediate product from the second temperature is warming up to the 3rd temperature, obtains the 3rd intermediate product; Described the 3rd temperature is 800 DEG C～900 DEG C.In the present invention, the heating rate that described the second intermediate product is warming up to the 3rd temperature from the second temperature is preferably 20 DEG C/min～50 DEG C/min.In the present invention, the temperature retention time of described the second intermediate product from the second temperature is warming up to the 3rd temperature be preferably 3.5 hours～7 hours.In the present invention, the kind of described protective gas is consistent with the kind of protective gas described in technique scheme, does not repeat them here.
Obtain after the 3rd intermediate product, the present invention preferably, under the condition of protective gas, is incubated described the 3rd intermediate product from the 3rd temperature is warming up to the 4th temperature, obtains the 4th intermediate product; Described the 4th temperature is 1100 DEG C～1300 DEG C.In the present invention, the heating rate that described the 3rd intermediate product is warming up to the 4th temperature from the 3rd temperature is preferably 50 DEG C/min～60 DEG C/min.In the present invention, the temperature retention time of described the 3rd intermediate product from the 3rd temperature is warming up to the 4th temperature be preferably 6 hours～8 hours.In the present invention, the kind of described protective gas is consistent with the kind of protective gas described in technique scheme, does not repeat them here.
Obtain after the 4th intermediate product, the present invention preferably, under the condition of protective gas, is incubated described the 4th intermediate product from the 4th greenhouse cooling to the five temperature, obtains Graphene; Described the 5th temperature is 900 DEG C～1000 DEG C.In the present invention, described the 4th intermediate product is preferably 30 DEG C/min～50 DEG C/min from the rate of temperature fall of the 4th greenhouse cooling to the five temperature.In the present invention, the temperature retention time of described the 4th intermediate product from the 4th greenhouse cooling to the five temperature be preferably 2 hours～4 hours.In the present invention, the kind of described protective gas is consistent with the kind of protective gas described in technique scheme, does not repeat them here.
The preparation method who the invention provides a kind of binder for casting, comprising:
Benzylic ether phenolic resins, PIC, epoxy resin, acrylate, organic compound and Graphene are reacted, obtain binder for casting; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.
The mold that the binding agent that method provided by the invention prepares prepares or casting core have longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.
The present invention reacts benzylic ether phenolic resins, PIC, epoxy resin, acrylate, organic compound and Graphene, obtains binder for casting.In the present invention, kind, source and the consumption of described benzylic ether phenolic resins, PIC, epoxy resin, acrylate, organic compound and Graphene is consistent with kind, source and the consumption of benzylic ether phenolic resins, PIC, epoxy resin, acrylate, organic compound and Graphene described in technique scheme, does not repeat them here.
The present invention preferably carries out the first reaction by benzylic ether phenolic resins and PIC, obtains the first product;
Described the first product and epoxy resin are carried out to the second reaction, obtain the second product;
Described the second product, acrylate, organic compound and Graphene are carried out to the 3rd reaction, obtain binder for casting; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.
The present invention preferably carries out the first reaction by benzylic ether phenolic resins and PIC, obtains the first product; More preferably PIC is joined in benzylic ether phenolic resins and carry out the first reaction, obtain the first product.In the present invention, the temperature of described the first reaction is preferably 70 DEG C～90 DEG C, more preferably 75 DEG C～85 DEG C, most preferably is 80 DEG C.In the present invention, described first reaction time be preferably 150 minutes～200 minutes, more preferably 180 minutes.In the present invention, the parts by weight of described benzylic ether phenolic resins and PIC are consistent with the parts by weight of benzylic ether phenolic resins and PIC described in technique scheme, do not repeat them here.
Before carrying out described the first reaction, the present invention preferably carries out processed to described benzylic ether phenolic resins.The present invention preferably carries out described processed under the condition stirring.The present invention preferably carries out described processed under the condition of vacuum.In the present invention, the temperature of described processed is preferably 100 DEG C～140 DEG C, more preferably 110 DEG C～130 DEG C, most preferably is 120 DEG C.
