CN102807661A - Method for preparing self-hardening furan resin for casting and mother liquor - Google Patents
Method for preparing self-hardening furan resin for casting and mother liquor Download PDFInfo
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- CN102807661A CN102807661A CN2012102551599A CN201210255159A CN102807661A CN 102807661 A CN102807661 A CN 102807661A CN 2012102551599 A CN2012102551599 A CN 2012102551599A CN 201210255159 A CN201210255159 A CN 201210255159A CN 102807661 A CN102807661 A CN 102807661A
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Abstract
The invention discloses a method for preparing a self-hardening furan resin for casting and mother liquor. Acetone, phenol, solid formaldehyde, urea and furfuryl alcohol are used as raw materials to be subjected to an addition reaction, a polycondensation reaction and other steps to prepare the furan resin mother liquor. The mother liquor and the furfuryl alcohol with substantially adjustable amount are matched with an enhancer to be stirred conventionally to obtain the self-hardening furan resin for casting. According to the preparation method of the self-hardening furan resin for casting, the preparation process is quick and simple, the production efficiency is high, the labor intensity is low, the furfuryl alcohol content of the resin has strong controllability and wider adjustment range, and is suitable for preparing industrially applied high furan resins, medium furan resins and low furan resins, and thus the method is suitable for industrial popularization and application.
Description
Technical field
The present invention relates to a kind of self-hardening furan resin mother liquor and the preparation method of casting, belong to the resin material preparing technical field with self-hardening furan resin.
Background technology
Furane resin are the thermosetting resins that contain furan nucleus in a kind of structure, processed by furfuryl alcohol and phenol, urea or various aldehyde modification furfuryl alcohol; Casting is exactly wherein one type with self-hardening furan resin, and casting use self-hardening furan resin is faint yellow to brown transparent or semitransparent uniform liquid generally speaking.Casting at room temperature can make sand mold (core) sclerosis through acid catalysis with self-hardening furan resin; Be one type of sticker that casting industry is the most frequently used, application quantity is maximum, be characterized in that moulding (core) is simple, sand mold (core) collapsibility is good, the regenerating used reclamation rate high, resin sand intensity is high, smell is little.Casting at present mainly exists furfuryl alcohol add-on height, a series of problems such as production efficiency is low, energy consumption is big, secondary pollution with the preparation of self-hardening furan resin.
CN101423594A discloses a kind of preparation method who does not have nitrogen furan resin; Adopting formaldehyde, phenol, furfuryl alcohol, properties-correcting agent and toughener is the feedstock production furane resin, and that the preparation process comprises is reinforced, heat temperature raising, dehydration, synthetic, discharging and packing are put several key steps in storage.Among this preparation method; The furfuryl alcohol consumption is 89~93%; The prepared furane resin that obtain are high furane resin (furfuryl alcohol content is greater than 80%); But can not be used for preparation furane resin (furfuryl alcohol content is 60~80%) and low furane resin (furfuryl alcohol content less than 60% greater than 40%), the very difficult furane resin that obtain different furfuryl alcohol content as required; And furfuryl alcohol need be in heat temperature raising, synthetic and discharging in batches adding, can cause the furfuryl alcohol add-on higher like this, the efficient of producing is exerted an influence; And building-up process need the dehydration, be prone to cause secondary pollution.
Summary of the invention
The purpose of this invention is to provide a kind of self-hardening furan resin mother liquor, be used for producing fast as required the furane resin of different furfuryl alcohol content, to satisfy demand of practical production.Another object of the present invention is to utilize the method for the casting of the different furfuryl alcohol content of self-hardening furan resin mother liquor production rapidly and efficiently simultaneously, to enhance productivity, to reduce the controllability of secondary pollution, reduction labour intensity and production with self-hardening furan resin.
