CN104162625B - A kind of binder for casting and preparation method thereof - Google Patents
A kind of binder for casting and preparation method thereof Download PDFInfo
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- CN104162625B CN104162625B CN201410401065.7A CN201410401065A CN104162625B CN 104162625 B CN104162625 B CN 104162625B CN 201410401065 A CN201410401065 A CN 201410401065A CN 104162625 B CN104162625 B CN 104162625B
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Abstract
The invention provides a kind of binder for casting, prepared by benzylic ether phenolic resin, polyisocyanate, epoxy resin, acrylate, organic compound and Graphene are reacted；Described organic compound includes one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.The invention provides the preparation method of a kind of binder for casting, including: benzylic ether phenolic resin, polyisocyanate, epoxy resin, acrylate, organic compound and Graphene are reacted, obtains binder for casting；Described organic compound includes one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.Mold or casting core that the binder for casting that the present invention provides prepares have longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.
Description
Technical field
The present invention relates to adhesive techniques field, particularly relate to a kind of binder for casting and preparation method thereof.
Background technology
In foundary industry, generally using cold-box process to prepare core, cold-box process refers to gas or aerosol catalyst
At room temperature catalytic resin sand is to reach quick-setting process.Cold-box process presses gas, aerosol catalyst and resin
The difference of binding agent in sand, can be divided into amine method, SO2-epoxy resin method, CO2Resin method and methyl formate method.Wherein, SO2-epoxy
The core sand up time that resin method prepares is longer, and solves the production problems such as core box fouling and sticking to mould, is suitable for big
Batch production.
The Chinese patent of Application No. 201010176020.6 discloses a kind of binding agent for casting core, will fusing
Good 10g benzylic ether phenolic resin puts in reactor, heated and stirred, dehydrated under vacuum (vacuum is 15mm mercury column), to temperature
Till degree reaches 120 DEG C of bubble-free.It is cooled to 60 DEG C, adds the polyisocyanate of 7.5g；Reactor condenser is adjusted to backflow
State, under agitation leads to steam and heats up, make temperature rise to 70 DEG C in 30 minutes, and insulation reaction 180 at 70 DEG C～90 DEG C
Minute；After insulation terminates, material is cooled to 60 DEG C, adds the epoxy resin of 750g, made temperature in the kettle rise in 60 minutes
110 DEG C, and 110 DEG C～150 DEG C of insulation reaction 180 minutes；Cool to 60 DEG C, by the acrylate of 200g, 22.5g
High boiling ester, the hydrocarbon diluent of 10g add in mixing kettle, start stirring, mix 2 hours, make material mix homogeneously, obtain for
The binding agent of casting core.
Although the core strength that this core binder for casting that prior art provides prepares is higher, but this
The high-temperature heat-resistance time of the core that binding agent prepares and high temperature compression strength are poor, limit the application of this binding agent.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of binder for casting and preparation method thereof, use the present invention
Mold or casting core that the binder for casting provided prepares have longer high-temperature heat-resistance time and higher high-temperature heat-resistance
Intensity.
The invention provides a kind of binder for casting, by benzylic ether phenolic resin, polyisocyanate, epoxy resin and third
Olefin(e) acid ester, organic compound and Graphene are reacted to be prepared；Described organic compound include diacid diol-lipid compound,
One or more in alcohol compound and hydrocarbon compound.
Preferably, the parts by weight of described benzylic ether phenolic resin are 1 part～30 parts, the weight portion of described polyisocyanate
Number is 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
Part～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
Part.
Preferably, the parts by weight of described Graphene are 0.5 part～8 parts.
Preferably, the mass ratio of described benzylic ether phenolic resin and epoxy resin is (1～50): 100.
Preferably, the mass ratio of described polyisocyanate and benzylic ether phenolic resin is (1～30): 100.
Preferably, the weight average molecular weight of described benzylic ether phenolic resin is 500～2000.
Preferably, one during described polyisocyanate includes aliphatic polymeric isocyanate and aromatic poly-isocyanate or
Several.
Preferably, the one during described aliphatic polymeric isocyanate includes diisocyanate and hexamethylene diisocyanate
Or two kinds.
Preferably, described aromatic poly-isocyanate includes diphenyl methane-4, and 4-diisocyanate and polymethylene are many
One or both in phenyl polyisocyanates.
Preferably, described epoxy resin includes novolac epoxy resin, amino polyfunctional epoxy resin and alicyclic epoxy tree
One or more in fat.
Preferably, described diacid diol-lipid compound includes dibutyl phthalate, dioctyl phthalate, neighbour
Phthalic acid diisobutyl ester, diisooctyl phthalate, adipic acid dibutyl ester, dimethyl succinate, Glutaric Acid Dimethyl ester and
One or more in dimethyl adipate.
Preferably, one or more during described alcohol compound includes methanol, ethanol, butanol and isopropanol.
Preferably, one or both during described hydrocarbon compound includes aromatic hydrocarbon and kerosene.
The invention provides the preparation method of a kind of binder for casting, including:
Benzylic ether phenolic resin, polyisocyanate, epoxy resin, acrylate, organic compound and Graphene are carried out
Reaction, obtains binder for casting；Described organic compound includes diacid diol-lipid compound, alcohol compound and hydro carbons
One or more in compound.
Preferably, the raw material of preparing of described Graphene is biomass carbon source.
Preferably, the preparation method of described Graphene comprises the following steps:
1), under the effect of catalyst, biomass carbon source is carried out catalytic treatment, obtains the first intermediate product, described in urge
Agent includes one or more in the chlorate of manganese, iron compound, cobalt compounds and nickel compounds；
2), under conditions of protective gas, by described first intermediate product after the first temperature is warming up to the second temperature
Insulation, obtains the second intermediate product, and described first temperature is 20 DEG C～40 DEG C, and described second temperature is 300 DEG C～400 DEG C；
3), under conditions of protective gas, by described second intermediate product after the second temperature is warming up to the 3rd temperature
Insulation, obtains the 3rd intermediate product；Described 3rd temperature is 800 DEG C～900 DEG C；
4), under conditions of protective gas, by described 3rd intermediate product after the 3rd temperature is warming up to the 4th temperature
Insulation, obtains the 4th intermediate product, and described 4th temperature is 1100 DEG C～1300 DEG C；
5), under conditions of protective gas, by described 4th intermediate product after the 4th greenhouse cooling to the 5th temperature
Insulation, obtains Graphene, and described 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 resin and polyisocyanate are carried out the first reaction, obtains the first product；
Described first product and epoxy resin are carried out the second reaction, obtains the second product；
Described second product, acrylate, organic compound and Graphene are carried out the 3rd reaction, obtains casting and use
Binding agent.
