CN113414344B - Preparation method of low-moisture self-hardening furan resin for casting - Google Patents
Preparation method of low-moisture self-hardening furan resin for casting Download PDFInfo
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- CN113414344B CN113414344B CN202110694956.6A CN202110694956A CN113414344B CN 113414344 B CN113414344 B CN 113414344B CN 202110694956 A CN202110694956 A CN 202110694956A CN 113414344 B CN113414344 B CN 113414344B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/224—Furan polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
- B22C1/10—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
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- Chemical Kinetics & Catalysis (AREA)
- Mold Materials And Core Materials (AREA)
Abstract
The invention relates to a preparation method of low-moisture self-hardening furan resin for casting, which comprises, by mass, 4% -20% of phenolic compounds, 3% -13% of aldehyde compounds, 0.02% -0.18% of acid catalysts, 0.02% -0.18% of alkaline catalysts, 63.3% -87.3% of solvents, 0.5% -3.5% of modifiers, 0.5% -2.5% of dehydrating agents and 0.5% -1.5% of coupling agents. The water content of the traditional self-hardening furan resin for casting is more than or equal to 1.0%, and the prepared sand mould and sand core have a 1H hard penetration depth of only 5-15mm under the conditions of the ambient humidity of 80RH and the ambient temperature of 25 ℃; the self-hardening furan resin for low-moisture casting can realize the water content less than or equal to 0.5%, and the prepared sand mould and sand core have the hard penetration depth of 1H at the environmental humidity of 80RH% and the environmental temperature of 25 ℃ of more than or equal to 100mm.
Description
Technical Field
The invention relates to the technical field of casting auxiliary materials, in particular to a preparation method of self-hardening furan resin for low-moisture casting.
Background
The traditional self-hardening furan resin for casting has poor hard permeability in the environment with the environmental humidity more than or equal to 70RH percent due to the excessive sensitivity to the environmental humidity, and severely restricts the adaptability of self-hardening furan resin products in the high humidity environment in rainy seasons. At present, the casting industry generally adopts a technical scheme of matching with a high-acidity curing agent to solve the problem of poor hard permeability of self-hardening furan resin products in a high-humidity environment, but the technical scheme has a plurality of defects, such as shortness of sand mold and sand core after the acidity of the curing agent is improved, strength reduction and the like.
At present, the furan resin production enterprises generally reduce the water content of resin products through technical schemes such as improving the dehydration vacuum degree, prolonging the dehydration time, improving the dehydration temperature and the like. Although the technical schemes can reduce the water content of the resin products from high to low, and meet the demands of most customers, when the water content of the resin is required to be less than 1.0%, the technical schemes can not meet the demands. And as the dehydration time is prolonged and the dehydration temperature is increased, the viscosity of the resin product is increased sharply, and furfuryl alcohol is added to reduce the viscosity so as to meet the technical requirements, thus the production cost of the resin is increased. The dehydration time is prolonged, the energy consumption is correspondingly increased, and the production efficiency is reduced.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a preparation method of self-hardening furan resin for low-moisture casting, which can realize that the moisture content of the self-hardening furan resin is less than or equal to 0.5 percent, and the prepared sand mold and sand core have a 1H hard penetration depth of more than or equal to 100mm under the conditions of 80RH of ambient humidity and 25 ℃.
The technical scheme of the invention is as follows:
the self-hardening furan resin for low-moisture casting comprises, by mass, 4% -20% of phenolic compounds, 3% -13% of aldehyde compounds, 0.02% -0.18% of acid catalysts, 0.02% -0.18% of alkaline catalysts, 63.3% -87.3% of solvents, 0.5% -3.5% of modifiers, 0.5% -2.5% of dehydrating agents and 0.5% -1.5% of coupling agents.
Further, the phenolic compound is one or a combination of a plurality of hydroquinone, dimethylphenol, bisphenol A, bisphenol F and naphthol.
Preferably, the phenolic compound is one or two of hydroquinone and bisphenol A.