In order to realize above purpose; The technical scheme that self-hardening furan resin mother liquor of the present invention is adopted is: a kind of self-hardening furan resin mother liquor is that main raw material adopts following method to be prepared from acetone 10~25%, phenol 15~30%, solid formaldehyde 10~25%, urea 0.5~25%, the furfuryl alcohol 25~50% of weight percent:
1) urea of measuring by acetone, phenol, solid formaldehyde and the part of composition of raw materials amount feeds intake, uniform mixing, and adjustment pH is 7.0~9.0, under 70~100 ℃ of temperature, reacts 1~3 hour;
2) furfuryl alcohol of adding 25~50%, adjustment pH is 4.0~6.0, under 80~110 ℃ of temperature, reacts 1.5~3.5 hours;
3) adjustment pH is 7.0~8.0, adds the urea of remaining amount, under 80~90 ℃ of temperature, reacts 0.5~1 hour;
4) be cooled to below 40 ℃ and can obtain the self-hardening furan resin mother liquor.
As further improvement, adopt acid or alkali adjustment pH value among the self-hardening furan resin mother liquor preparation method.The said acid of selection as optimizing is phosphoric acid, and said alkali is sodium hydroxide.
As further improvement, the urea of the said part amount of step 1) accounts for 0~80% of urea total amount.
As further improvement, step 2) to adjust system temperature before the said adding furfuryl alcohol be below 80 ℃.
The technical scheme that the preparation method adopted that the present invention casts with self-hardening furan resin is: a kind ofly adopt the casting of self-hardening furan resin mother liquor to use the self-hardening furan resin preparation method; Self-hardening furan resin mother liquor 20~80%, furfuryl alcohol 20~80% and the toughener 0.1~0.5% of weight percent are stirred at normal temperatures, can obtain casting and use self-hardening furan resin.
As further optimized choice, said toughener is a silane coupling agent, specifically can select silane coupling agent KH 550 or silane coupling agent KH 602.
The application's self-hardening furan resin mother liquor adopts acetone, phenol, (trioxymethylene has another name called 1 to solid formaldehyde; 3; The 5-trioxane) and urea be that raw material carries out addition, polycondensation and generates prepolymer, wherein the acetone low price can reduce cost significantly; Phenol is more commonly used, is mainly used in the high-temperature behavior that improves resin; Solid formaldehyde replaces traditional liquid formaldehyde, and price is lower, need not dehydration, environmental protection more; The effect of urea has two: one of which, can generate urea-formaldehyde resin with formolite reaction, and the furfuryl alcohol polycondensation that adds the back again is urea aldehyde furane resin; Its two, add urea in the polycondensation later stage and remove free formaldehyde (utilizing the easy characteristics of reacting of urea and formaldehyde), play the aldehydes removal effect.The self-hardening furan resin mother liquor that the present invention makes can stir under normal temperature condition with furfuryl alcohol and toughener and process casting and use self-hardening furan resin, the preparation process fast and simply, production efficiency height, non-secondary pollution, labour intensity are low.
Casting of the present invention is as shown in Figure 1 with the preparation technology of self-hardening furan resin; In the preparation process; The weight ratio of mother liquor and furfuryl alcohol is between 0.25~4; The part by weight of adjustment mother liquor and furfuryl alcohol can obtain furfuryl alcohol content at 40% self-hardening furan resin to the different furfuryl alcohol content more than 80%.The self-hardening furan resin preparation method is used in casting of the present invention; Compare the CN101423594A patent; The controllability of furfuryl alcohol content and nitrogen content is strong, the setting range broad; Be fit to preparation industry and go up high furane resin, middle furane resin and the low furane resin of using, also can prepare no nitrogen furan resin (promptly can be considered no nitrogen furan resin), be fit to carry out industrialization promotion and use according to JB/T 7526-2008 regulation nitrogen content≤0.5%.
Description of drawings
Fig. 1 casts the process flow sheet with the self-hardening furan resin preparation method for the present invention.
Embodiment
Embodiment 1
The self-hardening furan resin mother liquor of present embodiment adopts acetone 10%, phenol 18%, solid formaldehyde 18%, urea 4%, the furfuryl alcohol 50% of weight percent to be the main raw material preparation, and concrete preparation method is following:
Adopt following method preparation:
1) in reaction kettle, add 10% acetone, 18% phenol, 18% solid formaldehyde and 2% urea (urea total amount 50%), adopting sodium hydroxide adjustment pH is 7.0, and reaction is 1 hour under 70 ℃ of temperature;
2) treat that system is cooled to the furfuryl alcohol of adding 50% below 80 ℃, using phosphoric acid adjustment pH is 4.0, and reaction is 1.5 hours under 80 ℃ of temperature;
3) using sodium hydroxide adjustment pH is 7.0, adds 2% remaining urea, and reaction is 0.5 hour under 80 ℃ of temperature;
4) be cooled to below 40 ℃ and can obtain the self-hardening furan resin mother liquor.