Preferably, the temperature of described first reaction is 70 DEG C～90 DEG C.
Preferably, the temperature of described second reaction is 110 DEG C～150 DEG C.
Preferably, temperature ＜ 60 DEG C of described 3rd reaction.
The invention provides a kind of binder for casting, by benzylic ether phenolic resin, polyisocyanate, epoxy resin, third
Olefin(e) acid ester, organic compound and Graphene are reacted to be prepared；Described organic compound include diacid diol-lipid compound,
One or more in alcohol compound and hydrocarbon compound.The mold for preparing of binder for casting that the present invention provides or
Casting core has longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.Test result indicate that, use the present invention to provide
The casting core that binder for casting prepares is 107 seconds～128 seconds at the heat-resistant time of 1100 DEG C, the comprcssive strength of 1100 DEG C
For 0.28MPa～0.5MPa.
The invention provides the preparation method of a kind of binder for casting, including: by benzylic ether phenolic resin, polyisocyanate
Ester, epoxy resin, acrylate, organic compound and Graphene react, and obtain binder for casting；Described organic compound
Thing includes one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.The side that the present invention provides
Mold or casting core that the binder for casting that method prepares prepares have longer high-temperature heat-resistance time and higher height
Temperature high-temperature capability.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment
It is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under not making creative work premise, broadly falls into the model of present invention protection
Enclose.
The invention provides a kind of binder for casting, by benzylic ether phenolic resin, polyisocyanate, epoxy resin and third
Olefin(e) acid ester, organic compound and Graphene are reacted to be prepared；Described organic compound include diacid diol-lipid compound,
One or more in alcohol compound and hydrocarbon compound.
The mold for preparing of binder for casting that the present invention provides or casting core have the 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 resin are preferably 1 part～30 parts, more preferably 5 parts～
25 parts, most preferably 10 parts～20 parts.In the present invention, described benzylic ether phenolic resin is preferably high ortho position benzylic ether phenolic aldehyde tree
Fat.In the present invention, the weight average molecular weight of described benzylic ether phenolic resin be preferably 500～2000, more preferably 1000～
1500.The present invention does not has special restriction to the source of described benzylic ether phenolic resin, can be bought by market and obtain, it is possible to according to
Preparation method well known to those skilled in the art prepares.In the present invention, described high ortho position benzylic ether phenolic resin is preferred
Preparation method system according to the high ortho position benzylic ether phenolic resin disclosed in the Chinese patent of Application No. 200710188114.3
For obtaining.
In the present invention, on the basis of the parts by weight of described benzylic ether phenolic resin, the weight of described polyisocyanate
Number is preferably 0.1 part～10 parts, more preferably 0.5 part～8 parts, most preferably 1 part～6 parts, the most preferably 2 parts～4 parts.
In the present invention, the one or several during described polyisocyanate is preferably aliphatic polymeric isocyanate and aromatic poly-isocyanate
Kind, more preferably one or more in aromatic poly-isocyanate.In the present invention, described aliphatic polymeric isocyanate is preferred
For one or both in diisocyanate and hexamethylene diisocyanate.In the present invention, described aromatic series polyisocyanate
Ester is preferably one or both in diphenyl methane-4,4-diisocyanate and polymethylene polyphenyl polyisocyanates.This
Invent the source to described polyisocyanate and there is no special restriction, can be bought by market and obtain.
In the present invention, on the basis of the parts by weight of described benzylic ether phenolic resin, the weight portion of described epoxy resin
Number is preferably 40 parts～70 parts, more preferably 45 parts～60 parts, most preferably 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
It is preferably novolac epoxy resin.In the present invention, described novolac epoxy resin preferably includes bisphenol A epoxide resin and Bisphenol F ring
One or both in epoxy resins.The present invention does not has special restriction to the source of described epoxy resin, can be bought by market and obtain
?.
In the present invention, the mass ratio of described benzylic ether phenolic resin and epoxy resin is preferably (1～50): 100, more excellent
Elect as (5～35): 100, most preferably (10～30): 100, be the most preferably (15～25): 100.In the present invention, described poly-
The mass ratio of isocyanates and benzylic ether phenolic resin is preferably (1～30): 100, more preferably (5～25): 100, most preferably
For (10～20): 100.
In the present invention, on the basis of the parts by weight of described benzylic ether phenolic resin, the weight portion of described acrylate
Number is preferably 20 parts～30 parts, more preferably 24 parts～28 parts, most preferably 25 parts.In the present invention, described acrylate is excellent
Choosing include one in tripropylene glycol diacrylate, hexanediyl ester and trimethylolpropane trimethacrylate or
Several, more preferably tripropylene glycol diacrylate, hexanediyl ester or trimethylolpropane trimethacrylate.This
Invent the source to described acrylate and there is no special restriction, can be bought by market and obtain.
In the present invention, on the basis of the parts by weight of described benzylic ether phenolic resin, the weight of described organic compound
Number is preferably 1 part～30 parts, more preferably 5 parts～25 parts, most preferably 10 parts～20 parts.In the present invention, described organic
Compound includes one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound, preferably diacid
One or more in diol-lipid compound and alcohol compound.In the present invention, described diacid diol-lipid compound is excellent
Elect as dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate, diisooctyl phthalate,
One or more in adipic acid dibutyl ester, dimethyl succinate, Glutaric Acid Dimethyl ester and dimethyl adipate, more preferably neighbour
Phthalic acid dibutyl ester, dioctyl phthalate, diisobutyl phthalate, adipic acid dibutyl ester, dimethyl succinate
With one or more in Glutaric Acid Dimethyl ester, most preferably dibutyl phthalate, dioctyl phthalate, adipic acid
One or more in dibutyl ester and dimethyl succinate.