Further, the aldehyde compound is one or two of formaldehyde and paraformaldehyde.
Further, the acid catalyst is one or a combination of more of formic acid, hydrochloric acid, acetic acid and acrylic acid.
Further, the alkaline catalyst is one or a combination of more of sodium hydroxide, potassium hydroxide, ammonia water and triethylamine.
The acidic catalyst and the alkaline catalyst have the function of catalyzing reaction, have the function of regulating PH, and are beneficial to further catalyzing reaction.
Further, the solvent is furfuryl alcohol.
Further, the modifier is one or a combination of more of aniline, N-dimethylaniline, phenylethanolamine, sodium lignate and ammonium chloride.
Further, the dehydrating agent is one or a combination of more of anhydrous sodium sulfate, anhydrous potassium sulfate and anhydrous magnesium sulfate.
Further, the coupling agent is one or more of KH550, KH560 and KH 602.
A preparation method of self-hardening furan resin for low-moisture casting comprises the following steps:
s1, adding a phenolic compound and an aldehyde compound into a reaction kettle, stirring, adding furfuryl alcohol, and continuously stirring for 0.5-1.5h;
s2, adding an alkaline catalyst, and adjusting the PH to 8-10;
s3, heating, slowly heating to 85-100 ℃, and preserving heat for 0.5-3h;
s4, cooling to below 45 ℃, adding an acid catalyst, and adjusting the PH to 3-5;
s5, adding furfuryl alcohol, heating, slowly heating to 105-125 ℃, and preserving heat for 0.5-5h;
s6, cooling to below 45 ℃, and adding a modifier;
s7, heating, slowly heating to 80-110 ℃, and preserving heat for 1-4 hours;
s8, vacuum dehydration;
s9, cooling to below 70 ℃, adding a dehydrating agent, and stirring for 0.5-2h at regular time;
s10, continuously cooling, cooling to below 45 ℃, adding a coupling agent, and stirring for 0.5-2h.
Preferably, in step S3, heating is performed, and the temperature is slowly raised to 90-92 ℃.
The furan resin self-hardening sand for casting comprises the low-moisture self-hardening furan resin for casting.
Preferably, the furan resin self-hardening sand for casting can be further applied to the preparation of cast products.
The invention has the beneficial effects that:
(1) The self-hardening furan resin for low-moisture casting has excellent hardness and permeability of sand mold and sand core, the 1H hardness penetration depth is more than or equal to 100mm under the conditions of 80RH% of ambient humidity and 25 ℃ of ambient temperature, and the 1H hardness penetration depth of sand mold/sand core using the traditional self-hardening furan resin for casting is only 5-15mm under the conditions of 80RH% of ambient humidity and 25 ℃ of ambient temperature.
(2) The water content of the low-moisture self-hardening furan resin for casting is less than or equal to 0.5 percent, and the water content of the traditional self-hardening furan resin for casting is more than or equal to 1.0 percent.
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Detailed Description
In order to enable those skilled in the art to better understand the technical scheme of the present invention, the present invention will be further described in detail with reference to specific embodiments.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The self-hardening furan resin for low-moisture casting comprises phenolic compounds, aldehyde compounds, acid catalysts, alkaline catalysts, solvents, modifiers and coupling agents.
In an embodiment of the present invention, the aldehyde compound is one or a combination of two of formaldehyde and paraformaldehyde.
In an embodiment of the present invention, the phenolic compound is one or more of hydroquinone, dimethylphenol, bisphenol a, bisphenol F, naphthol.
Preferably, the phenolic compound is one or two of hydroquinone and bisphenol A.
The hydroquinone, bisphenol A and formaldehyde can more easily form a branched chain structure under the alkaline condition, so that excessive unidirectional growth of molecular chains is inhibited, and the hardening reaction activity of the resin is improved.
In an embodiment of the present invention, the acidic catalyst is one or more of formic acid, hydrochloric acid, acetic acid, and acrylic acid.