Obtain after the first product, the present invention preferably carries out the second reaction by described the first product and epoxy resin, obtains the second product; More preferably epoxy resin is joined in described the first product and carry out the second reaction, obtain the second product.In the present invention, the temperature of described the second reaction is preferably 110 DEG C～150 DEG C, more preferably 120 DEG C～140 DEG C, most preferably is 130 DEG C.In the present invention, described second reaction time be preferably 150 minutes～200 minutes, more preferably 180 minutes.In the present invention, the parts by weight of described epoxy resin are consistent with the parts by weight of epoxy resin described in technique scheme, do not repeat them here.
Obtain after the second product, the present invention preferably carries out the 3rd reaction by described the second product, acrylate, organic compound and Graphene, obtains binder for casting; More preferably acrylate, organic compound and Graphene are joined in the second product and carry out the 3rd reaction, obtain binder for casting.In the present invention, 60 DEG C of the preferred < of temperature of described the 3rd reaction,, most preferably are 20 DEG C～40 DEG C by more preferably 10 DEG C～50 DEG C.In the present invention, described the 3rd reaction time be preferably 100 minutes～150 minutes, more preferably 120 minutes.In the present invention, the parts by weight of described acrylate, organic compound and Graphene are consistent with the parts by weight of acrylate, organic compound and Graphene described in technique scheme, do not repeat them here.
The method that adopts binder for casting provided by the invention to prepare mold or casting core is preferably:
Molding sand, organic peroxide and binder for casting provided by the invention are mixed, obtain mixed material;
In described mixed material, pass into sulfur dioxide, prepare mold or casting core.
The present invention preferably mixes molding sand, organic peroxide and binder for casting provided by the invention, obtains mixed material.The present invention does not have special restriction to the kind of described molding sand and source, adopts molding sand well known to those skilled in the art, can be bought and be obtained by market.In an embodiment of the present invention, described molding sand can be great Lin normal sand.In the present invention, the mass ratio of described molding sand, organic peroxide and binder for casting provided by the invention is preferably (1500～2500): (3～5): (20～30), more preferably (1800～2200): (4～4.7): (24～28), most preferably are 2000:4.5:25.5.In the present invention, described organic peroxide is preferably one or more in cumyl hydroperoxide, methyl ethyl ketone peroxide and t-butyl hydroperoxide, more preferably cumyl hydroperoxide, methyl ethyl ketone peroxide or t-butyl hydroperoxide.
Obtain after mixed material, the present invention preferably passes into sulfur dioxide in described mixed material, prepares mold or casting core.In the present invention, the pressure that passes into of described sulfur dioxide is preferably 0.1MPa～0.3MPa, more preferably 0.2MPa.In the present invention, the time that passes into of described sulfur dioxide is preferably 10 seconds～and 20 seconds, more preferably 15 seconds.
The present invention does not have special restriction to the equipment of preparing mold or casting core, adopts core making machine well known to those skilled in the art.In an embodiment of the present invention, described core making machine can be MLA1 core making machine.In the present invention, the shooting pressure of described core making machine is preferably 0.2MPa～0.6MPa, more preferably 0.4MPa.In the present invention, the washing pressure of described core making machine is preferably 0.1MPa～0.3MPa, more preferably 0.2MPa.
Adopt binder for casting provided by the invention to prepare casting core, concrete grammar is: by great Lin standard molding sand, cumyl hydroperoxide and binder for casting provided by the invention, the ratio that is 2000:4.5:25.5 according to mass ratio is mixed, and obtains mixed material; In MLA1 core making machine, in described mixed material, pass into the sulfur dioxide of 15 seconds, prepare casting core, the pressure that passes into of described sulfur dioxide is 0.2MPa, and the shooting pressure of described core making machine is 0.4MPa, and the washing pressure of described core making machine is 0.2MPa.It is 12mm, the high cylindrical sample for 20mm that described casting core is processed into diameter, by the sample obtaining in QX-GWY-1 type multifunctional high-temperature tester, measure high-temperature heat-resistance time and the high temperature compression strength of sample, test result is, the casting core that binder for casting provided by the invention prepares is 107 seconds～128 seconds at the heat-resistant time of 1100 DEG C, is 0.28MPa～0.5MPa in the compression strength of 1100 DEG C of temperature.
