CN103302234A - Easy-release isocure cold box binder - Google Patents
Easy-release isocure cold box binder Download PDFInfo
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- CN103302234A CN103302234A CN2013102326148A CN201310232614A CN103302234A CN 103302234 A CN103302234 A CN 103302234A CN 2013102326148 A CN2013102326148 A CN 2013102326148A CN 201310232614 A CN201310232614 A CN 201310232614A CN 103302234 A CN103302234 A CN 103302234A
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Abstract
The invention provides an easy-release isocure cold box binder which comprises a composite release agent consisting of an olefin release agent and an ester release agent, wherein the olefin release agent is C12-C16 monoolefine; and the ester release agent is one or more in a group composed of C12-C18 monohydroxy-alcohol alkanoate, C12-C18 polyhydroxy-alcohol alkanoate, C12-C18 mono-alcohol alkyldiacid and C12-C18 alkyl deacid glycol. The technical scheme provided by the invention obviously increases the continuous core-making times in preparation of a complicated core, and remarkably improves the production efficiency.
Description
Technical field
The present invention relates to binding agent, specifically, the present invention relates to a kind of amine method cold core box resinoid bond of the easy demoulding, this binder system is used for the casting resin sand compound, in the presence of the gaseous state amine catalyst, solidify to form the core mould of making the cast metal foundry goods, be applicable to cast various types of cast steels, cast iron and non-ferrous alloy spare.
Background technology
In foundary industry, cold-box process refers to gas or the aerosol catalyst process of the instantaneous curing of catalytic resin sand at room temperature.Press the difference of gas or aerosol catalyst, cold-box process can be divided into amine method, SO2 method, CO2 resin method and methyl formate method.
The spendable catalyst of amine method cold core box technique has triethylamine, dimethyl amine, dimethyl isopropylamine etc., because triethylamine is cheap, usually adopt triethylamine to make catalyst, be characterized in, setting rate is fast, coremaking efficient is high, the core sand good fluidity, the core sand up time is long, the core dimensional accuracy is high and energy savings etc., Foundry Production high-quality, efficient, energy-conservation requirement have been satisfied, be fit to the production of complicated core in enormous quantities, now be widely used in the industries such as automobile, internal combustion engine, rolling stock, aircraft, pump processed, become the main flow of various core manufacturing crafts.
Along with more large batch of Foundry Production demand, and the demand of high coremaking productivity ratio, foundry goods high accuracy, high-quality, high duplication, Core-making unit pipelining degree is more and more higher, be integrated into a Core making center, namely with robot automation, continuous productive process ground the various cores that cold-box core blower produces are got the sequence of operations such as core, core assembly, dip-coating, the production efficiency of a Core making center per hour can reach more than the 50 core groups, and this frequency that just is desirably in spraying releasing agent on the mould is more low better.
But present amine method cold core box resinoid bond then not too adapts to the operating type of this high pipelining.Although may have the binding agent of part can satisfy the preparation of the core of simple shape, when the core of preparation complicated shape, can produce defective.Be embodied in: when the core of preparation complicated shape; binding agent in the core is easy to bond with die surface; after carrying out continuously the inferior coremaking of minority; core (having cured) can be bonded on the mould; this just needs to shut down frequently; to carry out the labor cleaning, behind the spraying releasing agent, rerun again, limited the performance of automatization level.On the other hand, high-frequency sticking to mould will certainly make more sand core surface be pulled, and causes blemish, causes the percent defective of product high, Quality Down.
Summary of the invention
The present invention has overcome above-mentioned shortcoming, proposed a kind of easy demoulding amine method cold core box binder.
The amine method cold core box binder of the easy demoulding of the present invention comprises the compound releasing agent that is comprised of alkene releasing agent and ester class releasing agent, described alkene releasing agent is the C12-C16 monoolefine, and described ester class releasing agent is for by in the single methanol ester of C12-C18 alkanoic acid monohydroxy alcohol ester, C12-C18 alkanoic acid polyhydroxy alkyl ester, C12-C18 alkyl acid, the group that C12-C18 alkyl acid diol ester consists of one or more.
