CN105273151A - Modified phenolic furan resin and binder adopting same - Google Patents
Modified phenolic furan resin and binder adopting same Download PDFInfo
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- CN105273151A CN105273151A CN201510683510.8A CN201510683510A CN105273151A CN 105273151 A CN105273151 A CN 105273151A CN 201510683510 A CN201510683510 A CN 201510683510A CN 105273151 A CN105273151 A CN 105273151A
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Abstract
The invention belongs to the technical field of organic chemistry and discloses modified phenolic furan resin. The modified phenolic furan resin is prepared through steps as follows: formaldehyde and phenol are stirred and mixed in certain mole ratio and are subjected to heating, heat preservation and dehydration under the action of a basic catalyst, a polyamine compound is added for an addition reaction, meanwhile, long-chain molecules are introduced and taken as a chain-extension toughening modifier, furfuryl alcohol is added, a product is subjected to acidic heating and heat preservation, and the resin is obtained; finally, furfuryl alcohol and silane are added, and a binder is obtained. The furan resin has good high temperature deformability and is suitable for steel casting production.
Description
Technical field
The invention belongs to technical field of organic chemistry, be specifically related to resin, the furan resin for casting that particularly a kind of hot deformability is excellent and binding agent.
Background technology
Foundry Production has the history of more than 5000 year, the application of the synthetic binding agent only thing of 50 or six ten years.In recent years, self-hardening resin sand is widely used in the Foundry Production of countries in the world, is one that in foundry resin, consumption is maximum at China's furane resin.
Furan resin-sand can be hardened by additional acid curing agent at normal temperatures, core strength is high, ventilation property is strong, is out of shape little, and collapsibility is good, and surface finish of casting is good, and dimensional precision is high; Reduce labor intensity, production efficiency advantages of higher.The exploitation of furan resin-sand Modeling Technology, change the labour intensity that cast steel exists for a long time large, dust is high, and production efficiency is low, the backward situation of casting quality difference.
But Castings Produce with Furan Resin foundry goods, particularly the hot cracking tendency of steel casting is serious, its major cause is that furan resin-sand is within the scope of 300-600 DEG C, along with the rising of temperature, intensity just sharply declines, and Castings Produce with Furan Resin has heat insulating ability, in its core, the change of temperature is slowly, within latter 7 hours, just can reach 330 DEG C pouring into a mould apart from the molding sand at foundry goods and mold―metal interface 100mm place, this shows that the overwhelming majority of sand mold can keep higher intensity and rigidity, that is the overall deformability of casting mold is very poor, foundry goods will be hindered in casting solidification contraction process to shrink, cast-internal is made to produce larger string stress, even crack.Solve this defect, generally take the increasing sulphur, the phosphorization that suppress steel casting; Reduce resin amount; Add the measure such as wood powder and prevent crackle, but this all do not have from furane resin production technique set about making the producer of production foundry goods on the basis not changing original tooling device by original explained hereafter foundry goods come facilitate feasible.
A kind of fast mould is lacked for sand mold casting in prior art.The present invention therefore.
Summary of the invention
The object of the invention is to provide a kind of furan resin for casting and binding agent thereof, very poor to overcome the overall deformability of casting mold in prior art, in casting solidification contraction process, hinder foundry goods to shrink, make cast-internal produce larger string stress, the defect even cracked.
In order to solve these problems of the prior art, casting modified phenolic furane resin provided by the invention, it prepares as follows:
(1) formaldehyde, phenol are uniformly mixed by the mol ratio 1.4 ~ 2.5 of aldehyde/phenol, pH value 8 ~ 10 under basic catalyst, heating and thermal insulation, dehydration;
(2) in reaction system, add polyhydric amine compounds and carry out addition reaction, add-on is reaction system gross weight 0.5wt ~ 8wt%; Add the long chain type molecule as chain extension plasticized modifier, add-on is reaction system gross weight 1wt ~ 20wt% simultaneously, reaction 0.5-1.5 hour;
(3) add furfuryl alcohol again, furfuryl alcohol add-on is the 40wt ~ 70wt% of reaction system gross weight, regulates pH to be 4.5 ~ 5.0, temperature rising reflux 1 ~ 2 hour; Cooling is neutralized to pH=7 ± 0.7, obtains phenolic aldehyde furane resin product.