The invention provides a kind of binder for casting, prepared through reaction by benzylic ether phenolic resins, PIC, epoxy resin, acrylate, organic compound and Graphene; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.The mold that binder for casting provided by the invention prepares or casting core have longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.
The preparation method who the invention provides a kind of binder for casting, comprising: benzylic ether phenolic resins, PIC, epoxy resin, acrylate, organic compound and Graphene are reacted, obtain binder for casting; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.The mold that the binding agent that method provided by the invention prepares prepares or casting core have longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.
Benzylic ether phenolic resins used in following examples of the present invention, is the disclosed method of Chinese patent that is 200710188114.3 according to application number, the high ortho position benzylic ether phenolic resins preparing, and other raw materials are commercial goods.
Embodiment 1
At 90 DEG C, corncob is carried out in sulfuric acid to the hydrolysis of 10min, obtain lignocellulosic, the quality of described sulfuric acid is 3% of described corncob quality;
At 70 DEG C, described lignocellulosic is carried out to the acid sulfite process processing of 1 hour, obtain porous cellulose, pH value in described acid sulfite process processing procedure is 1, acid is sulfuric acid, sulphite is magnesium sulfite, and the quality of described sulfuric acid is 4% of described lignocellulosic quality, and liquid-solid ratio is 2:1.
The porous cellulose obtaining is carried out to hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is 5% of described porous cellulose quality, and the bleaching temperature of described hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
By described porous cellulose and manganese chloride, at 20 DEG C, stir and within 2 hours, carry out catalytic treatment, the mass ratio of described manganese chloride and porous cellulose is 0.01:1; Product after the catalytic treatment obtaining is dry at 70 DEG C, obtain first intermediate product of water content lower than 10wt%.
Described the first intermediate product is placed in to retort, gas intake using 200mL/min passes into nitrogen as protection gas in described carbide furnace, described the first intermediate product is warming up to 300 DEG C with the speed of 5 DEG C/min from 25 DEG C, is incubated 4 hours, obtain the second intermediate product; Described the second intermediate product is warming up to 800 DEG C with the speed of 20 DEG C/min from 300 DEG C, is incubated 3.5 hours, obtain the 3rd intermediate product; Described the 3rd intermediate product is warming up to 1100 DEG C with the speed of 50 DEG C/min from 800 DEG C, is incubated 6 hours, obtain the 4th intermediate product; Described the 4th intermediate product is cooled to 900 DEG C with the speed of 30 DEG C/min from 1100 DEG C, is incubated 2 hours; The 4th intermediate product after described cooling is cooled to 60 DEG C.
At 60 DEG C, in the sodium hydrate aqueous solution that is 3% in mass concentration by above-mentioned cooled the 4th intermediate product, wash 4 hours, obtain the first washed product; At 70 DEG C, in the aqueous hydrochloric acid solution that is 4% in mass concentration by described the first washed product, wash 4 hours, obtain the second washed product; Described the second washed product is washed with distilled water to neutral rear being dried, obtains Graphene.
Embodiment 2
At 180 DEG C, corncob is carried out in nitric acid to the hydrolysis of 10h, obtain lignocellulosic, the quality of described nitric acid is 20% of described corncob quality;
At 180 DEG C, described lignocellulosic is carried out to the acid sulfite process processing of 6 hours, obtain porous cellulose, pH value in described acid sulfite process processing procedure is 7, acid is sulfuric acid, sulphite is sodium sulfite, and the quality of described sulfuric acid is 30% of described lignocellulosic quality, and liquid-solid ratio is 20:1.
Described porous cellulose is carried out to hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is 5% of described porous cellulose quality, and the bleaching temperature of described hydrogen peroxide bleaching is 100 DEG C, and bleaching time is 5h.