The casting of present embodiment is adopted following method with self-hardening furan resin; Self-hardening furan resin mother liquor 40%, furfuryl alcohol 59.8% and the silane coupling agent (specifically selecting KH 550) 0.2% that adopts present embodiment to prepare is raw materials mix; Stir at normal temperatures, can obtain casting and use self-hardening furan resin.It is about 80% that the furfuryl alcohol content of self-hardening furan resin is used in the casting of present embodiment preparation, belongs to high furane resin.
Embodiment 2
The self-hardening furan resin mother liquor of present embodiment adopts acetone 16%, phenol 30%, solid formaldehyde 13%, urea 0.5%, the furfuryl alcohol 40.5% of weight percent to be the main raw material preparation, and concrete preparation method is following:
Adopt following method preparation:
1) acetone, 30% phenol and 13% solid formaldehyde of adding 16% in reaction kettle, adopting sodium hydroxide adjustment pH is 7.5, reaction is 1.8 hours under 80 ℃ of temperature;
2) treat that system is cooled to the furfuryl alcohol of adding 40.5% below 80 ℃, using phosphoric acid adjustment pH is 5.0, and reaction is 2 hours under 95 ℃ of temperature;
3) using sodium hydroxide adjustment pH is 7.0, adds 0.5% urea, and reaction is 0.5 hour under 80 ℃ of temperature;
4) be cooled to below 40 ℃ and can obtain the self-hardening furan resin mother liquor.
The casting of present embodiment is adopted following method with self-hardening furan resin; Self-hardening furan resin mother liquor 20%, furfuryl alcohol 79.7% and the silane coupling agent (specifically selecting KH 602) 0.3% that adopts present embodiment to prepare is raw materials mix; Stir at normal temperatures, can obtain casting and use self-hardening furan resin.It is about 88% that the furfuryl alcohol content of self-hardening furan resin is used in the casting of present embodiment preparation, belongs to high furane resin.
Embodiment 3
The self-hardening furan resin mother liquor of present embodiment adopts acetone 12%, phenol 16%, solid formaldehyde 25%, urea 12%, the furfuryl alcohol 35% of weight percent to be the main raw material preparation, and concrete preparation method is following:
Adopt following method preparation:
1) in reaction kettle, add 12% acetone, 16% phenol, 25% solid formaldehyde and 9% urea (account for urea total amount 75%), adopting sodium hydroxide adjustment pH is 8.0, under 90 ℃ of temperature, reacts 1~3 hour;
2) treat that system is cooled to the furfuryl alcohol of adding 35% below 80 ℃, using phosphoric acid adjustment pH is 4.5, and reaction is 3 hours under 100 ℃ of temperature;
3) using sodium hydroxide adjustment pH is 7.5, adds 3% remaining urea, and reaction is 0.8 hour under 85 ℃ of temperature;
4) be cooled to below 40 ℃ and can obtain the self-hardening furan resin mother liquor.
The casting of present embodiment is adopted following method with self-hardening furan resin; Self-hardening furan resin mother liquor 79.6%, furfuryl alcohol 20% and the silane coupling agent (specifically selecting KH 602) 0.4% that adopts present embodiment to prepare is raw materials mix; Stir at normal temperatures, can obtain casting and use self-hardening furan resin.It is about 48% that the furfuryl alcohol content of self-hardening furan resin is used in the casting of present embodiment preparation, belongs to low furane resin.