In an embodiment of the present invention, the basic catalyst is one or a combination of more of sodium hydroxide, potassium hydroxide, ammonia water and triethylamine.
In an embodiment of the invention, the solvent is furfuryl alcohol.
In an embodiment of the present invention, the modifier is one or more of aniline, N-dimethylaniline, phenylethanolamine, sodium wood, and ammonium chloride.
In an embodiment of the present invention, the dehydrating agent is one or a combination of more of anhydrous sodium sulfate, anhydrous potassium sulfate, and anhydrous magnesium sulfate.
In an embodiment of the present invention, the coupling agent is one or more of KH550, KH560, KH 602.
Example 1
A preparation method of self-hardening furan resin for low-moisture casting comprises the following steps:
s1, adding 12% of phenolic compounds and 8% of aldehyde compounds into a reaction kettle, starting stirring, adding 15% of furfuryl alcohol, and continuously stirring for 0.8h;
s2, adding 0.1% of alkaline catalyst by mass fraction, and adjusting the PH to 8.8;
s3, heating, slowly heating to 90-92 ℃, and preserving heat for 2 hours;
s4, cooling to below 45 ℃, adding 0.1% of acid catalyst by mass fraction, and adjusting the PH to 4.2;
s5, adding 60.3% of furfuryl alcohol by mass, heating, slowly heating to 110-115 ℃, and preserving heat for 3 hours;
s6, cooling to below 45 ℃, and adding a modifier with the mass fraction of 2%;
s7, heating, slowly heating to 98-110 ℃, and preserving heat for 2.5 hours;
s8, vacuum dehydration;
s9, cooling to below 70 ℃, adding a dehydrating agent with the mass fraction of 1.5%, and stirring for 0.8h at regular time;
s10, continuously cooling, cooling to below 45 ℃, adding 1% of coupling agent by mass fraction, and stirring for 0.8h.
The low-moisture self-hardening furan resin for casting described in this example had a water content of 0.32%, and the self-hardening furan resin for casting described in this example was excellent in hardness penetration of sand mold and sand core, and had a hardness penetration depth of 118mm of 1H at an ambient humidity of 80RH and an ambient temperature of 25 ℃.
Example two
A preparation method of self-hardening furan resin for low-moisture casting comprises the following steps:
s1, adding 10% of phenolic compounds and 10% of aldehyde compounds into a reaction kettle, starting stirring, adding 20% of furfuryl alcohol, and continuing stirring for 1h;
s2, adding 0.16 mass percent of alkaline catalyst, and adjusting the PH to 9.6;
s3, heating, slowly heating to 90-92 ℃, and preserving heat for 2.5 hours;
s4, cooling to below 45 ℃, adding 0.12% of an acidic catalyst by mass fraction, and adjusting the PH to 3.8;
s5, adding 55.42% of furfuryl alcohol, heating, slowly heating to 115-118 ℃, and preserving heat for 2.5h;
s6, cooling to below 45 ℃, and adding a modifier with the mass fraction of 2.5%;
s7, heating, slowly heating to 102-104 ℃, and preserving heat for 3 hours;
s8, vacuum dehydration;
s9, cooling to below 70 ℃, adding a dehydrating agent with the mass fraction of 1.0%, and stirring for 0.8h at regular time;
s10, continuously cooling, cooling to below 45 ℃, adding 0.8% of coupling agent by mass fraction, and stirring for 0.8h.
The low-moisture self-hardening furan resin for casting described in this example had a water content of 0.37%, and the self-hardening furan resin for casting described in this example was excellent in hardness penetration of sand mold and sand core, and had a hardness penetration depth of 132mm of 1H at an ambient humidity of 80RH% and an ambient temperature of 25 ℃.