In the present invention, the one or several during described alcohol compound preferably includes methanol, ethanol, butanol and isopropanol
Kind, more preferably one or more in methanol, ethanol and butanol, most preferably methanol or ethanol.
In the present invention, described hydrocarbon compound is preferably one or more in aromatic hydrocarbon and kerosene, more preferably virtue
Fragrant hydrocarbon.The present invention does not has special restriction to the source of described organic compound, can be bought by market and obtain, it is possible to according to ability
Method known to field technique personnel prepares.
In the present invention, on the basis of the parts by weight of described benzylic ether phenolic resin, the parts by weight of described Graphene
It is preferably 0.1 part～10 parts, more preferably 0.5 part～8 parts, most preferably 1 part～6 parts, the most preferably 2 parts～4 parts.At this
In invention, the raw material of preparing of described Graphene is preferably biomass carbon source.In the present invention, the preparation method of described Graphene is excellent
Choosing comprises the following steps:
1), under the effect of catalyst, biomass carbon source is carried out catalytic treatment, obtains the first intermediate product, described in urge
Agent includes one or more in the chlorate of manganese, iron compound, cobalt compounds and nickel compounds；
2), under conditions of protective gas, by described first intermediate product after the first temperature is warming up to the second temperature
Insulation, obtains the second intermediate product, and described first temperature is 20 DEG C～40 DEG C, and described second temperature is 300 DEG C～400 DEG C；
3), under conditions of protective gas, by described second intermediate product after the second temperature is warming up to the 3rd temperature
Insulation, obtains the 3rd intermediate product；Described 3rd temperature is 800 DEG C～900 DEG C；
4), under conditions of protective gas, by described 3rd intermediate product after the 3rd temperature is warming up to the 4th temperature
Insulation, obtains the 4th intermediate product, and described 4th temperature is 1100 DEG C～1300 DEG C；
5), under conditions of protective gas, by described 4th intermediate product after the 4th greenhouse cooling to the 5th temperature
Insulation, obtains Graphene, and described 5th temperature is 900 DEG C～1000 DEG C.
Biomass carbon source, preferably under the effect of catalyst, is carried out catalytic treatment by the present invention, obtains the first intermediate product,
Described catalyst includes one or more in the chlorate of manganese, iron compound, cobalt compounds and nickel compounds.At this
In invention, described biomass carbon source be preferably in cellulose and lignin one or both, more preferably cellulose, most preferably
For porous cellulose.In the present invention, the preparation method of described porous cellulose preferably includes following steps:
A), biomass resource is hydrolyzed in acid, obtains lignocellulose, described biomass resource include plant and
One or more in agriculture and forestry organic waste material；
B), processing described lignocellulose, obtain porous cellulose, described process includes acid treatment, salt treatment
Or organic solvent processes.
Biomass resource is preferably hydrolyzed in acid by the present invention, obtains lignocellulose, described biomass resource bag
Include one or more in plant and agriculture and forestry organic waste material.In the present invention, described biomass resource is more preferably agriculture and forestry organic waste material,
Most preferably in corn stalk, corn cob, kaoliang stalk, megasse, bagasse, furfural dregs, xylose residue, wood flour, cotton stalk and phragmites communis
One or more, the most preferably corn cob.
In the present invention, during the acid of described hydrolysis is preferably sulphuric acid, nitric acid, hydrochloric acid, formic acid, sulfurous acid, phosphoric acid and acetic acid
One or more.In the present invention, the consumption of the acid of described hydrolysis is preferably 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.
After obtaining lignocellulose, described wood fibre is preferably processed by the present invention, obtains porous cellulose, described
Process includes that acid treatment, salt treatment or organic solvent process.In the present invention, the method for described lignocellulose is processed more preferably
Process for salt treatment, most preferably acid sulfite process or alkali sulfite process processes.In the present invention, described acid sub-
The pH that sulfate process processes is preferably 1～7.In the present invention, when described acid sulfite process processes, the consumption of acid is preferably
4wt%～30wt% of lignocellulose.In the present invention, the concentration expressed in percentage by weight of acid when described acid sulfite process processes
Preferably making liquid-solid ratio is (2～20): 1.In the present invention, described acid sulfite process process temperature be preferably 70 DEG C～
180℃.In the present invention, the time that described acid sulfite process processes is preferably 1 hour～6 hours.
In the present invention, the pH that described alkali sulfite process processes is preferably 7～14.In the present invention, described alkalescence
When sulphite process processes, the consumption of alkali is preferably 4wt%～30wt% of lignocellulose.In the present invention, described alkalescence is sub-
When sulfate process processes, the concentration expressed in percentage by weight of alkali preferably makes liquid-solid ratio be (2～20): 1.In the present invention, described alkalescence sulfurous
The temperature that hydrochlorate method processes is preferably 70 DEG C～180 DEG C.In the present invention, the time that described alkali sulfite process processes is preferred
It it is 1 hour～6 hours.
In the present invention, the catalyst preparing described Graphene preferably includes the chlorate of ferrum, the cyanide of ferrum, Fe-laden acid
Salt, the chlorate of cobalt, containing cobaltatess, the chlorate of nickel and containing one or more in nickelate；More preferably include iron chloride, chlorine
Change ferrous iron, ferric nitrate, ferrous nitrate, iron sulfate, ferrous sulfate, the potassium ferricyanide, potassium ferrocyanide, three oxalic acid conjunction potassium ferrite, chlorine
Change one or more in cobalt, cobalt nitrate, cobaltous sulfate, cobalt acetate, Nickel dichloride., nickel nitrate, nickel sulfate and nickel acetate.
In the present invention, when preparing described Graphene, the mass ratio of catalyst and biomass 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, described catalytic treatment time
Between be preferably 2 hours～10 hours.