Embodiment 4
The self-hardening furan resin mother liquor of present embodiment adopts acetone 25%, phenol 15%, solid formaldehyde 10%, urea 25%, the furfuryl alcohol 25% of weight percent to be the main raw material preparation, and concrete preparation method is following:
Adopt following method preparation:
1) in reaction kettle, add 25% acetone, 15% phenol, 10% solid formaldehyde and 20% urea (account for urea total amount 80%), adopting sodium hydroxide adjustment pH is 9.0, and reaction is 3 hours under 100 ℃ of temperature;
2) treat that system is cooled to the furfuryl alcohol of adding 25% below 80 ℃, using phosphoric acid adjustment pH is 6.0, and reaction is 3.5 hours under 110 ℃ of temperature;
3) using sodium hydroxide adjustment pH is 8.0, adds 5% remaining urea, and reaction is 1 hour under 90 ℃ of temperature;
4) be cooled to below 40 ℃ and can obtain the self-hardening furan resin mother liquor.
The casting of present embodiment is adopted following method with self-hardening furan resin; Self-hardening furan resin mother liquor 45%, furfuryl alcohol 54.8% and the silane coupling agent (specifically selecting KH 550) 0.2% that adopts present embodiment to prepare is raw materials mix; Stir at normal temperatures, can obtain casting and use self-hardening furan resin.It is about 66% that the furfuryl alcohol content of self-hardening furan resin is used in the casting of present embodiment preparation, belongs to middle furane resin.
Comparative Examples 1
The self-hardening furan resin finished product of this Comparative Examples; Adopt acetone 4%, phenol 7.2%, solid formaldehyde 7.2%, urea 1.6%, furfuryl alcohol 79.8%, silane coupling agent (specifically the selecting KH 550) 0.2% of weight percent to be the main raw material preparation, concrete preparation method is following:
Adopt following method preparation:
1) acetone, 7.2% phenol, 7.2% solid formaldehyde and 0.8% urea of adding 4% in reaction kettle, adopting sodium hydroxide adjustment pH is 7.0, reaction is 1 hour under 70 ℃ of temperature;
2) treat that system is cooled to the furfuryl alcohol of adding 79.8% below 80 ℃, using phosphoric acid adjustment pH is 4.0, and reaction is 1.5 hours under 80 ℃ of temperature;
3) using sodium hydroxide adjustment pH is 7.0, adds 0.8% remaining urea, and reaction is 0.5 hour under 80 ℃ of temperature;
4) be cooled to below 40 ℃ and can obtain self-hardening furan resin, add 0.2% silane coupling agent and stir and be finished product.
This Comparative Examples is the Comparative Examples of embodiment 1, belongs to conventional cast and uses the self-hardening furan resin preparation method.It is about 80% that the furfuryl alcohol content of self-hardening furan resin is used in the casting of this Comparative Examples preparation, belongs to high furane resin.
Comparative Examples 2
The self-hardening furan resin finished product of this Comparative Examples; Adopt acetone 9.55%, phenol 12.74%, solid formaldehyde 19.9%, urea 9.55%, furfuryl alcohol 47.86%, silane coupling agent (specifically the selecting KH 602) 0.4% of weight percent to be the main raw material preparation, concrete preparation method is following:
Adopt following method preparation:
1) acetone, 12.74% phenol, 19.9% solid formaldehyde and 7.16% urea of adding 9.55% in reaction kettle, adopting sodium hydroxide adjustment pH is 8.0, under 90 ℃ of temperature, reacts 1~3 hour;
2) treat that system is cooled to the furfuryl alcohol of adding 47.86% below 80 ℃, using phosphoric acid adjustment pH is 4.5, and reaction is 3 hours under 100 ℃ of temperature;
3) using sodium hydroxide adjustment pH is 7.5, adds 1.84% remaining urea, and reaction is 0.8 hour under 85 ℃ of temperature;
4) be cooled to below 40 ℃ and can obtain self-hardening furan resin, add 0.4% silane coupling agent and stir and be finished product.
This Comparative Examples is the Comparative Examples of embodiment 3, belongs to conventional cast and uses the self-hardening furan resin preparation method.It is about 48% that the furfuryl alcohol content of self-hardening furan resin is used in the casting of this Comparative Examples preparation, belongs to low furane resin.