By described porous cellulose and ferric nitrate, at 180 DEG C, stir and within 10 hours, carry out catalytic treatment, the mass ratio of described ferric nitrate and porous cellulose is 2:1; Product after the catalytic treatment obtaining is dry at 120 DEG C, obtain first intermediate product of water content lower than 5wt%.
Described the first intermediate product is placed in to retort, gas intake using 800mL/min passes into argon gas as protection gas in described carbide furnace, described the first intermediate product is warming up to 400 DEG C with the speed of 20 DEG C/min from 20 DEG C, is incubated 8 hours, obtain the second intermediate product; Described the second intermediate product is warming up to 900 DEG C with the speed of 50 DEG C/min from 400 DEG C, is incubated 7 hours, obtain the 3rd intermediate product; Described the 3rd intermediate product is warming up to 1300 DEG C with the speed of 60 DEG C/min from 900 DEG C, is incubated 8 hours, obtain the 4th intermediate product; Described the 4th intermediate product is cooled to 1000 DEG C with the speed of 50 DEG C/min from 1300 DEG C, is incubated 4 hours; The 4th intermediate product after described cooling is cooled to 20 DEG C.
At 120 DEG C, in the sodium hydrate aqueous solution that is 55% in mass concentration by above-mentioned cooled the 4th intermediate product, wash 24 hours, obtain the first washed product; At 150 DEG C, in the aqueous hydrochloric acid solution that is 10% in mass concentration by described the first washed product, wash 24 hours, obtain the second washed product; Described the second washed product is washed with distilled water to neutral rear being dried, obtains Graphene.
Embodiment 3
The disclosed method of Chinese patent that is 200810113596.0 according to application number is prepared Graphene, and detailed process is:
Silicon substrate is cleaned to post-drying by deionized water, ethanol, acetone successively, is that the zinc sulphide of 100 nanometers is as catalyst by gas phase deposition technology in surface of silicon deposition a layer thickness;
The described silicon substrate that deposits zinc sulphide is placed in to clean quartz ampoule middle part, quartz ampoule is put into electric furnace, make the middle part of quartz ampoule be positioned at the central area of electric furnace, then in quartz ampoule, pass into the hydrogen of 100sccm and the argon gas gaseous mixture of 100sccm after 60 minutes, start heating;
When the temperature of electric furnace central area is during up to 850 DEG C, in electric furnace, pass into ethanol as carbon source, reaction starts to carry out;
Reaction is carried out, after 20 minutes, stopping passing into ethanol, closes electric furnace simultaneously, continues to pass into gaseous mixture to the temperature of the hydrogen of 100sccm and the argon gas of 100sccm and is down to room temperature, obtains depositing the substrate of Graphene;
The hydrochloric acid solution that the described substrate that deposits Graphene is put into 0.1mol/L soaks 60 minutes, removes zinc sulphide, then cleans and dries by deionized water, obtains Graphene.
Embodiment 4
Under the condition stirring, the benzylic ether phenolic resins of 140 kilograms having melted is put in reactor, be heated to 120 DEG C, be to dewater under the condition of 10mm mercury column in vacuum, obtain bubble-free benzylic ether phenolic resins;
Described bubble-free benzylic ether phenolic resins is cooled to 60 DEG C, to the PM-200 poly methylene poly phenyl poly isocyanate that adds 10 kilograms in described bubble-free benzylic ether phenolic resins; Reactor condenser is adjusted into reflux state, and under agitation logical steam heats up, and makes temperature rise to 85 DEG C in 30 minutes, carries out first reaction of 180 minutes, obtains the first product;
Under the condition stirring, the DER331 epoxy resin of 540 kilograms is joined in described the first product, at 120 DEG C, carry out second reaction of 180 minutes, obtain the second product;
Described the second product is cooled to 30 DEG C, under the condition stirring, the Graphene that the embodiment 1 of the dibutyl phthalate of the trimethylolpropane triacrylate of 200 kilograms, 120 kg, the Solvesso100 aromatic hydrocarbon solvent of 30 kilograms and 10 kilograms is prepared adds in mixing kettle, carry out the 3rd reaction of 2 hours, obtain binder for casting.