Example III
A preparation method of self-hardening furan resin for low-moisture casting comprises the following steps:
s1, adding 8% of phenolic compounds and 9% of aldehyde compounds into a reaction kettle, starting stirring, adding 15% of furfuryl alcohol, and continuously stirring for 0.6h;
s2, adding 0.09 mass percent of alkaline catalyst, and adjusting the pH to 8.4;
s3, heating, slowly heating to 90-92 ℃, and preserving heat for 2.8 hours;
s4, cooling to below 45 ℃, adding 0.11 mass percent of acid catalyst, and adjusting the PH to 4.5;
s5, adding 61.6% of furfuryl alcohol by mass, heating, slowly heating to 120-122 ℃, and preserving heat for 3.5 hours;
s6, cooling to below 45 ℃, and adding 3% of modifier by mass fraction;
s7, heating, slowly heating to 95-100 ℃, and preserving heat for 2.5 hours;
s8, vacuum dehydration;
s9, cooling to below 70 ℃, adding a dehydrating agent with the mass fraction of 2.0%, and stirring for 0.8h at regular time;
s10, continuously cooling, cooling to below 45 ℃, adding 1.2% of coupling agent by mass fraction, and stirring for 0.8h.
The low-moisture self-hardening furan resin for casting described in this example had a water content of 0.27%, and the self-hardening furan resin for casting described in this example was excellent in hardness penetration of sand mold and sand core, and had a hardness penetration depth of 1H of 126mm at ambient humidity of 80RH and ambient temperature of 25 ℃.
Example IV
A preparation method of self-hardening furan resin for low-moisture casting comprises the following steps:
s1, adding a phenolic compound with the mass fraction of 15% and an aldehyde compound with the mass fraction of 12% into a reaction kettle, starting stirring, adding furfuryl alcohol with the mass fraction of 25%, and continuing stirring for 1.5h;
s2, adding 0.15 mass percent of alkaline catalyst, and adjusting the PH to 9.5;
s3, heating, slowly heating to 90-92 ℃, and preserving heat for 2 hours;
s4, cooling to below 45 ℃, adding 0.15% of an acidic catalyst by mass fraction, and adjusting the PH to 3.5;
s5, adding 41.9% of furfuryl alcohol by mass, heating, slowly heating to 110-115 ℃, and preserving heat for 4 hours;
s6, cooling to below 45 ℃, and adding a modifier with the mass fraction of 2.5%;
s7, heating, slowly heating to 95-100 ℃, and preserving heat for 2 hours;
s8, vacuum dehydration;
s9, cooling to below 70 ℃, adding a dehydrating agent with the mass fraction of 1.8%, and stirring for 0.8h at regular time;
s10, continuously cooling, cooling to below 45 ℃, adding 1.5% of coupling agent by mass fraction, and stirring for 0.8h.
The low-moisture self-hardening furan resin for casting described in this example had a water content of 0.19%, and the self-hardening furan resin for casting described in this example was excellent in hardness penetration of sand mold and sand core, and had a hardness penetration depth of 1H of 138mm at an ambient humidity of 80RH and an ambient temperature of 25 ℃.
Example five
A preparation method of self-hardening furan resin for low-moisture casting comprises the following steps:
s1, adding 14% of phenolic compounds and 10% of aldehyde compounds into a reaction kettle, starting stirring, adding 20% of furfuryl alcohol, and continuing stirring for 1h;
s2, adding 0.14 mass percent of alkaline catalyst, and adjusting the PH to 10;
s3, heating, slowly heating to 90-92 ℃, and preserving heat for 3 hours;
s4, cooling to below 45 ℃, adding 0.12% of an acidic catalyst by mass fraction, and adjusting the PH to 3;
s5, adding 50.34% of furfuryl alcohol, heating, slowly heating to 118-122 ℃, and preserving heat for 3.5h;
s6, cooling to below 45 ℃, and adding a modifier with the mass fraction of 2%;
s7, heating, slowly heating to 106-110 ℃, and preserving heat for 3.5 hours;
s8, vacuum dehydration;
s9, cooling to below 70 ℃, adding a dehydrating agent with the mass fraction of 2.5%, and stirring for 0.8h at regular time;
s10, continuously cooling, cooling to below 45 ℃, adding 0.9% of coupling agent by mass fraction, and stirring for 0.8h.