The preferred technical scheme of the present invention: the formaldehyde in described step (1), the mol ratio of phenol are preferably 1.7 ~ 2.0.
The preferred technical scheme of the present invention: the polyhydric amine compounds in described step (2) is selected from: aliphatic polyhydric amine compounds or aromatic polyvalent amine compound.
The preferred technical scheme of the present invention: the polyhydric amine compounds in described step (2) is selected from: one or more in Diethylenetriaminee (DETA), triethylenetetramine, diethylamine, quadrol, pentanoic, tolylene diamine, pentanoic.
The preferred technical scheme of the present invention: the long chain type molecule in described step (2) is selected from: alkylene substituted phenol long chain type molecule, monose long chain type molecule, polyphenol long chain type molecule.
The preferred technical scheme of the present invention: the long chain type molecule in described step (2) is selected from: cardanol, wooden chaff, glucose, semi-lactosi, Resorcinol, pyrocatechol, the ninth of the ten Heavenly Stems one or more in phenol, flavan-3-alcohol.
Temperature of reaction in the preparation method of resin of the present invention is 60 ~ 100 DEG C.
Long chain type molecule adds and belongs to a kind of resol chemical modification, belongs to molecule intrinsic toughening material.The viscous liquid that cashew nut shell oil is a kind of extraction from ripe cashew nut shell and obtains, its primary structure position is with monoene or the diolefin long-chain of 15 carbon between phenol, namely phenolic compound feature is had, there is again the flexibility of fatty compounds, use its modified phenolic resins, toughness has clear improvement, then the introducing of long molecular chain affects its thermotolerance again greatly, thus, when long molecular chain is introduced, add the diamine compound rigid radical that thermotolerance is good, increase the deflection of resol by external force, thus add the toughness of resin molding, improve the cohesive strength of resin molding.
Modified phenolic furane resin are used in casting, and it prepares as follows:
(1) formaldehyde, phenol are uniformly mixed by the mol ratio 1.4 ~ 2.5 of aldehyde/phenol, pH value 8 ~ 10 under basic catalyst, temperature rising reflux 1-2 hour, is cooled to 60 DEG C, vacuum hydro-extraction;
(2) in reaction system, add polyhydric amine compounds and carry out addition reaction, add-on is reaction system gross weight 0.5wt ~ 8wt%; Add the long chain type molecule as chain extension plasticized modifier, add-on is reaction system gross weight 1wt ~ 20wt% simultaneously, temperature rising reflux reaction 0.5-1.5 hour;
(3) lower the temperature, then add furfuryl alcohol, furfuryl alcohol add-on is the 40wt ~ 70wt% of reaction system gross weight, regulates pH to be 4.5 ~ 5.0, temperature rising reflux 1 ~ 2 hour; Cooling is neutralized to pH=7 ± 0.7, and obtain resin product, in whole reaction process, temperature of reaction is 60 ~ 100 DEG C.
A second aspect of the present invention provides a kind of casting modified phenolic furane resin binding agent, and it is characterized in that, it according to mass percent is: modified phenolic furane resin 20-65wt%, furfuryl alcohol 20-79wt%, silane 0.1-1.0wt%.
Preferably, a kind of casting modified phenolic furane resin binding agent, it according to mass percent is: modified phenolic furane resin 30-50wt%, furfuryl alcohol 49.9-69wt%, silane 0.1-1.0wt%.
Preferably, a kind of casting modified phenolic furane resin binding agent, it according to mass percent is: modified phenolic furane resin 30wt%, furfuryl alcohol 69wt%, silane 1wt%.