According to the method described in technique scheme, the binder for casting preparation casting core that adopts the embodiment of the present invention 4 to prepare, described casting core is processed into sample, carry out high-temperature heat-resistance time and high temperature compression strength test, test result is as shown in table 1, high-temperature heat-resistance time and the high temperature compression strength test result of the sample that table 1 prepares for the embodiment of the present invention 4～embodiment 7 and comparative example 1.
Embodiment 5
Under the condition stirring, the benzylic ether phenolic resins of 88 kilograms having melted is put in reactor, be heated to 120 DEG C, be to dewater under the condition of 10mm mercury column in vacuum, obtain bubble-free benzylic ether phenolic resins;
Described bubble-free benzylic ether phenolic resins is cooled to 60 DEG C, to the PM-200 poly methylene poly phenyl poly isocyanate that adds 12 kilograms in described bubble-free benzylic ether phenolic resins; Reactor condenser is adjusted into reflux state, and under agitation logical steam heats up, and makes temperature rise to 88 DEG C in 30 minutes, carries out first reaction of 180 minutes, obtains the first product;
Under the condition stirring, the DER331 epoxy resin of 700 kilograms is joined in described the first product, at 130 DEG C, carry out second reaction of 180 minutes, obtain the second product;
Described the second product is cooled to 20 DEG C, under the condition stirring, the Graphene that the embodiment 2 of the trimethylolpropane triacrylate of 290 kilograms, the dibutyl phthalate of 200 kilograms, the Solvesso100 aromatic hydrocarbon solvent of 50 kilograms and 16 kilograms is prepared adds in mixing kettle, carry out the 3rd reaction of 2 hours, obtain binder for casting.
According to the method described in technique scheme, the binder for casting preparation casting core that adopts the embodiment of the present invention 5 to prepare, is processed into sample by described casting core, carries out high-temperature heat-resistance time and high temperature compression strength test, and test result is as shown in table 1.
Embodiment 6
Under the condition stirring, the benzylic ether phenolic resins of 180 kilograms having melted is put in reactor, be heated to 120 DEG C, be to dewater under the condition of 10mm mercury column in vacuum, obtain bubble-free benzylic ether phenolic resins;
Described bubble-free benzylic ether phenolic resins is cooled to 60 DEG C, in described bubble-free benzylic ether phenolic resins, adds 14 kilograms of PM-200 poly methylene poly phenyl poly isocyanates; Reactor condenser is adjusted into reflux state, and under agitation logical steam heats up, and makes temperature rise to 80 DEG C in 30 minutes, carries out first reaction of 180 minutes, obtains the first product;
Under the condition stirring, just the DER331 epoxy resin of 450 kilograms joins in described the first product, carries out reaction in 180 minutes second at 110 DEG C, obtains the second product;
Described the second product is cooled to 50 DEG C, under the condition stirring, the Graphene that the embodiment 3 of the trimethylolpropane triacrylate of 300 kilograms, the dibutyl phthalate of 90 kilograms, the Solvesso100 aromatic hydrocarbon solvent of 20 kilograms and 6 kilograms is prepared adds in mixing kettle, carry out the 3rd reaction of 2 hours, obtain binder for casting.
According to the method described in technique scheme, the binder for casting preparation casting core that adopts the embodiment of the present invention 6 to prepare, is processed into sample by described casting core, carries out high-temperature heat-resistance time and high temperature compression strength test, and test result is as shown in table 1.
Embodiment 7
Under the condition stirring, the benzylic ether phenolic resins of 25 kilograms having melted is put in reactor, be heated to 120 DEG C, be to dewater under the condition of 10mm mercury column in vacuum, obtain bubble-free benzylic ether phenolic resins;
Described bubble-free benzylic ether phenolic resins is cooled to 60 DEG C, to the PM-200 poly methylene poly phenyl poly isocyanate that adds 5 kilograms in described bubble-free benzylic ether phenolic resins; Reactor condenser is adjusted into reflux state, and under agitation logical steam heats up, and makes temperature rise to 90 DEG C in 30 minutes, carries out first reaction of 180 minutes, obtains the first product;
Under the condition stirring, the DER331 epoxy resin of 760 kilograms is joined in described the first product, carry out second reaction of 180 minutes minutes at 150 DEG C, obtain the second product.