Use amine method cold core box binder of the present invention, significantly improve the demolding performace of core, especially be fit to the preparation of complex-shaped core, when greatly reducing coremaking on the mould number of times of spraying releasing agent, protected environment; Yield rate and the production efficiency of product have been improved.
The specific embodiment
Among the present invention, monoolefine and the ester class releasing agent of C10 to C16 is used in conjunction with, resulting amine method cold core box binder can significantly improve the demolding performace of resin sand.Term " monoolefine " refers to only have straight chain or the branched alkene of the two keys of a C-C in hydrocarbon chain, wherein preferred linear alkene.Typical example comprises the straight or branched monoolefine of 1-decene, 2-decene, 1-hendecene, 2-hendecene, 1-laurylene, 2-laurylene, 1-tridecylene, 2-tridecylene, 1-tetradecylene, 2-tetradecene, 1-ten pentaenes, 2-ten pentaenes, 1-hexadecylene, 2-hexadecylene and other double bond positions, and wherein the side chain monoolefine preferably only comprises the monoolefine of methyl, ethyl, propyl group or isopropyl.The alkene of the especially preferred C12-C14 of the present invention, most preferably linear alkene.
Be applicable to the single methanol ester that ester class releasing agent of the present invention comprises C12-C18 alkanoic acid monohydroxy alcohol ester, C12-C18 alkanoic acid polyhydroxy alkyl ester, C12-C18 alkyl acid, the diol ester of C12-C18 alkyl acid, wherein, term " single hydroxyl alcohol " refers to only contain the C1-C6 alcohol of a hydroxyl, wherein preferred C1-C4 is pure, for example methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butyl alcohol, 2-butanols.Term " polyhydroxy-alcohol " refers to contain the alcohol of two, three or four hydroxyls, such as ethylene glycol, glycerine (glycerine), pentaerythrite etc.Term " C12-C18 alkanoic acid polyhydroxy alkyl ester " comprises C12-C18 alkanoic acid polyhydroxy-alcohol single methanol ester and C12-C18 alkanoic acid polyhydroxy-alcohol polyol esters.Typical example comprises tristerin, glyceryl tristearate, pentaerythritol monostearate, pentaerythritol stearic acid ester 2, pentaerythrite tristearate, pentaerythritol tetrastearate, butyl stearate etc.These ester class releasing agents can use separately, also can be two kinds or two or more combinations.
Among the present invention, the mass ratio of alkene releasing agent and ester class releasing agent is preferably in the scope of 1:1 to 10:1, more preferably in the scope of 1:1 ~ 5:1, most preferably in the scope of 1:1 ~ 3:1.
In further scheme of the present invention, in releasing agent, further comprise the amide-type releasing agent.Typical example comprises a kind of or its combination of oleamide, stearic amide, the two oleamides of ethylene, the two oleamide of hexa-methylene, an xyxylene bis-stearamides etc.Such releasing agent account for the releasing agent total amount 0.05 ~ 10% between.
In a kind of specific embodiment of the present invention, this amine method cold core box binder is comprised of the raw material of following weight portion:
As the improvement of the above-mentioned specific embodiment, this amine method cold core box binder is comprised of the raw material of following weight portion:
Phenolic resins in the amine method cold core box binder is benzylic ether type phenolic resins normally.In the present invention, the weight average molecular weight of benzylic ether phenolic resins is preferably 500～2000, is preferably between the 600-1200.By selecting this specific benzylic ether phenolic resins, can reduce the viscosity of binding agent, so that be mixed with the sand mold sand core strength that the casting model powder of binding agent has higher free-running property and Geng Gao.The preferred high ortho position benzylic ether phenolic resins that uses among the present invention, so-called high ortho position benzylic ether phenolic resins refer to neighbour/contrast greater than 1 phenolic resins, and major part is the phenolic resins at ortho position in other words.Use high ortho position benzylic ether phenolic resins can obtain faster curing rate.The example of the preparation of this high ortho position benzylic ether phenolic resins has disclosure in applicant's Chinese patent CN 200710188114.3.That adopts among the embodiment hereinafter is this benzylic ether phenolic resins.