After obtaining the first intermediate product, the present invention is preferably under conditions of protective gas, by described first intermediate product
It is incubated after the first temperature is warming up to the second temperature, obtains the second intermediate product；Described first temperature is 20 DEG C～40 DEG C, described
Second temperature is 300 DEG C～400 DEG C.In the present invention, described first intermediate product is warming up to the second temperature from the first temperature
Heating rate is preferably 5 DEG C/min～20 DEG C/min.In the present invention, described first intermediate product is warming up to from the first temperature
Temperature retention time after two temperature is preferably 4 hours～8 hours.In the present invention, described protective gas is preferably nitrogen and lazy
One or more in property gas, more preferably nitrogen.
After obtaining the second intermediate product, the present invention is preferably under conditions of protective gas, by described second intermediate product
It is incubated after the second temperature is warming up to the 3rd temperature, obtains the 3rd intermediate product；Described 3rd temperature is 800 DEG C～900 DEG C.?
In the present invention, the heating rate that described second intermediate product is warming up to the 3rd temperature from the second temperature is preferably 20 DEG C/min～50
℃/min.In the present invention, described second intermediate product temperature retention time after the second temperature is warming up to the 3rd temperature is preferably
3.5 hours～7 hours.In the present invention, the kind of described protective gas and protective gas described in technique scheme
Kind is consistent, does not repeats them here.
After obtaining the 3rd intermediate product, the present invention is preferably under conditions of protective gas, by described 3rd intermediate product
It is incubated after the 3rd temperature is warming up to the 4th temperature, obtains the 4th intermediate product；Described 4th temperature is 1100 DEG C～1300 DEG C.
In the present invention, described 3rd intermediate product from the 3rd temperature be warming up to the heating rate of the 4th temperature be preferably 50 DEG C/min～
60℃/min.In the present invention, described 3rd intermediate product temperature retention time after the 3rd temperature is warming up to the 4th temperature is preferred
It it is 6 hours～8 hours.In the present invention, the kind of described protective gas and protective gas described in technique scheme
Kind is consistent, does not repeats them here.
After obtaining the 4th intermediate product, the present invention is preferably under conditions of protective gas, by described 4th intermediate product
It is incubated after the 4th greenhouse cooling to the 5th temperature, obtains Graphene；Described 5th temperature is 900 DEG C～1000 DEG C.At this
In bright, described 4th intermediate product from the rate of temperature fall of the 4th greenhouse cooling to the 5th temperature be preferably 30 DEG C/min～50 DEG C/
min.In the present invention, to be preferably 2 little for described 4th intermediate product temperature retention time after the 4th greenhouse cooling to the 5th temperature
Time～4 hours.In the present invention, the kind one of protective gas described in the kind of described protective gas and technique scheme
Cause, do not repeat them here.
The invention provides the preparation method of a kind of binder for casting, including:
Benzylic ether phenolic resin, polyisocyanate, epoxy resin, acrylate, organic compound and Graphene are carried out
Reaction, obtains binder for casting；Described organic compound includes diacid diol-lipid compound, alcohol compound and hydro carbons
One or more in compound.
It is resistance to that mold that the binding agent for preparing of method that the present invention provides prepares or casting core have longer high temperature
Heat time and higher high-temperature heat-resistance intensity.
The present invention is by benzylic ether phenolic resin, polyisocyanate, epoxy resin, acrylate, organic compound and graphite
Alkene reacts, and obtains binder for casting.In the present invention, described benzylic ether phenolic resin, polyisocyanate, asphalt mixtures modified by epoxy resin
The kind of fat, acrylate, organic compound and Graphene, source and consumption and benzylic ether phenolic aldehyde tree described in technique scheme
Fat, polyisocyanate, epoxy resin, acrylate, organic compound and the kind of Graphene, source are consistent with consumption, at this
Repeat no more.
Benzylic ether phenolic resin and polyisocyanate are preferably carried out the first reaction by the present invention, obtain the first product；
Described first product and epoxy resin are carried out the second reaction, obtains the second product；
Described second product, acrylate, organic compound and Graphene are carried out the 3rd reaction, obtains casting and use
Binding agent；Described organic compound include the one in diacid diol-lipid compound, alcohol compound and hydrocarbon compound or
Several.
Benzylic ether phenolic resin and polyisocyanate are preferably carried out the first reaction by the present invention, obtain the first product；
More preferably polyisocyanate is joined in benzylic ether phenolic resin and carry out the first reaction, obtain the first product.At this
In bright, the temperature of described first reaction is preferably 70 DEG C～90 DEG C, more preferably 75 DEG C～85 DEG C, most preferably 80 DEG C.At this
In invention, the time of described first reaction is preferably 150 minutes～200 minutes, more preferably 180 minutes.In the present invention, institute
State the parts by weight of benzylic ether phenolic resin and polyisocyanate and benzylic ether phenolic resin described in technique scheme and poly-different
The parts by weight of cyanate are consistent, do not repeat them here.
Before carrying out described first reaction, the present invention preferably carries out processed to described benzylic ether phenolic resin.This
Invention preferably carries out described processed under conditions of stirring.The present invention is preferably carried out at described dehydration under conditions of vacuum
Reason.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, optimum
Elect 120 DEG C as.
After obtaining the first product, described first product and epoxy resin are preferably carried out the second reaction by the present invention,
To the second product；More preferably epoxy resin is joined in described first product and carry out the second reaction, obtain second
Product.In the present invention, the temperature of described second reaction is preferably 110 DEG C～150 DEG C, more preferably 120 DEG C～140
DEG C, most preferably 130 DEG C.In the present invention, the time of described second reaction is preferably 150 minutes～200 minutes, more preferably
180 minutes.In the present invention, the parts by weight of epoxy resin described in the parts by weight of described epoxy resin and technique scheme
Unanimously, do not repeat them here.