Described the second product is cooled to 40 DEG C, under the condition stirring, the Graphene that the embodiment 3 of the trimethylolpropane triacrylate of 300 kilograms, the dibutyl phthalate of 216 kilograms, the Solvesso100 aromatic hydrocarbon solvent of 100 kilograms and 28 kilograms is prepared adds in mixing kettle, carry out the 3rd reaction of 2 hours, obtain binder for casting.
According to the method described in technique scheme, the binder for casting preparation casting core that adopts the embodiment of the present invention 7 to prepare, is processed into sample by described casting core, carries out high-temperature heat-resistance time and high temperature compression strength test, and test result is as shown in table 1.
Comparative example 1
Disclosed method described in the Chinese patent that is 201010176020.6 according to application number, for the preparation of the binding agent of casting core, detailed process is:
The 10g benzylic ether phenolic resins that melted is dropped in reactor, add thermal agitation, dehydration (vacuum is 15mm mercury column) under vacuum, reaches 120 DEG C without till bubble to temperature; Described benzylic ether phenolic resins is cooled to 60 DEG C, adds the PIC of 7.5g; Reactor condenser is adjusted into reflux state, and under agitation logical steam heats up, and makes temperature rise to 70 DEG C in 30 minutes, and at 80 DEG C insulation reaction 180 minutes; After insulation finishes, material is cooled to 60 DEG C, adds the epoxy resin of 750g, in 60 minutes, make temperature in the kettle rise to 110 DEG C, and 130 DEG C of insulation reaction 180 minutes; Cool to 60 DEG C, the methyl alcohol of the dibutyl phthalate of the acrylate of 200g, 22.5g, 10g is added in mixing kettle, start stirring, mix 2 hours, make mixing of materials even, obtain the binding agent for casting core.
According to the method described in technique scheme, the preparation of the binding agent for the casting core casting core that adopts comparative example 1 of the present invention to prepare, is processed into sample by described casting core, carries out high-temperature heat-resistance time and high temperature compression strength test, and test result is as shown in table 1.
The high-temperature heat-resistance time of the sample that table 1 embodiment of the present invention 4～embodiment 7 and comparative example 1 prepare and high temperature compression strength test result
| Embodiment | 1100 DEG C of heat-resistant times | 1100 DEG C of compression strength |
| 4 | 120 seconds | 0.42MPa |
| 5 | 128 seconds | 0.50MPa |
| 6 | 107 seconds | 0.28MPa |
| 7 | 106 seconds | 0.29MPa |
| Comparative example 1 | 92 seconds | 0.23MPa |
As seen from the above embodiment, the invention provides a kind of binder for casting, prepared through reaction by benzylic ether phenolic resins, PIC, epoxy resin, acrylate, organic compound and Graphene; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.The mold that binder for casting provided by the invention prepares or casting core have longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.
The preparation method who the invention provides a kind of binder for casting, comprising: benzylic ether phenolic resins, PIC, epoxy resin, acrylate, organic compound and Graphene are reacted, obtain binder for casting; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.The mold that the binding agent that method provided by the invention prepares prepares or casting core have longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.
Claims (20)
1. a binder for casting, is prepared through reaction by benzylic ether phenolic resins, PIC, epoxy resin and acrylate, organic compound and Graphene; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.
2. binder for casting according to claim 1, is characterized in that, the parts by weight of described benzylic ether phenolic resins are 1 part～30 parts, and the parts by weight of described PIC are 0.1 part～10 parts; The parts by weight of described epoxy resin are 40 parts～70 parts; The parts by weight of described acrylate are 20 parts～30 parts; The parts by weight of described organic compound are 1 part～30 parts; The parts by weight of described Graphene are 0.1 part～10 parts.