Can be used for PIC of the present invention and include but not limited to diphenyl methane-4,4 '-vulcabond (referred to as " MDI "), thick diphenyl methane-4,4 '-vulcabond (referred to as thick " MDI ") or polymethylene polyphenyl polyisocyanates (referred to as " PAPI ").The gaseous state amine catalyst can be triethylamine, dimethyl amine or dimethyl isopropylamine, is preferably triethylamine.
In most of the cases, need in cold-box binder, introduce diluent (solvent), so that this resinoid bond is suitable for mixing with molding sand.Operable solvent comprises liquid high boiling ester, lower alcohol and hydro carbons, for example aromatic hydrocarbons.In the present invention, high boiling ester refers to that boiling point is between 100～400 ℃, especially between 150～400 ℃, the carboxylate between 200～400 ℃ particularly, example comprises dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate, diisooctyl phthalate, adipic acid dibutyl ester, dimethyl succinate, dimethyl glutarate, dimethyl adipate; The example of lower alcohol comprises methyl alcohol, ethanol, butanols, isopropyl alcohol; The example of aromatic hydrocarbons comprises that benzene,toluene,xylene and ethylbenzene and boiling range are 150～290 ℃ petroleum liquid aromatic hydrocarbons fraction and in the kerosene one or more.
In a kind of preferred embodiment of the present invention, use the mixed diluent that is formed by high boiling ester and aromatic solvent, wherein introduce the effect that high boiling ester can play plasticising.The mass ratio of high boiling ester and aromatic solvent is preferably in the scope of 1:1 to 5:1, more preferably in the scope of 1:1 ~ 3:1, most preferably in the scope of 1:1 ~ 2:1.
In a kind of specific embodiment of the present invention, this amine method cold core box binder is comprised of the raw material of following weight portion:
Those skilled in the art should understand can add other additives such as siloxanes, defoamer, wetting agent etc. in aggregate or the cast mixture.Designer's specific purposes are depended in the selection of special additive.The selection of these auxiliary agents and consumption all are that prior art is known, no longer are described in detail at this.
It can be independent component that above-mentioned each forms, and perhaps mix with other component, but benzylic ether phenolic resins can not mix storage with PIC.Preferably, this binding agent is made of component I and component I I; Component I comprises phenolic resins, solvent and the releasing agent of all wt part; Component I I comprises the PIC of all wt part.Typically embodiment is, binder system is with bicomponent system packing and use, and component I comprises the phenolic resins of all wt part and releasing agent and the hydrocarbon solvent of part weight portion; Component I I comprises the PIC of all wt part and releasing agent and the solvent of all the other parts.
This resin mixes formation casting resin sand compound with the casting aggregate, described casting resin sand compound is for the manufacture of the core mould of cast metal foundry goods.
Employing is difficult for sticking to mould according to amine method cold core box resinoid bond of the present invention when carrying out coremaking.When producing the core of complicated shape, the continuous core-making number of times of mould reaches more than 90 times, even more than 100 times, better state is more than 100 times.And the continuous production number of times of traditional amine method cold core box resin is generally about 10 times.In addition, resinoid bond quick solidifying of the present invention, first intensity is high, makes things convenient for manipulator clamping; Reduce the percent defective of core sand mold, improved casting quality.
Embodiment 1
The preparation of component I: be equipped with in the mixing kettle of agitator one, add 580 kilograms in high ortho position benzylic ether phenolic resins, 200 kilograms of dibutyl phthalates, 196 kilograms of Solvesso 150 hydrocarbon solvents, 9 kilograms in A-187 silane starts stirring, mixed approximately 2 hours, and made mixing of materials even.
The preparation of component I I: be equipped with in the mixing kettle of agitator one, add 800 kilograms of MDI, 131 kilograms of Solvesso 150 hydrocarbon solvents, 18 kilograms of butyl stearates, 9 kilograms in A-187 silane, 50 kilograms of 1-tetradecylenes, 6 kilograms of phosphorus trichlorides are driven agitator, mixed approximately 2 hours, and made mixing of materials even.With container aforesaid liquid component I and liquid component II are packed respectively, namely obtain easy demoulding amine method cold core box resin.