Preferably, a kind of casting modified phenolic furane resin binding agent, it according to mass percent is: modified phenolic furane resin 50wt%, furfuryl alcohol 49.9wt%, silane 0.1-1.0wt%.
Compared to solution of the prior art, the furane resin of gained of the present invention have good hot deformability energy, are applicable to the production of steel casting.Obtained by the present invention, the plasticity-of sand mold too increases, and improves deformability.This just greatly reduces the hot cracking tendency with Furan Resin-Bonded Sand foundry goods.
Accompanying drawing explanation
Fig. 1 is the thermal distortion comparison diagram of the Castings Produce with Furan Resin of furane resin of the present invention and prior art.
Embodiment
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiments are not limited to for illustration of the present invention limit the scope of the invention.The implementation condition adopted in embodiment can do further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
Embodiment 1
The preparation of modified furan resin: by the oil bath pan adding 100 gram of 37% formaldehyde, the four-hole boiling flask having agitator, reflux exchanger and thermometer of 77.8 grams of phenol is placed in temperature-adjustable, open and stir, between appropriate 10% sodium hydroxide solution adjust pH 8 ~ 10, temperature rising reflux 1 ~ 2 hour, be cooled to less than 60 DEG C, vacuum removal moisture content.Cooling adds quadrol 15 grams of cardanols 25 grams, glucose 20 grams, temperature rising reflux 0.5 ~ 1 hour; Cooling adds 114 grams of furfuryl alcohols, adjusts pH4.5 ~ 5.0, temperature rising reflux 1 ~ 2 hour with 10% hydrochloric acid soln; Cooling is neutralized to pH=7 ± 0.7, namely produces to obtain base resin of the present invention.
Embodiment 2-1
Modified phenolic furane resin binding agent, according to mass percent is: the resin 30wt% that embodiment 1 prepares, furfuryl alcohol 69.7wt%, silane 0.3wt%, and stirring at normal temperature is even, makes finished product.
Embodiment 2-2
Modified phenolic furane resin binding agent, according to mass percent is: the resin 50wt% that embodiment 1 obtains, furfuryl alcohol 49.7wt%, silane 0.3wt%, and stirring at normal temperature is even, makes finished product.
Illustrate with the heat distortion amount of obtained its heat distortion amount of sample of furane resin of the present invention much smaller than general furane resin (without nitrogen) according to the test of heat distortion amount below.As can be seen from the data of thermal distortion test, the heat distortion amount of general furane resin (without nitrogen) is 2.58mm, is 1.54mm with base resin (embodiment 2-1) of the present invention, (embodiment 2-2), its heat distortion amount just only has 1.01mm, is only original 39%.Seen by the shape of thermomechanical curve, obtained by the present invention, the plasticity-of sand mold too increases, and improves deformability.This just greatly reduces the hot cracking tendency with Furan Resin-Bonded Sand foundry goods.
Table 1 binding agent composition and thermal distortion test thereof
Above-mentioned example, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to spirit of the present invention or modification, all should be encompassed within protection scope of the present invention.
Claims (8)
1. modified phenolic furane resin, it prepares as follows:
(1) formaldehyde, phenol are uniformly mixed by the mol ratio 1.4 ~ 2.5 of aldehyde/phenol, pH value 8 ~ 10 under basic catalyst, heating and thermal insulation, dehydration;
(2) in reaction system, add polyhydric amine compounds and carry out addition reaction, add-on is reaction system gross weight 0.5wt ~ 8wt%; Add the long chain type molecule as chain extension plasticized modifier, add-on is reaction system gross weight 1wt ~ 20wt% simultaneously, reaction 0.5-1.5 hour;
(3) add furfuryl alcohol again, furfuryl alcohol add-on is the 40wt ~ 70wt% of reaction system gross weight, regulates pH to be 4.5 ~ 5.0, temperature rising reflux 1 ~ 2 hour; Cooling is neutralized to pH=7 ± 0.7, obtains resin product.