After obtaining the second product, the present invention preferably by described second product, acrylate, organic compound and
Graphene carries out the 3rd reaction, obtains binder for casting；More preferably acrylate, organic compound and Graphene are joined
Second product carries out the 3rd reaction, obtains binder for casting.In the present invention, the temperature of described 3rd reaction is preferred
＜ 60 DEG C, more preferably 10 DEG C～50 DEG C, most preferably 20 DEG C～40 DEG C.In the present invention, the time of described 3rd reaction is excellent
Elect 100 minutes～150 minutes as, more preferably 120 minutes.In the present invention, described acrylate, organic compound and graphite
The parts by weight of alkene are consistent, at this with the parts by weight of acrylate, organic compound and Graphene described in technique scheme
Repeat no more.
The binder for casting using the present invention to provide is prepared the method for mold or casting core and is preferably:
Binder for casting mixing molding sand, organic peroxide and the present invention provided, obtains mixed material；
In described mixed material, it is passed through sulfur dioxide, prepares mold or casting core.
The binder for casting mixing that molding sand, organic peroxide and the present invention are preferably provided by the present invention, is mixed
Material.The present invention does not has special restriction to kind and the source of described molding sand, uses molding sand well known to those skilled in the art
, can be bought by market and obtain.In an embodiment of the present invention, described molding sand can be great Lin normal sand.In the present invention,
The mass ratio of the binder for casting that described molding sand, organic peroxide and the present invention provide is preferably (1500～2500): (3
～5): (20～30), more preferably (1800～2200): (4～4.7): (24～28), most preferably 2000:4.5:25.5.?
In the present invention, described organic peroxide is preferably cumyl hydroperoxide, methyl ethyl ketone peroxide and t-butyl hydroperoxide
In one or more, more preferably cumyl hydroperoxide, methyl ethyl ketone peroxide or t-butyl hydroperoxide.
After obtaining mixed material, the present invention is preferably passed through sulfur dioxide in described mixed material, prepare mold or
Casting core.In the present invention, the pressure that is passed through of described sulfur dioxide is preferably 0.1MPa～0.3MPa, more preferably 0.2MPa.?
In the present invention, the time that is passed through of described sulfur dioxide is preferably 10 seconds～20 seconds, more preferably 15 seconds.
The present invention does not has special restriction to the equipment preparing mold or casting core, uses system well known to those skilled in the art
Core machine.In an embodiment of the present invention, described core making machine can be MLA1 core making machine.In the present invention, described core making machine
Shooting pressure be preferably 0.2MPa～0.6MPa, more preferably 0.4MPa.In the present invention, the washing pressure of described core making machine
It is preferably 0.1MPa～0.3MPa, more preferably 0.2MPa.
The binder for casting using the present invention to provide prepares casting core, method particularly includes: by great Lin standard molding sand, mistake
The binder for casting that oxidation hydroxyl isopropylbenzene and the present invention provide, according to the ratio mixing that mass ratio is 2000:4.5:25.5,
Obtain mixed material；In MLA1 core making machine, in described mixed material, it is passed through the sulfur dioxide of 15 seconds, prepares casting core,
The pressure that is passed through of described sulfur dioxide is 0.2MPa, and the shooting pressure of described core making machine is 0.4MPa, the washing of described core making machine
Pressure is 0.2MPa.Described casting core is processed into a diameter of 12mm, the cylindrical sample of a height of 20mm, the sample obtained is existed
In QX-GWY-1 type multifunctional high-temperature tester, measuring high-temperature heat-resistance time and the high temperature compression strength of sample, test result is,
The casting core that the binder for casting that the present invention provides prepares is 107 seconds～128 seconds at the heat-resistant time of 1100 DEG C, 1100
The comprcssive strength of DEG C temperature is 0.28MPa～0.5MPa.
The invention provides a kind of binder for casting, by benzylic ether phenolic resin, polyisocyanate, epoxy resin, third
Olefin(e) acid ester, organic compound and Graphene are reacted to be prepared；Described organic compound include diacid diol-lipid compound,
One or more in alcohol compound and hydrocarbon compound.The mold for preparing of binder for casting that the present invention provides or
Casting core has longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.
The invention provides the preparation method of a kind of binder for casting, including: by benzylic ether phenolic resin, polyisocyanate
Ester, epoxy resin, acrylate, organic compound and Graphene react, and obtain binder for casting；Described organic compound
Thing includes one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.The side that the present invention provides
Mold or casting core that the binding agent that method prepares prepares have longer high-temperature heat-resistance time and higher high-temperature heat-resistance
Intensity.
Benzylic ether phenolic resin used in following example of the present invention, for according to Application No. 200710188114.3
The method disclosed in Chinese patent, the high ortho position benzylic ether phenolic resin prepared, other raw materials are commercial goods.
Embodiment 1
At 90 DEG C, corn cob is carried out in sulphuric acid the hydrolysis of 10min, obtain lignocellulose, the matter of described sulphuric acid
Amount is the 3% of described corn cob quality；
At 70 DEG C, the acid sulfite process carried out described lignocellulose 1 hour processes, and obtains porous fibre
Element, the pH value in described acid sulfite process processing procedure is 1, and acid is sulphuric acid, and sulphite is magnesium sulfite, described sulphuric acid
Quality is described lignocellulose quality 4%, liquid-solid ratio is 2:1.
The porous cellulose obtained is carried out hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is described porous cellulose quality
5%, 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, stirring carries out catalytic treatment for 2 hours, and described manganese chloride is with many
The mass ratio of hole cellulose is 0.01:1；Product after the catalytic treatment that will obtain is dried at 70 DEG C, obtains water content and is less than
First intermediate product of 10wt%.
Described first intermediate product is placed in retort, with the gas intake of 200mL/min in described carbide furnace
It is passed through nitrogen as protection gas, described 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 little
Time, obtain the second intermediate product；Described second intermediate product is warming up to 800 DEG C with the speed of 20 DEG C/min from 300 DEG C, insulation
3.5 hours, obtain the 3rd intermediate product；Described 3rd intermediate product is warming up to 1100 with the speed of 50 DEG C/min from 800 DEG C
DEG C, it is incubated 6 hours, obtains the 4th intermediate product；By described 4th intermediate product with the speed of 30 DEG C/min from 1100 DEG C of coolings
To 900 DEG C, it is incubated 2 hours；The 4th intermediate product after described cooling is cooled to 60 DEG C.