The intensity detection of this amine method cold core box resin is with reference to GB2684 " Foundry sand and test mixture method ".Ratio according to 100 weight portion Da Lin normal sands, 0.77 parts by weight of component I, 0.63 parts by weight of component II is made into resin sand.At first add component I and mixed with sand 1 minute, add component I I again and mixed 2 minutes, then this resin sand being blown by the MLA1 core making machine is pressed into the tension dog-bone.Its core manufacturing craft parameter is: shooting pressure 0.4MPa, blow amine pressure 0.2MPa, and washing pressure 0.2MPa blows 3.0 seconds amine time, wash time 5.0 seconds.
Measure respectively 5 seconds initial strengths of Eight characters tension test block, 24 hours whole intensity, 24 hours high wet strength (humidity 〉=95%), the results are shown in Table 1.
Table 1. uses the tensile strength of the sand mold of embodiment 1 cold box resin
With the resin of the present embodiment, the core shooter suitability for industrialized production of producing with German Lan Pei company connects the manifold core, working condition: 50/100 cleans addition 1.4 % of sand resin, and wherein the ratio of component I and component I I is 55:45.Producing continuously core group number of times is not less than 100 times.
Embodiment 2
The preparation of component I: be equipped with in the mixing kettle of agitator one, add 580 kilograms in high ortho position benzylic ether phenolic resins, 200 kilograms of dibutyl phthalates, 5 kilograms of stearic amides, 196 kilograms of Solvesso 150 hydrocarbon solvents, 9 kilograms in A-187 silane, start stirring, mixed approximately 2 hours, make mixing of materials even.
The preparation of component I I: be equipped with in the mixing kettle of agitator one, add 800 kilograms of MDI, 131 kilograms of Solvesso 150 hydrocarbon solvents, 18 kilograms of butyl stearates, 9 kilograms in A-187 silane, 50 kilograms of 1-tetradecylenes, 6 kilograms of phosphorus trichlorides are driven agitator, mixed approximately 2 hours, and made mixing of materials even.
With container aforesaid liquid component I and liquid component II are packed respectively, namely obtain easy demoulding amine method cold core box resin.Press embodiment 1 method and measure tensile strength, the results are shown in Table 2.
Table 2. uses the tensile strength of the sand mold of embodiment 2 cold box resins
Press embodiment 1 method and produce connection manifold core, produce continuously core group number of times and be not less than 120 times.
Comparative Examples
The preparation of component I: be equipped with in the mixing kettle of agitator one, add 580 kilograms in high ortho position benzylic ether phenolic resins, 200 kilograms of dibutyl phthalates, 196 kilograms of Solvesso 150 hydrocarbon solvents, 9 kilograms in A-187 silane starts stirring, mixed approximately 2 hours, and made mixing of materials even.
The preparation of component I I: be equipped with in the mixing kettle of agitator one, add 800 kilograms of MDI, 131 kilograms of Solvesso 150 hydrocarbon solvents, 18 kilograms of butyl stearates, 9 kilograms in A-187 silane, 6 kilograms of phosphorus trichlorides are driven agitator, mixed approximately 2 hours, and made mixing of materials even.
With container aforesaid liquid component I and liquid component II are packed respectively, namely obtain the amine method cold core box resin.Press embodiment 1 method and measure tensile strength, the results are shown in Table 3.
The tensile strength of the sand mold of table 3. usage comparison example cold box resin
Press embodiment 1 method and produce to connect the manifold core, behind the type of production core 7 times, sticking to mould is serious, needs can produce behind cleaning, the release agent spraying continuously.
Below in conjunction with specific embodiments easy demoulding amine method cold core box resin of the present invention is set forth, these embodiment just are used for exemplifying explanation.For a person skilled in the art, some details of foregoing is carried out multiple change and changes not needing to make creative work.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (13)
1. the amine method cold core box binder of an easy demoulding, wherein comprise the compound releasing agent that is formed by alkene releasing agent and ester class releasing agent, described alkene releasing agent is the C12-C16 monoolefine, and described ester class releasing agent is for by in the single methanol ester of C12-C18 alkanoic acid monohydroxy alcohol ester, C12-C18 alkanoic acid polyhydroxy alkyl ester, C12-C18 alkyl acid, the group that C12-C18 alkyl acid diol ester consists of one or more.
