CN104262560A - Furan resin for cast iron and synthesis method thereof - Google Patents
Furan resin for cast iron and synthesis method thereof Download PDFInfo
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- CN104262560A CN104262560A CN201410434225.8A CN201410434225A CN104262560A CN 104262560 A CN104262560 A CN 104262560A CN 201410434225 A CN201410434225 A CN 201410434225A CN 104262560 A CN104262560 A CN 104262560A
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- furfuryl alcohol
- coupling agent
- furane resin
- formaldehyde
- cast iron
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Abstract
The invention relates to a furan resin for cast iron and a synthesis method thereof. The invention is characterized in that the furan resin is prepared from the following raw materials in parts by weight: 60-80% of furfuryl alcohol, 5-15% of solid formaldehyde, 5-15% of urea, 0.2-1.0% of coupling agent and 5-10% of water. The solid formaldehyde is used instead of liquid formaldehyde in the synthesis process, thereby solving the problem of the sewage generated in the production process of the furan resin for cast iron; and the furan resin for cast iron has the characteristics of high strength, low viscosity, favorable molding-sand property and the like.
Description
Technical field
The invention belongs to the manufacture field of cast iron resin, particularly relate to a kind of cast iron furane resin and synthetic method thereof.
Background technology
In sand mold casting, the features such as it is high that self-hardening furan resin sand molding and core making has intensity, and dimensional precision is high, setting rate is fast, production efficiency is high, molding sand collapsibility is good, labour intensity is low, apply widely in producing at present.Furane resin are condensation resins that application quantity is maximum in Foundry Production up to now, and annual consumption has reached more than 500,000 tons.The furfuryl alcohol that furane resin refer to have furan nucleus does the general name of the resene of raw material production, and it is cured as insoluble and not molten solid substance in acidic medium, and the main raw material producing furane resin is furfuryl alcohol, formaldehyde and urea.First, carry out addition reaction in the basic conditions by urea and formaldehyde, generate monomethylolurea and dimethylolurea.Hydroxymethyl derivative carries out condensation reaction with furfuryl alcohol in acid condition, after vacuum hydro-extraction, obtains furane resin.The water deviate from resins synthesis, mainly from formaldehyde solution, is easy to be deviate from because boiling point is low at vacuum hydro-extraction stage unreacted formaldehyde, and furfuryl alcohol is due to hydrogen bond effect simultaneously, and also easy and water azeotropic steams.Cause in water, there is a large amount of furfuryl alcohols and a small amount of formaldehyde.If this waste water direct oxidation will consume a large amount of oxygenant, if the direct biochemical treatment of this waste water, will directly make bacterial classification inactivation.
At present, generally adopt the method such as burning, High Dose Oxygen agent oxide treatment to the process of furan resin waste water, energy consumption is large, and costly, and in waste water, active substance is underutilized.In addition, furane resin Free-formaldehyde content is the important technology index weighing resin, if resin Free-formaldehyde too high levels, then when operations such as mulling, moulding, sclerosis, formaldehyde can discharge, both contaminate environment, endangers again the healthy of operator.
Relevant furane resin and synthetic method thereof, we retrieve with Publication about Document:
1, Chinese patent, title: a kind of production technique Application Number (patent) of furan resin for casting: CN 201110407561.X open (bulletin) number: CN 102516482A applies for (patent right) people: Ningxia Gongxiang Group Co., Ltd. address: No. 199, concentric South Road, Xixia District, Yinchuan City of Ningxia Hui Autonomous Region invention (design) people: Jin Yi; He Long; Yang Yang; Make a summary in Korean: a kind of production technique of furan resin for casting, is characterized in that: it comprises the steps: to feed in raw material, heat temperature raising, dewater, open steam valve, is warming up to 80-108 DEG C, be incubated 60-90 minute, discharging and packaging put in storage in 20-30 minute; Technique provided by the invention can provide the product of a kind of low content of free formaldehyde, high strength, and the environmental protection that production link produces without the three wastes.
2, Chinese patent, title: a kind of furan resin for casting and preparation method thereof Application Number (patent): 201210377741.2 open (bulletin) number: CN102863600A apply for (patent right) people: Shengquan Group Co. Ltd., Jinan, address: Jinan City, Shandong Province Zhangqiu City Diao Zhen industrial economy development area, invention (design) people: Zhu Jianxun; Liu Zhao recommends; Sun Yongfeng, summary: a kind of furan resin for casting and preparation method thereof, its each composition synthesis primarily of following weight parts forms: 15-35 part formaldehyde, 5-10 part urea, 60-90 part furfuryl alcohol, 5-40 part xylogen.The present invention is by utilizing lignin modification furfuryl alcohol, and while reducing costs, its free formaldehyde content decrease to some degree, its first intensity and whole intensity are also improved to some extent simultaneously.