At 60 DEG C, by the 4th intermediate product after above-mentioned cooling in the sodium hydrate aqueous solution that mass concentration is 3%
Wash 4 hours, obtain the first washed product；At 70 DEG C, it is the hydrochloric acid water of 4% by described first washed product in mass concentration
Solution washs 4 hours, obtains the second washed product；It is dried after described second washed product is washed with distilled water to neutrality,
Obtain Graphene.
Embodiment 2
At 180 DEG C, corn cob is carried out in nitric acid the hydrolysis of 10h, obtain lignocellulose, the quality of described nitric acid
For described corn cob quality 20%；
At 180 DEG C, the acid sulfite process carried out described lignocellulose 6 hours processes, and obtains porous fibre
Element, the pH value in described acid sulfite process processing procedure is 7, and acid is sulphuric acid, and sulphite is sodium sulfite, described sulphuric acid
Quality is described lignocellulose quality 30%, liquid-solid ratio is 20:1.
Described porous cellulose carries out hydrogen peroxide bleaching, and the quality of described hydrogen peroxide is described porous cellulose quality
5%, 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, stirring carries out catalytic treatment for 10 hours, described ferric nitrate and
The mass ratio of porous cellulose is 2:1；Product after the catalytic treatment that will obtain is dried at 120 DEG C, obtains water content and is less than
First intermediate product of 5wt%.
Described first intermediate product is placed in retort, with the gas intake of 800mL/min in described carbide furnace
Be passed through argon as protection gas, described first intermediate product is warming up to 400 DEG C with the speed of 20 DEG C/min from 20 DEG C, insulation 8
Hour, obtain the second intermediate product；Described second intermediate product is warming up to 900 DEG C with the speed of 50 DEG C/min from 400 DEG C, protects
Temperature 7 hours, obtains the 3rd intermediate product；Described 3rd intermediate product is warming up to 1300 with the speed of 60 DEG C/min from 900 DEG C
DEG C, it is incubated 8 hours, obtains the 4th intermediate product；By described 4th intermediate product with the speed of 50 DEG C/min from 1300 DEG C of coolings
To 1000 DEG C, it is incubated 4 hours；The 4th intermediate product after described cooling is cooled to 20 DEG C.
At 120 DEG C, it is the sodium hydrate aqueous solution of 55% by the 4th intermediate product after above-mentioned cooling in mass concentration
Middle washing 24 hours, obtains the first washed product；At 150 DEG C, it is 10% by described first washed product in mass concentration
Aqueous hydrochloric acid solution washs 24 hours, obtains the second washed product；Described second washed product is washed with distilled water to neutrality
Rear dry, obtain Graphene.
Embodiment 3
Preparing Graphene according to method disclosed in the Chinese patent of Application No. 200810113596.0, detailed process is:
Silicon substrate is cleaned post-drying, by gas phase deposition technology at silicon substrate table with deionized water, ethanol, acetone successively
Face deposits zinc sulfide that a layer thickness is 100 nanometers as catalyst；
Described deposition has the silicon substrate of zinc sulfide be placed in the middle part of the quartz ampoule of cleaning, quartz ampoule is put in electric furnace, make
The middle part of quartz ampoule is positioned at the central area of electric furnace, is then passed through the hydrogen of 100sccm and the argon of 100sccm in quartz ampoule
After gaseous mixture 60 minutes, begin to warm up；
When the temperature in center of electric furnace region is up to 850 DEG C, in electric furnace, be passed through ethanol as carbon source, reaction start into
OK；
After reaction carries out 20 minutes, stop being passed through ethanol, simultaneously close off electric furnace, continue to be passed through 100sccm hydrogen and
The gaseous mixture of the argon of 100sccm is down to room temperature to temperature, obtains depositing the substrate of Graphene；
Described deposition has the substrate of Graphene put in the hydrochloric acid solution of 0.1mol/L soak 60 minutes, remove sulfuration
Zinc, is then washed with deionized water clean drying, obtains Graphene.
Embodiment 4
Under conditions of stirring, the benzylic ether phenolic resin of melted 140 kilograms is put in reactor, is heated to
120 DEG C, it is dehydrated under conditions of vacuum is 10mm mercury column, obtains bubble-free benzylic ether phenolic resin；
Described bubble-free benzylic ether phenolic resin is cooled to 60 DEG C, in described bubble-free benzylic ether phenolic resin
Add the PM-200 poly methylene poly phenyl poly isocyanate of 10 kilograms；Reactor condenser is adjusted to reflux state, is stirring
Mix lower logical steam to heat up, made temperature rise to 85 DEG C in 30 minutes, carry out first reaction of 180 minutes, obtain the first reaction and produce
Thing；
Under conditions of stirring, the DER331 epoxy resin of 540 kilograms is joined in described first product,
Carry out second reaction of 180 minutes at 120 DEG C, obtain the second product；
Described second product is cooled to 30 DEG C, under conditions of stirring, by the trimethylolpropane tris of 200 kilograms
Acrylate, the dibutyl phthalate of 120 kg, the Solvesso100 aromatic hydrocarbon solvent of 30 kilograms and the reality of 10 kilograms
Execute in the Graphene addition mixing kettle that example 1 prepares, carry out the 3rd reaction of 2 hours, obtain binder for casting.
According to the method described in technique scheme, use the binder for casting system that the embodiment of the present invention 4 prepares
Standby casting core, is processed into sample by described casting core, carries out high-temperature heat-resistance time and high temperature compression strength test, test result such as table 1
Shown in, the high-temperature heat-resistance time of the sample that table 1 be the embodiment of the present invention 4～embodiment 7 and comparative example 1 prepares and high temperature are anti-
Compressive Strength test result.