2. amine method cold core box binder according to claim 1, wherein, described C12-C16 monoolefine is 1-position linear alkene.
3. amine method cold core box binder according to claim 1, wherein, described ester class releasing agent is one or more in tristerin, glyceryl tristearate, pentaerythritol monostearate, pentaerythritol stearic acid ester 2, pentaerythrite tristearate, pentaerythritol tetrastearate and the butyl stearate.
4. amine method cold core box binder according to claim 1, wherein, the mass ratio of described alkene releasing agent and ester class releasing agent is in the scope of 1:1 to 10:1, preferably in the scope of 1:1 ~ 5:1, more preferably in the scope of 1:1 ~ 3:1.
5. amine method cold core box binder according to claim 1, mainly the raw material by following weight portion forms:
6. amine method cold core box binder according to claim 5 further comprises the amide-type releasing agent, accounts for 0.05 ~ 10% of releasing agent total amount.
7. amine method cold core box binder according to claim 6, described amide-type releasing agent are a kind of or its combination of oleamide, stearic amide, the two oleamides of ethylene, the two oleamide of hexa-methylene and an xyxylene bis-stearamides.
8. amine method cold core box binder according to claim 5, mainly the raw material by following weight portion forms:
9. amine method cold core box binder according to claim 1, it is bicomponent system, component I comprises the phenolic resins of all wt part and releasing agent and the hydrocarbon solvent of part weight portion; Component I I comprises the PIC of all wt part and releasing agent and the solvent of all the other parts.
10. amine method cold core box binder claimed in claim 1, wherein: described phenolic resins is that the weight average average molecular weight is 500～2000 high ortho position benzylic ether phenolic resins.
11. amine method cold core box binder claimed in claim 1, wherein, described PIC is diphenyl methane-4,4 '-vulcabond, thick diphenyl methane-4,4 '-vulcabond or polymethylene polyphenyl polyisocyanates.
12. amine method cold core box binder claimed in claim 8, wherein, described high boiling ester solvent is a kind of or its mixture of dibutyl phthalate, o-phthalic acid dibutyl ester, diisobutyl phthalate, diisooctyl phthalate, adipic acid dibutyl ester and dimethyl adipate, dimethyl succinate, dimethyl glutarate.
13. amine method cold core box binder claimed in claim 8, wherein, described high boiling hydrocarbon solvent is the petroleum liquid aromatic hydrocarbons fraction of 150～290 ℃ of boiling ranges, a kind of or its combination in the kerosene.
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Cited By (3)
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| CN104889314A (en) * | 2015-06-08 | 2015-09-09 | 谢伟杰 | Heat-resisting releasing agent |
| CN106040966A (en) * | 2015-06-18 | 2016-10-26 | 济南圣泉集团股份有限公司 | Cold core box binder and casting molding body |
| CN112548023A (en) * | 2020-12-08 | 2021-03-26 | 四川东树新材料有限公司 | Cold core box resin for high-collapsibility cast aluminum engine cylinder body and preparation method thereof |
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| CN106040966A (en) * | 2015-06-18 | 2016-10-26 | 济南圣泉集团股份有限公司 | Cold core box binder and casting molding body |
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| CN112548023A (en) * | 2020-12-08 | 2021-03-26 | 四川东树新材料有限公司 | Cold core box resin for high-collapsibility cast aluminum engine cylinder body and preparation method thereof |
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| CN103302234B (en) | 2015-10-14 |
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Denomination of invention: Amine method cold core box adhesive easy to demould Effective date of registration: 20211227 Granted publication date: 20151014 Pledgee: CITIC Bank Limited by Share Ltd. Ji'nan branch Pledgor: JINAN SHENGQUAN GROUP SHARE HOLDING Co.,Ltd. Registration number: Y2021980016380 |