Comparative Examples 3
The self-hardening furan resin finished product of this Comparative Examples; Adopt acetone 11.25%, phenol 6.75%, solid formaldehyde 4.5%, urea 11.25%, furfuryl alcohol 66.05%, silane coupling agent (specifically the selecting KH 550) 0.2% of weight percent to be the main raw material preparation, concrete preparation method is following:
Adopt following method preparation:
1) acetone, 6.75% phenol, 4.5% solid formaldehyde and 9% urea of adding 11.25% in reaction kettle, adopting sodium hydroxide adjustment pH is 9.0, reaction is 3 hours under 100 ℃ of temperature;
2) treat that system is cooled to the furfuryl alcohol of adding 66.05% below 80 ℃, using phosphoric acid adjustment pH is 6.0, and reaction is 3.5 hours under 110 ℃ of temperature;
3) using sodium hydroxide adjustment pH is 8.0, adds 2.25% remaining urea, and reaction is 1 hour under 90 ℃ of temperature;
4) be cooled to below 40 ℃ and can obtain self-hardening furan resin, add 0.2% silane coupling agent and stir and be finished product.
This Comparative Examples is the Comparative Examples of embodiment 4, belongs to conventional cast and uses the self-hardening furan resin preparation method.It is about 66% that the furfuryl alcohol content of self-hardening furan resin is used in the casting of this Comparative Examples preparation, belongs to middle furane resin.
Reference standard JB/T 7526-2008 compares experiment, result such as table 1:
Table 1 embodiment and Comparative Examples comparison of test results
Can find out from table 1; Adopt the prepared self-hardening furan resin of preparation method of the present invention; Furfuryl alcohol content has covered high furane resin, middle furane resin and low furane resin, and the performance of the furane resin of preparation is basic identical with the furane resin that adopt the ordinary method preparation.
Claims (9)
1. self-hardening furan resin mother liquor, it is characterized in that: acetone 10~25%, phenol 15~30%, solid formaldehyde 10~25%, urea 0.5~25%, furfuryl alcohol 25~50% with weight percent are that main raw material adopts following method to be prepared from:
1) urea of measuring by acetone, phenol, solid formaldehyde and the part of composition of raw materials amount feeds intake, uniform mixing, and adjustment pH is 7.0~9.0, under 70~100 ℃ of temperature, reacts 1~3 hour;
2) furfuryl alcohol of adding 25~50%, adjustment pH is 4.0~6.0, under 80~110 ℃ of temperature, reacts 1.5~3.5 hours;
3) adjustment pH is 7.0~8.0, adds the urea of remaining amount, under 80~90 ℃ of temperature, reacts 0.5~1 hour;
4) be cooled to below 40 ℃ and can obtain the self-hardening furan resin mother liquor.
2. self-hardening furan resin mother liquor according to claim 1 is characterized in that: adopt acid or alkali adjustment pH value.
3. self-hardening furan resin mother liquor according to claim 2 is characterized in that: said acid is phosphoric acid.
4. self-hardening furan resin mother liquor according to claim 1 is characterized in that: said alkali is sodium hydroxide.
5. self-hardening furan resin mother liquor according to claim 1 is characterized in that: the urea of the said part amount of step 1) accounts for 0~80% of urea total amount.
6. self-hardening furan resin mother liquor according to claim 1 is characterized in that: step 2) to adjust system temperature before the said adding furfuryl alcohol be below 80 ℃.
7. one kind is adopted the casting of mother liquor according to claim 1 to use the self-hardening furan resin preparation method; It is characterized in that: self-hardening furan resin mother liquor 19~79%, furfuryl alcohol 19~79% and the toughener 0.1~0.5% of weight percent are stirred at normal temperatures, can obtain casting and use self-hardening furan resin.
8. the self-hardening furan resin preparation method is used in casting according to claim 7, it is characterized in that: said toughener is a silane coupling agent.
9. the self-hardening furan resin preparation method is used in casting according to claim 8, it is characterized in that: said silane coupling agent is selected silane coupling agent KH 550 or silane coupling agent KH 602.