3, Chinese patent, title: a kind of low-cost high-strength furane resin and preparation method thereof Application Number (patent): CN201210398634.8 open (bulletin) number: CN 102875757A application (patent right) people: Chongqing Hao Jiang refractory materials limited liability company address: No. 200, great Ping village, Tong Guanyi town, Jiulongpo District, Chongqing City, invention (design) people: Liu Wei, summary: a kind of low-cost high-strength furane resin and preparation method thereof, , its formula and weight percentage thereof consist of: the formaldehyde 12%-30% of 36.5%, urea 3%-12%, furfuryl alcohol 35%-70%, trimeric cyanamide 0.5%-5%, industry Xylitol mother liquor 0.1%-25% and coupling agent 0.2%-0.8%, comprise the following steps: formaldehyde alkali reaction, urea alkali reaction, furfuryl alcohol acid-reaction, vacuum hydro-extraction and discharging.The invention has the beneficial effects as follows: obviously can reduce the consumption of furfuryl alcohol and reduce discharge of wastewater, thus realize the effect reducing production cost and energy consumption.
Although the furane resin of above-mentioned document and synthetic method thereof can synthesize the furane resin of casting, all adopt in raw material concentration be about 37% liquid formaldehyde, in formaldehyde solution moisture 63%, in polycondensation process, also to generate a certain amount of water.Therefore in the building-up process of resin, need to slough a large amount of processing wastewaters, the small organic molecule such as to mutter containing a large amount of free formaldehyde, methyl alcohol, methyl in waste water, COD value, up to tens thousand of, enter in water body and can cause very serious environmental pollution.
Summary of the invention
The object of this invention is to provide non-wastewater discharge in a kind of production process, the furane resin free formaldehyde content of synthesis lower than 0.1%, the cast iron furane resin that specific tenacity is high, viscosity is low and synthetic method thereof,
Technical scheme of the present invention is:
A kind of cast iron furane resin, it is characterized in that, its raw material and weight proportion are: furfuryl alcohol 60-80%, solid formaldehyde 5-15%, urea 5-15%, coupling agent 0.2-1.0% and water 5-10%.
The synthetic method of cast iron furane resin of the present invention, is characterized in that, comprise the following steps:
(1) water, furfuryl alcohol are added in reactor, start stirrer and stir, regulate pH value to 8.9-9.1 with basic catalyst;
(2) add urea, solid formaldehyde, add steam and heat up, keep heating up 8 DEG C for every 5 minutes, be warming up to 105-115 DEG C, insulation 120-180 minute;
(3) be cooled to 50 DEG C, add furfuryl alcohol and coupling agent, after stirring, obtain finished product.
The weight percentage of the furfuryl alcohol added in above-described step (1) is the 70%-80% of formula composition, and the furfuryl alcohol amount that described step (3) adds is the remaining part of furfuryl alcohol in formula composition.
Above-described solid formaldehyde is the paraformaldehyde of low polymerization degree, and content is 90.0-99.9%.
Above-described basic catalyst is one or more in sodium hydroxide, potassium hydroxide, trimeric cyanamide, vulkacit H.
Above-described coupling agent is silane coupling agent, for one or more in γ-aminopropyl triethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, silane coupling agent X-602, silane coupling agent Y-603.
Above-described cast iron furane resin building-up process can also add the polyvinyl alcohol of raw material total amount 2-3%, polyvinyl alcohol is a kind of macromolecular compound with great amount of hydroxy group, polyvinyl alcohol hemiacetal and polyvinyl acetal can be obtained with formaldehyde reaction, polyvinyl alcohol and polyvinyl formal itself have adhesiveproperties, make furane resin have good cementability.In addition, the part polyethylene alcohol not participating in reacting will become the trapping agent of formaldehyde, makes the free formaldehyde content in furane resin be reduced to 0.005%.
The substantive distinguishing features that the present invention gives prominence to and significant progress are:
1, solid formaldehyde is adopted to replace liquid formaldehyde in cast iron furane resin building-up process of the present invention, decrease the link of dewatering in building-up process, not only fundamentally solve the difficult problem that former technique produces contaminated wastewater, and dehydration required time 1 hour can also be reduced, reduce the energy consumption 100 yuan/ton of dewatering and producing, reduce discharge of wastewater 100kg/ ton, product performance improve 10%, reach environmental protection, energy-conservation, the object that increases benefit, there is significant Social and economic benef@.