The low-moisture self-hardening furan resin for casting described in this example had a water content of 0.41%, and the self-hardening furan resin for casting described in this example was excellent in hardness penetration of sand mold and sand core, and had a 1H hardness penetration depth of 131mm at ambient humidity of 80RH% and ambient temperature of 25 ℃.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
1. The preparation method of the self-hardening furan resin for low-moisture casting is characterized in that the self-hardening furan resin for low-moisture casting comprises, by mass, 4% -20% of phenolic compounds, 3% -13% of aldehyde compounds, 0.02% -0.18% of acid catalysts, 0.02% -0.18% of alkaline catalysts, 63.3% -87.3% of solvents, 0.5% -3.5% of modifiers, 0.5% -2.5% of dehydrating agents and 0.5% -1.5% of coupling agents;
the phenolic compound is one or a combination of a plurality of hydroquinone, dimethylphenol, bisphenol A, bisphenol F and naphthol;
the preparation method of the self-hardening furan resin for low-moisture casting comprises the following steps:
adding a phenolic compound and an aldehyde compound into a reaction kettle, stirring, adding furfuryl alcohol, and continuously stirring;
adding an alkaline catalyst, heating to 85-100 ℃, and carrying out heat preservation reaction;
cooling to below 45 ℃, adding an acid catalyst and furfuryl alcohol, heating to 105-125 ℃, and carrying out heat preservation reaction;
cooling to below 45 ℃, adding a modifier, heating to 80-110 ℃, and carrying out heat preservation reaction;
vacuum dewatering, cooling to below 70 ℃, adding a dehydrating agent, stirring for reaction, cooling to below 45 ℃, adding a coupling agent, and stirring for reaction.
2. The method for producing a self-hardening furan resin for low-moisture casting according to claim 1, wherein the aldehyde compound is one or a combination of two of formaldehyde and paraformaldehyde.
3. The method for producing a low-moisture casting self-hardening furan resin according to claim 1, wherein the acidic catalyst is one or a combination of a plurality of formic acid, hydrochloric acid, acetic acid and acrylic acid.
4. The method for producing a low-moisture casting self-hardening furan resin according to claim 1, wherein the basic catalyst is one or a combination of a plurality of sodium hydroxide, potassium hydroxide, ammonia water and triethylamine.
5. The method for producing a low-moisture casting self-hardening furan resin according to claim 1, wherein said solvent is furfuryl alcohol.
6. The method for preparing a low-moisture casting self-hardening furan resin according to claim 1, wherein the modifier is one or more of aniline, N-dimethylaniline, phenylethanolamine, sodium wood and ammonium chloride.
7. The method for producing a self-hardening furan resin for low-moisture casting according to claim 1, wherein the dehydrating agent is one or a combination of a plurality of anhydrous sodium sulfate, anhydrous potassium sulfate, and anhydrous magnesium sulfate.
8. The method for producing a low-moisture casting self-hardening furan resin according to claim 1, wherein the coupling agent is one or a combination of a plurality of KH550, KH560, KH 602.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5865543A (en) * | 1981-10-14 | 1983-04-19 | Hitachi Chem Co Ltd | Resin composition for self-curing mold |
| CN102532450B (en) * | 2011-12-12 | 2013-03-06 | 宁夏共享集团有限责任公司 | Production method for quickly curing nitrogen-free furane resin |
| CN105085852A (en) * | 2015-08-04 | 2015-11-25 | 宁夏共享化工有限公司 | Preparation method of low-nitrogen hot core box furan resin for casting |
| CN105273151B (en) * | 2015-10-20 | 2018-08-03 | 苏州兴业材料科技股份有限公司 | Modified phenolic furane resins and its binder |
| CN112409556A (en) * | 2020-11-27 | 2021-02-26 | 苏州兴业材料科技股份有限公司 | Method for preparing furan resin for casting from waste water |
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