Embodiment 5
Under conditions of stirring, the benzylic ether phenolic resin of melted 88 kilograms is put in reactor, is heated to
120 DEG C, it is dehydrated under conditions of vacuum is 10mm mercury column, obtains bubble-free benzylic ether phenolic resin；
Described bubble-free benzylic ether phenolic resin is cooled to 60 DEG C, in described bubble-free benzylic ether phenolic resin
Add the PM-200 poly methylene poly phenyl poly isocyanate of 12 kilograms；Reactor condenser is adjusted to reflux state, is stirring
Mix lower logical steam to heat up, made temperature rise to 88 DEG C in 30 minutes, carry out first reaction of 180 minutes, obtain the first reaction and produce
Thing；
Under conditions of stirring, the DER331 epoxy resin of 700 kilograms is joined in described first product,
Carry out second reaction of 180 minutes at 130 DEG C, obtain the second product；
Described second product is cooled to 20 DEG C, under conditions of stirring, by the trimethylolpropane tris of 290 kilograms
Acrylate, the dibutyl phthalate of 200 kilograms, the Solvesso100 aromatic hydrocarbon solvent of 50 kilograms and the reality of 16 kilograms
Execute in the Graphene addition mixing kettle that example 2 prepares, carry out the 3rd reaction of 2 hours, obtain binder for casting.
According to the method described in technique scheme, use the binder for casting system that the embodiment of the present invention 5 prepares
Standby casting core, is processed into sample by described casting core, carries out high-temperature heat-resistance time and high temperature compression strength test, test result such as table 1
Shown in.
Embodiment 6
Under conditions of stirring, the benzylic ether phenolic resin of melted 180 kilograms is put in reactor, is heated to
120 DEG C, it is dehydrated under conditions of vacuum is 10mm mercury column, obtains bubble-free benzylic ether phenolic resin；
Described bubble-free benzylic ether phenolic resin is cooled to 60 DEG C, in described bubble-free benzylic ether phenolic resin
Add 14 kilograms of PM-200 poly methylene poly phenyl poly isocyanates；Reactor condenser is adjusted to reflux state, in stirring
The most 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 conditions of stirring, the DER331 epoxy resin of just 450 kilograms joins in described first product,
Carry out reaction in 180 minutes second at 110 DEG C, obtain the second product；
Described second product is cooled to 50 DEG C, under conditions of stirring, by the trimethylolpropane tris of 300 kilograms
Acrylate, the dibutyl phthalate of 90 kilograms, the Solvesso100 aromatic hydrocarbon solvent of 20 kilograms and the enforcement of 6 kilograms
The Graphene that example 3 prepares adds in mixing kettle, carries out the 3rd reaction of 2 hours, obtains binder for casting.
According to the method described in technique scheme, use the binder for casting system that the embodiment of the present invention 6 prepares
Standby casting core, is processed into sample by described casting core, carries out high-temperature heat-resistance time and high temperature compression strength test, test result such as table 1
Shown in.
Embodiment 7
Under conditions of stirring, the benzylic ether phenolic resin of melted 25 kilograms is put in reactor, is heated to
120 DEG C, it is dehydrated under conditions of vacuum is 10mm mercury column, obtains bubble-free benzylic ether phenolic resin；
Described bubble-free benzylic ether phenolic resin is cooled to 60 DEG C, in described bubble-free benzylic ether phenolic resin
Add the PM-200 poly methylene poly phenyl poly isocyanate of 5 kilograms；Reactor condenser is adjusted to reflux state, in stirring
The most 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 conditions of stirring, the DER331 epoxy resin of 760 kilograms is joined in described first product,
150 DEG C of second reactions carrying out 180 minutes minutes, obtain the second product.
Described second product is cooled to 40 DEG C, under conditions of stirring, by the trimethylolpropane tris of 300 kilograms
Acrylate, the dibutyl phthalate of 216 kilograms, the Solvesso100 aromatic hydrocarbon solvent of 100 kilograms and the reality of 28 kilograms
Execute in the Graphene addition mixing kettle that example 3 prepares, carry out the 3rd reaction of 2 hours, obtain binder for casting.
According to the method described in technique scheme, use the binder for casting system that the embodiment of the present invention 7 prepares
Standby casting core, is processed into sample by described casting core, carries out high-temperature heat-resistance time and high temperature compression strength test, test result such as table 1
Shown in.
Comparative example 1
According to method disclosed described in the Chinese patent of Application No. 201010176020.6, preparation is for casting core
Binding agent, detailed process is:
Being put in reactor by the 10g benzylic ether phenolic resin melted, heated and stirred, (vacuum is dehydrated under vacuum
15mm mercury column), reaching 120 DEG C of bubble-free to temperature；Described benzylic ether phenolic resin is cooled to 60 DEG C, adds the poly-of 7.5g
Isocyanates；Reactor condenser is adjusted to reflux state, under agitation leads to steam and heat up, made temperature rise in 30 minutes
70 DEG C, and insulation reaction 180 minutes at 80 DEG C；After insulation terminates, material is cooled to 60 DEG C, adds the asphalt mixtures modified by epoxy resin of 750g
Fat, made temperature in the kettle rise to 110 DEG C in 60 minutes, and 130 DEG C of insulation reaction 180 minutes；Cool to 60 DEG C, will
The acrylate of 200g, the dibutyl phthalate of 22.5g, the methanol of 10g add in mixing kettle, start stirring, and mixing 2 is little
Time, make material mix homogeneously, obtain the binding agent for casting core.
According to the method described in technique scheme, use that comparative example 1 of the present invention prepares for casting core
Binding agent preparation casting core, is processed into sample by described casting core, carries out high-temperature heat-resistance time and high temperature compression strength test, test knot
Fruit 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
Intensity test result
| Embodiment | 1100 DEG C of heat-resistant times | 1100 DEG C of comprcssive 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, by benzylic ether phenolic resin, poly-isocyanide
Acid esters, epoxy resin, acrylate, organic compound and Graphene are reacted to be prepared；Described organic compound includes two
One or more in acid diol-lipid compound, alcohol compound and hydrocarbon compound.The casting bonding that the present invention provides
Mold or casting core that agent prepares have longer high-temperature heat-resistance time and higher high-temperature heat-resistance intensity.