2, add coupling agent in hot core box for casting resin synthesis process of the present invention, the intensity of resin is greatly improved, and 24h intensity reaches more than 2.6MPa, can reduce its add-on, thus reduces ton sand cost.
3, to have viscosity low for cast iron furane resin of the present invention, and be convenient to metering, easy mulling, sand fluidity is good; Specific tenacity is high, can reduce resin amount, reduces production cost, simultaneously favourable raising casting quality.
4, cast iron furane resin free formaldehyde content of the present invention is lower than 0.1%, and in production process, smell is little, improves workman's working conditions, decreases environmental pollution.
5, the molding sand collapsibility of cast iron furane resin of the present invention is good, reduces sand removal workload after producing, and improves working efficiency, and the casting dimension accuracy of producing is high, clear-cut, any surface finish.
Embodiment
embodiment 1
By furfuryl alcohol 1600kg, solid formaldehyde 137kg, urea 130kg, coupling agent 9kg and water 124kg, make through following steps:
(1) water, furfuryl alcohol are added in reactor, start stirrer and stir, regulate pH value to 8.9-9.1 with sodium hydroxide;
(2) add urea, solid formaldehyde, add steam and heat up, keep heating up 8 DEG C for every 5 minutes, be warming up to 105-115 DEG C, be incubated 120 minutes;
(3) be cooled to 50 DEG C, add furfuryl alcohol and coupling agent, after stirring, obtain finished product.
Above-described solid formaldehyde is the paraformaldehyde of low polymerization degree, and content is 90.0%.
The weight percentage of the furfuryl alcohol added in above-described step (1) is 70% of formula composition, and the furfuryl alcohol amount that described step (3) adds is the remaining part of furfuryl alcohol in formula composition.
embodiment 2
By furfuryl alcohol 3850kg, solid formaldehyde 396kg, urea 377kg, coupling agent 27kg and water 350kg, make through following steps:
(1) water, furfuryl alcohol are added in reactor, start stirrer and stir, regulate pH value to 8.9-9.1 with potassium hydroxide;
(2) add urea, solid formaldehyde, add steam and heat up, keep heating up 8 DEG C for every 5 minutes, be warming up to 105-115 DEG C, be incubated 140 minutes;
(3) be cooled to 50 DEG C, add furfuryl alcohol and coupling agent, after stirring, obtain finished product.
Above-described solid formaldehyde is the paraformaldehyde of low polymerization degree, and content is 96.0%.
The weight percentage of the furfuryl alcohol added in above-described step (1) is 75% of formula composition, and the furfuryl alcohol amount that described step (3) adds is the remaining part of furfuryl alcohol in formula composition.
embodiment 3
By furfuryl alcohol 1480kg, solid formaldehyde 180kg, urea 170kg, coupling agent 10kg and water 160kg, make through following steps:
(1) water, furfuryl alcohol are added in reactor, start stirrer and stir, regulate pH value to 8.9-9.1 with sodium hydroxide;
(2) add urea, solid formaldehyde, add steam and heat up, keep heating up 8 DEG C for every 5 minutes, be warming up to 105-115 DEG C, be incubated 160 minutes;
(3) be cooled to 50 DEG C, add furfuryl alcohol and coupling agent, after stirring, obtain finished product.
Above-described solid formaldehyde is the paraformaldehyde of low polymerization degree, and content is 93.0%.
The weight percentage of the furfuryl alcohol added in above-described step (1) is 78% of formula composition, and the furfuryl alcohol amount that described step (3) adds is the remaining part of furfuryl alcohol in formula composition.
embodiment 4
By furfuryl alcohol 675kg, solid formaldehyde 112kg, urea 108kg, coupling agent 4kg and water 100kg, make through following steps:
(1) water, furfuryl alcohol are added in reactor, start stirrer and stir, regulate pH value to 8.9-9.1 with potassium hydroxide and trimeric cyanamide;
(2) add urea, solid formaldehyde, add steam and heat up, keep heating up 8 DEG C for every 5 minutes, be warming up to 105-115 DEG C, be incubated 180 minutes;
(3) be cooled to 50 DEG C, add furfuryl alcohol and coupling agent, after stirring, obtain finished product.
Above-described solid formaldehyde is the paraformaldehyde of low polymerization degree, and content is 99.9%.