2. modified phenolic furane resin according to claim 1, is characterized in that, the formaldehyde in described step (1), the mol ratio of phenol are preferably 1.7 ~ 2.0.
3. modified phenolic furane resin according to claim 1, is characterized in that, the polyhydric amine compounds in described step (2) is selected from: aliphatic polyhydric amine compounds or aromatic polyvalent amine compound.
4. modified phenolic furane resin according to claim 1, it is characterized in that, the polyhydric amine compounds in described step (2) is selected from: one or more in Diethylenetriaminee (DETA), triethylenetetramine, diethylamine, quadrol, pentanoic, tolylene diamine, pentanoic.
5. modified phenolic furane resin according to claim 1, is characterized in that, the long chain type molecule in described step (2) is selected from: alkylene substituted phenol long chain type molecule, monose long chain type molecule, polyphenol long chain type molecule.
6. modified phenolic furane resin according to claim 1, it is characterized in that, the long chain type molecule in described step (2) is selected from: cardanol, wooden chaff, glucose, semi-lactosi, Resorcinol, pyrocatechol, the ninth of the ten Heavenly Stems one or more in phenol, flavan-3-alcohol.
7. a modified phenolic furane resin binding agent, is characterized in that, it is the modified phenolic furane resin 20-65wt% as described in any one of claim 1-6, furfuryl alcohol 20-79wt%, silane 0.1-1.0wt% according to mass percent.
8. modified phenolic furane resin binding agent according to claim 7, it is characterized in that, it according to mass percent is: modified phenolic furane resin 30-50wt%, furfuryl alcohol 49.9-69wt%, silane 0.1-1.0wt%.
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| CN201510683510.8A CN105273151B (en) | 2015-10-20 | 2015-10-20 | Modified phenolic furane resins and its binder |
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| CN105273151B CN105273151B (en) | 2018-08-03 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110653332A (en) * | 2019-09-30 | 2020-01-07 | 宁夏共享化工有限公司 | Furan resin for casting and preparation method thereof |
| CN113414344A (en) * | 2021-06-23 | 2021-09-21 | 宁夏共享化工有限公司 | Self-hardening furan resin for low-moisture casting and preparation method thereof |
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| CN101121191A (en) * | 2007-09-26 | 2008-02-13 | 济南圣泉集团股份有限公司 | Casting core sand synthetic resin adhesive |
| CN103242500A (en) * | 2013-05-24 | 2013-08-14 | 山东圣泉化工股份有限公司 | Preparation method of phenol modified urea resin |
| CN104193935A (en) * | 2014-08-29 | 2014-12-10 | 玉林市兰科铸造材料有限公司 | Furan resin for cast steel and synthesis method thereof |
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2015
- 2015-10-20 CN CN201510683510.8A patent/CN105273151B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121191A (en) * | 2007-09-26 | 2008-02-13 | 济南圣泉集团股份有限公司 | Casting core sand synthetic resin adhesive |
| CN103242500A (en) * | 2013-05-24 | 2013-08-14 | 山东圣泉化工股份有限公司 | Preparation method of phenol modified urea resin |
| CN104193935A (en) * | 2014-08-29 | 2014-12-10 | 玉林市兰科铸造材料有限公司 | Furan resin for cast steel and synthesis method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110653332A (en) * | 2019-09-30 | 2020-01-07 | 宁夏共享化工有限公司 | Furan resin for casting and preparation method thereof |
| CN110653332B (en) * | 2019-09-30 | 2021-05-11 | 宁夏共享化工有限公司 | Preparation method of furan resin for casting |
| CN113414344A (en) * | 2021-06-23 | 2021-09-21 | 宁夏共享化工有限公司 | Self-hardening furan resin for low-moisture casting and preparation method thereof |
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