The invention provides the preparation method of a kind of binder for casting, including: by benzylic ether phenolic resin, polyisocyanate
Ester, epoxy resin, acrylate, organic compound and Graphene react, and obtain binder for casting；Described organic compound
Thing includes one or more in diacid diol-lipid compound, alcohol compound and hydrocarbon compound.The side that the present invention provides
Mold or casting core that the binding agent that method prepares prepares have longer high-temperature heat-resistance time and higher high-temperature heat-resistance
Intensity.
Claims (20)
1. a binder for casting, by benzylic ether phenolic resin, polyisocyanate, epoxy resin and acrylate, organises
Compound and Graphene is reacted prepares；Described organic compound include diacid diol-lipid compound, alcohol compound and
One or more in hydrocarbon compound；
The raw material of preparing of described Graphene is biomass carbon source, described biomass carbon source be the one in cellulose and lignin or
Two kinds.
Binder for casting the most according to claim 1, it is characterised in that the parts by weight of described benzylic ether phenolic resin
Being 1 part～30 parts, the parts by weight of described polyisocyanate are 0.1 part～10 parts；The parts by weight of described epoxy resin are 40
Part～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
Part；The parts by weight of described Graphene are 0.1 part～10 parts.
Binder for casting the most according to claim 2, it is characterised in that the parts by weight of described Graphene are 0.5 part
～8 parts.
Binder for casting the most according to claim 2, it is characterised in that described benzylic ether phenolic resin and epoxy resin
Mass ratio be (5～35): 100.
Binder for casting the most according to claim 2, it is characterised in that described polyisocyanate and benzylic ether phenolic aldehyde tree
The mass ratio of fat is (1～30): 100.
Binder for casting the most according to claim 1, it is characterised in that the Weight-average molecular of described benzylic ether phenolic resin
Amount is 500～2000.
Binder for casting the most according to claim 1, it is characterised in that described polyisocyanate includes that aliphatic poly is different
One or more in cyanate and aromatic poly-isocyanate.
Binder for casting the most according to claim 7, it is characterised in that described aliphatic polymeric isocyanate includes that two is different
One or both in cyanate and hexamethylene diisocyanate.
Binder for casting the most according to claim 7, it is characterised in that described aromatic poly-isocyanate includes hexichol
One or both in methylmethane-4,4-diisocyanate and polymethylene polyphenyl polyisocyanates.
Binder for casting the most according to claim 1, it is characterised in that described epoxy resin includes epoxy novolac tree
One or more in fat, amino polyfunctional epoxy resin and cycloaliphatic epoxy resin.
11. binder for casting according to claim 1, it is characterised in that described diacid diol-lipid compound includes
Dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate, diisooctyl phthalate, oneself two
One or more in acid dibutyl ester, dimethyl succinate, Glutaric Acid Dimethyl ester and dimethyl adipate.
12. binder for casting according to claim 1, it is characterised in that described alcohol compound includes methanol, second
One or more in alcohol, butanol and isopropanol.
13. binder for casting according to claim 1, it is characterised in that described hydrocarbon compound include aromatic hydrocarbon and
One or both in kerosene.
The preparation method of 14. 1 kinds of binder for casting, including:
Benzylic ether phenolic resin, polyisocyanate, epoxy resin, acrylate, organic compound and Graphene are reacted,
Obtain binder for casting；Described organic compound includes diacid diol-lipid compound, alcohol compound and hydrocarbon compound
In one or more.
15. methods according to claim 14, it is characterised in that the raw material of preparing of described Graphene is biomass carbon source.
16. methods according to claim 15, it is characterised in that the preparation method of described Graphene comprises the following steps:
1), under the effect of catalyst, biomass carbon source is carried out catalytic treatment, obtain the first intermediate product, described catalyst
Including one or more in chlorate, iron compound, cobalt compounds and the nickel compounds of manganese；
2), under conditions of protective gas, described first intermediate product is incubated after the first temperature is warming up to the second temperature,
Obtaining the second intermediate product, described first temperature is 20 DEG C～40 DEG C, and described second temperature is 300 DEG C～400 DEG C；
3), under conditions of protective gas, described second intermediate product is incubated after the second temperature is warming up to the 3rd temperature,
Obtain the 3rd intermediate product；Described 3rd temperature is 800 DEG C～900 DEG C；
4), under conditions of protective gas, described 3rd intermediate product is incubated after the 3rd temperature is warming up to the 4th temperature,
Obtaining the 4th intermediate product, described 4th temperature is 1100 DEG C～1300 DEG C；
5), under conditions of protective gas, described 4th intermediate product is incubated after the 4th greenhouse cooling to the 5th temperature,
Obtaining Graphene, described 5th temperature is 900 DEG C～1000 DEG C.
17. methods according to claim 14, it is characterised in that the preparation method of described binder for casting includes following
Step:
Benzylic ether phenolic resin and polyisocyanate are carried out the first reaction, obtains the first product；
Described first product and epoxy resin are carried out the second reaction, obtains the second product；
Described second product, acrylate, organic compound and Graphene are carried out the 3rd reaction, obtains casting bonding
Agent.
18. methods according to claim 17, it is characterised in that the temperature of described first reaction is 70 DEG C～90 DEG C.
19. methods according to claim 17, it is characterised in that the temperature of described second reaction is 110 DEG C～150 DEG C.
20. methods according to claim 17, it is characterised in that temperature ＜ 60 DEG C of described 3rd reaction.
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| CN106040966B (en) * | 2015-06-18 | 2019-02-05 | 济南圣泉集团股份有限公司 | Cold-box binder and casting and forming body |
| DE102016125702A1 (en) * | 2016-12-23 | 2018-06-28 | Ask Chemicals Gmbh | Component system for the production of cores and molds |
| CN107459761A (en) * | 2017-07-03 | 2017-12-12 | 马鞍山瑞美塑业有限公司 | A kind of ultrathin fire-resistant phenoplasts |
| CN109794580B (en) * | 2019-03-21 | 2021-06-01 | 飞龙汽车部件股份有限公司 | Sand core for casting water pump of internal combustion engine and preparation method thereof |
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