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CN103878297A (en) * | 2014-03-25 | 2014-06-25 | 宁夏共享集团有限责任公司 | Production method for casting adhesive |
CN105384887A (en) * | 2015-12-29 | 2016-03-09 | 珠海市斗门福联造型材料实业有限公司 | Preparation process of environment-friendly urea formaldehyde ketone-based modified furan foundry resin |
CN106008871A (en) * | 2016-06-27 | 2016-10-12 | 霍山县忠福硅溶胶有限公司 | Furan resin and preparation method thereof |
CN106977677A (en) * | 2017-04-07 | 2017-07-25 | 保定永强合成材料有限公司 | A kind of production technology of novel environment friendly furane resins |
CN107151299A (en) * | 2017-07-12 | 2017-09-12 | 河北科技大学 | It is a kind of for delicate fragrance type phenol-formaldehyde resin modified of sand casting and preparation method thereof |
CN107236104A (en) * | 2017-06-22 | 2017-10-10 | 安徽银力铸造有限公司 | A kind of preparation method cast with modified furan resin binding agent |
CN107383301A (en) * | 2017-08-30 | 2017-11-24 | 石家庄丰联精细化工有限公司 | A kind of cast steel furane resins and preparation method thereof |
CN107880232A (en) * | 2017-12-19 | 2018-04-06 | 珠海市斗门福联造型材料实业有限公司 | A kind of special furane resins of increasing material manufacturing molding sand and preparation method |
WO2019001382A1 (en) * | 2017-06-28 | 2019-01-03 | 济南圣泉集团股份有限公司 | Bonding agent for use in 3d printing process and preparation method and application thereof |
CN109175220A (en) * | 2018-09-26 | 2019-01-11 | 保定永强合成材料有限公司 | A kind of efficient furan resin for casting and preparation method thereof |
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CN103878297A (en) * | 2014-03-25 | 2014-06-25 | 宁夏共享集团有限责任公司 | Production method for casting adhesive |
CN105384887B (en) * | 2015-12-29 | 2018-06-29 | 珠海市斗门福联造型材料实业有限公司 | A kind of environment-friendly type ureaformaldehyde ketone group is modified the preparation process of furans foundry resin |
CN105384887A (en) * | 2015-12-29 | 2016-03-09 | 珠海市斗门福联造型材料实业有限公司 | Preparation process of environment-friendly urea formaldehyde ketone-based modified furan foundry resin |
CN106008871A (en) * | 2016-06-27 | 2016-10-12 | 霍山县忠福硅溶胶有限公司 | Furan resin and preparation method thereof |
CN106008871B (en) * | 2016-06-27 | 2018-07-31 | 霍山县忠福硅溶胶有限公司 | A kind of furane resins and preparation method thereof |
CN106977677A (en) * | 2017-04-07 | 2017-07-25 | 保定永强合成材料有限公司 | A kind of production technology of novel environment friendly furane resins |
CN107236104A (en) * | 2017-06-22 | 2017-10-10 | 安徽银力铸造有限公司 | A kind of preparation method cast with modified furan resin binding agent |
WO2019001382A1 (en) * | 2017-06-28 | 2019-01-03 | 济南圣泉集团股份有限公司 | Bonding agent for use in 3d printing process and preparation method and application thereof |
CN107151299A (en) * | 2017-07-12 | 2017-09-12 | 河北科技大学 | It is a kind of for delicate fragrance type phenol-formaldehyde resin modified of sand casting and preparation method thereof |
CN107151299B (en) * | 2017-07-12 | 2019-07-30 | 河北科技大学 | A kind of delicate fragrance type phenol-formaldehyde resin modified and preparation method thereof for sand casting |
CN107383301A (en) * | 2017-08-30 | 2017-11-24 | 石家庄丰联精细化工有限公司 | A kind of cast steel furane resins and preparation method thereof |
CN107383301B (en) * | 2017-08-30 | 2019-11-01 | 石家庄丰联精细化工有限公司 | A kind of cast steel furane resins and preparation method thereof |
CN107880232A (en) * | 2017-12-19 | 2018-04-06 | 珠海市斗门福联造型材料实业有限公司 | A kind of special furane resins of increasing material manufacturing molding sand and preparation method |
CN107880232B (en) * | 2017-12-19 | 2020-04-28 | 广东省铸力铸材科技有限公司 | Special furan resin for additive manufacturing molding sand and preparation method |
CN109175220A (en) * | 2018-09-26 | 2019-01-11 | 保定永强合成材料有限公司 | A kind of efficient furan resin for casting and preparation method thereof |
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