The weight percentage of the furfuryl alcohol added in above-described step (1) is 80% of formula composition, and the furfuryl alcohol amount that described step (3) adds is the remaining part of furfuryl alcohol in formula composition.
The technical indicator of cast iron furane resin of the present invention:
Claims (6)
1. cast iron furane resin, is characterized in that, its raw material and weight proportion are: furfuryl alcohol 60-80%, solid formaldehyde 5-15%, urea 5-15%, coupling agent 0.2-1.0% and water 5-10%.
2. the synthetic method of cast iron furane resin according to claim 1, is characterized in that, comprise the following steps:
(1) water, furfuryl alcohol are added in reactor, start stirrer and stir, regulate pH value to 8.9-9.1 with basic catalyst;
(2) add urea, solid formaldehyde, add steam and heat up, keep heating up 8 DEG C for every 5 minutes, be warming up to 105-115 DEG C, insulation 120-180 minute;
(3) be cooled to 50 DEG C, add furfuryl alcohol and coupling agent, after stirring, obtain finished product.
3. the synthetic method of a kind of cast steel furane resin according to claim 2, it is characterized in that: the weight percentage of the furfuryl alcohol added in described step (1) is the 70%-80% of formula composition, the furfuryl alcohol amount that described step (3) adds is the remaining part of furfuryl alcohol in formula composition.
4. the synthetic method of a kind of cast steel furane resin according to claim 2, it is characterized in that: described solid formaldehyde is the paraformaldehyde of low polymerization degree, content is 90.0-99.9%.
5. the synthetic method of a kind of cast steel furane resin according to claim 2, is characterized in that: described basic catalyst is one or more in sodium hydroxide, potassium hydroxide, trimeric cyanamide, vulkacit H.
6. the synthetic method of a kind of cast steel furane resin according to claim 2, is characterized in that: described coupling agent is silane coupling agent; For one or more in γ-aminopropyl triethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, silane coupling agent X-602, silane coupling agent Y-603.
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| CN201410434225.8A CN104262560B (en) | 2014-08-29 | 2014-08-29 | Furane resins and synthetic method thereof for cast iron |
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| CN201410434225.8A CN104262560B (en) | 2014-08-29 | 2014-08-29 | Furane resins and synthetic method thereof for cast iron |
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| CN104262560B CN104262560B (en) | 2016-05-18 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105537503A (en) * | 2016-02-29 | 2016-05-04 | 无锡烨隆精密机械有限公司 | Sand burning preventive precoated sand for casting of turbine casing |
| 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 |
| CN107778491A (en) * | 2017-10-26 | 2018-03-09 | 苏州兴业材料科技股份有限公司 | A kind of preparation method of 3D printing furane resins |
| CN108715750A (en) * | 2018-06-06 | 2018-10-30 | 山东怡泰恒环保材料有限公司 | A kind of cast iron binder |
| CN108727549A (en) * | 2018-05-29 | 2018-11-02 | 宁夏共享化工有限公司 | A kind of modified urea-formaldehyde furane resins |
| CN108889898A (en) * | 2018-06-06 | 2018-11-27 | 山东怡泰恒环保材料有限公司 | A kind of cast aluminium binder |
| 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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| CN102532450A (en) * | 2011-12-12 | 2012-07-04 | 宁夏共享集团有限责任公司 | Production method for quickly curing nitrogen-free furane resin |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105537503A (en) * | 2016-02-29 | 2016-05-04 | 无锡烨隆精密机械有限公司 | Sand burning preventive precoated sand for casting of turbine casing |
| 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 |
| 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 |
| 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 |
| CN107778491A (en) * | 2017-10-26 | 2018-03-09 | 苏州兴业材料科技股份有限公司 | A kind of preparation method of 3D printing furane resins |
| CN107778491B (en) * | 2017-10-26 | 2020-12-11 | 苏州兴业材料科技股份有限公司 | Preparation method of furan resin for 3D printing |
| CN108727549A (en) * | 2018-05-29 | 2018-11-02 | 宁夏共享化工有限公司 | A kind of modified urea-formaldehyde furane resins |
| CN108715750A (en) * | 2018-06-06 | 2018-10-30 | 山东怡泰恒环保材料有限公司 | A kind of cast iron binder |
| CN108889898B (en) * | 2018-06-06 | 2019-12-31 | 孙梓宁 | Adhesive for cast aluminum |
| CN108889898A (en) * | 2018-06-06 | 2018-11-27 | 山东怡泰恒环保材料有限公司 | A kind of cast aluminium binder |
| 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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