3. binder for casting according to claim 2, is characterized in that, the parts by weight of described Graphene are 0.5 part～8 parts.
4. binder for casting according to claim 2, is characterized in that, the mass ratio of described benzylic ether phenolic resins and epoxy resin is (1～50): 100.
5. binder for casting according to claim 2, is characterized in that, the mass ratio of described PIC and benzylic ether phenolic resins is (1～30): 100.
6. binder for casting according to claim 1, is characterized in that, the weight average molecular weight of described benzylic ether phenolic resins is 500～2000.
7. binder for casting according to claim 1, is characterized in that, described PIC comprises one or more in aliphatic polymeric isocyanate and aromatic poly-isocyanate.
8. binder for casting according to claim 7, is characterized in that, described aliphatic polymeric isocyanate comprises one or both in vulcabond and hexamethylene diisocyanate.
9. binder for casting according to claim 7, is characterized in that, described aromatic poly-isocyanate comprises diphenyl methane-4, one or both in 4-vulcabond and polymethylene polyphenyl polyisocyanates.
10. binder for casting according to claim 1, is characterized in that, described epoxy resin comprises one or more in novolac epoxy resin, amino polyfunctional epoxy resin and cycloaliphatic epoxy resin.
11. binder for casting according to claim 1, it is characterized in that, described diacid diol-lipid compound comprises one or more in dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate, diisooctyl phthalate, adipic acid dibutyl ester, dimethyl succinate, dimethyl glutarate and dimethyl adipate.
12. binder for casting according to claim 1, is characterized in that, described alcohol compound comprises one or more in methyl alcohol, ethanol, butanols and isopropyl alcohol.
13. binder for casting according to claim 1, is characterized in that, described hydrocarbon compound comprises one or both in aromatic hydrocarbon and kerosene.
The preparation method of 14. 1 kinds of binder for casting, comprising:
Benzylic ether phenolic resins, PIC, epoxy resin, acrylate, organic compound and Graphene are reacted, obtain binder for casting; Described organic compound comprises one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.
15. methods according to claim 14, is characterized in that, the raw materials of described Graphene is living beings carbon source.
16. methods according to claim 15, is characterized in that, the preparation method of described Graphene comprises the following steps:
1), under the effect of catalyst, living beings carbon source is carried out to catalytic treatment, obtain the first intermediate product, described catalyst comprises one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese;
2), under the condition of protective gas, described the first intermediate product is incubated from the first temperature is warming up to the second temperature, obtain the second intermediate product, described the first temperature is 20 DEG C～40 DEG C, described the second temperature is 300 DEG C～400 DEG C;
3), under the condition of protective gas, described the second intermediate product is incubated from the second temperature is warming up to the 3rd temperature, obtain the 3rd intermediate product; Described the 3rd temperature is 800 DEG C～900 DEG C;
4), under the condition of protective gas, described the 3rd intermediate product is incubated from the 3rd temperature is warming up to the 4th temperature, obtain the 4th intermediate product, described the 4th temperature is 1100 DEG C～1300 DEG C;
5), under the condition of protective gas, described the 4th intermediate product is incubated from the 4th greenhouse cooling to the five temperature, obtain Graphene, described the 5th temperature is 900 DEG C～1000 DEG C.
17. methods according to claim 14, is characterized in that, the preparation method of described binder for casting comprises the following steps:
Benzylic ether phenolic resins and PIC are carried out to the first reaction, obtain the first product;
Described the first product and epoxy resin are carried out to the second reaction, obtain the second product;
Described the second product, acrylate, organic compound and Graphene are carried out to the 3rd reaction, obtain binder for casting.
18. methods according to claim 17, is characterized in that, the temperature of described the first reaction is 70 DEG C～90 DEG C.
19. methods according to claim 17, is characterized in that, the temperature of described the second reaction is 110 DEG C～150 DEG C.
20. methods according to claim 17, is characterized in that, 60 DEG C of the temperature < of described the 3rd reaction.
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