CN105273151B - Modified phenolic furane resins and its binder - Google Patents
Modified phenolic furane resins and its binder Download PDFInfo
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- CN105273151B CN105273151B CN201510683510.8A CN201510683510A CN105273151B CN 105273151 B CN105273151 B CN 105273151B CN 201510683510 A CN201510683510 A CN 201510683510A CN 105273151 B CN105273151 B CN 105273151B
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- furane resins
- modified phenolic
- furfuryl alcohol
- phenol
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Abstract
The invention belongs to technical field of organic chemistry, disclose a kind of modified phenolic furane resins, are prepared via a method which to obtain：Formaldehyde, phenol are stirred by certain mol proportion, under basic catalyst, heating and thermal insulation, dehydration is added polyhydric amine compounds and carries out addition reaction, while introducing long chain type molecule as chain extension plasticized modifier, and furfuryl alcohol, acid heating and thermal insulation is added to obtain resin；It is eventually adding furfuryl alcohol and silane obtains binder.The furane resins of gained of the invention have good hot deformability energy, are suitable for the production of steel-casting.
Description
Technical field
The invention belongs to technical field of organic chemistry, and in particular to resin, more particularly to a kind of hot deformability are excellent
Furan resin for casting and binder.
Background technology
Foundry Production has more than 5000 years history, the application of artificial synthesized binder only 50 or six ten years things.
In recent years, self-hardening resin sand is widely used in the Foundry Production of countries in the world, and in China, furane resins are foundry resins
The most one kind of middle dosage.
Furan resin-sand can be hardened at normal temperatures by additional acid curing agent, core strength is high, gas permeability is strong, be become
Shape is small, and collapsibility is good, and surface finish of casting is good, and dimensional accuracy is high；It reduces labor intensity, the advantages that production efficiency is high.Furans
The exploitation of phenolic sand molding technology, changing cast steel, existing labor intensity is big for a long time, and dust is high, low production efficiency, casting
The ropy backward situation of part.
But the hot cracking tendency of Castings Produce with Furan Resin casting, especially steel-casting is serious, the main reason is that furan resin-sand
Within the scope of 300-600 DEG C, with the rising of temperature, intensity just drastically declines, and Castings Produce with Furan Resin has thermal insulation, type
The variation of in-core temperature is slow, can be only achieved 330 within 7 hours after away from the molding sand cast at casting and mold―metal interface 100mm
DEG C, this shows that the overwhelming majority of sand mold can keep higher intensity and rigidity, that is to say, that the whole deformability of casting mold is very poor,
Casting will be hindered to shrink in casting solidification contraction process, so that cast-internal is generated larger shrinkage stress, or even generate and split
Line.This defect is solved, the increasing sulphur for inhibiting steel-casting, phosphorization are generally taken；Reduce resin amount；The measures such as wood powder are added to come
Crackle is prevented, but this does not all set about making the producer of production casting not changing original tooling device from furane resins production technology
On the basis of to facilitate by original technique productions casting it is feasible.
Lack a kind of fast mould in the prior art and is used for sand casting.The present invention is therefore.
Invention content
Present invention aims at providing a kind of furan resin for casting and its binder, to overcome casting mold in the prior art
Whole deformability is very poor, hinders casting to shrink in casting solidification contraction process, cast-internal is made to generate larger shrinkage stress,
The defect even cracked.
In order to solve the problems, such as it is in the prior art these, it is provided by the invention casting use modified phenolic furane resins, lead to
Following steps are crossed to be prepared：
(1) formaldehyde, phenol are stirred by the molar ratio 1.4~2.5 of aldehyde/phenol, under basic catalyst pH value 8~
10, heating and thermal insulation, dehydration；
(2) polyhydric amine compounds are added in the reaction system and carry out addition reaction, addition is reaction system total weight
0.5wt~8wt%；The long chain type molecule as chain extension plasticized modifier is added simultaneously, addition is reaction system total weight 1wt
~20wt% reacts 0.5-1.5 hours；
(3) add furfuryl alcohol, furfuryl alcohol addition is 40wt~70wt% of reaction system total weight, adjust pH be 4.5~
5.0, temperature rising reflux 1~2 hour；Cooling is neutralized to pH=7 ± 0.7, up to phenolic aldehyde furane resins product.
A currently preferred technical solution：The molar ratio of formaldehyde, phenol in the step (1) is preferably 1.7~
2.0。
A currently preferred technical solution：Polyhydric amine compounds in the step (2) are selected from：Aliphatic polyamine
Compound or aromatic polyvalent amine compounds.
A currently preferred technical solution：Polyhydric amine compounds in the step (2) are selected from：Diethylentriamine, three
One or more of ethylene tetramine, diethylamine, ethylenediamine, diphenylamines, toluenediamine, diphenylamines.
A currently preferred technical solution：Long chain type molecule in the step (2) is selected from：Alkylene substituted phenol long-chain
Type molecule, monosaccharide long chain type molecule, polyphenol long chain type molecule.
A currently preferred technical solution：Long chain type molecule in the step (2) is selected from：Anacardol, the wooden chaff, grape
Sugar, galactolipin, resorcinol, catechol, nonyl one or more of phenol, flavan-3-alcohol.
Reaction temperature in the preparation method of resin of the present invention is 60~100 DEG C.
The addition of long chain type molecule belongs to a kind of phenolic resin chemical modification, belongs to intramolecular plasticizing substance.Cashew nut shell oil is one
Kind viscous liquid obtained by being extracted in ripe cashew nut shell, primary structure is one 15 carbon of band in the meta position of phenol
Monoene or diolefin long-chain, that is, have phenolic compound feature, and has the flexibility of aliphatic compound, with its phenol-formaldehyde resin modified,
Toughness has clear improvement, and the then introducing of long chain largely effects on its heat resistance again, thus, when long chain introduces, add
Enter the good diamine compound rigid radical of heat resistance, increases deflection of the phenolic resin by external force, to increase resin
The toughness of film improves the cohesive strength of resin film.
Casting modified phenolic furane resins, are made by the steps to obtain：
(1) formaldehyde, phenol are stirred by the molar ratio 1.4~2.5 of aldehyde/phenol, under basic catalyst pH value 8~
10, temperature rising reflux 1-2 hours is cooled to 60 DEG C, vacuum dehydration；
(2) polyhydric amine compounds are added in the reaction system and carry out addition reaction, addition is reaction system total weight
0.5wt~8wt%；The long chain type molecule as chain extension plasticized modifier is added simultaneously, addition is reaction system total weight 1wt
~20wt%, temperature rising reflux react 0.5-1.5 hours；
(3) cool down, add furfuryl alcohol, furfuryl alcohol addition is 40wt~70wt% of reaction system total weight, adjusts pH and is
4.5~5.0, temperature rising reflux 1~2 hour；Cooling is neutralized to pH=7 ± 0.7 to get resin product, anti-in entire reaction process
It is 60~100 DEG C to answer temperature.
The second aspect of the present invention provides a kind of casting modified phenolic furane resins binder, which is characterized in that it is pressed
It is according to mass percent：Modified phenolic furane resins 20-65wt%, furfuryl alcohol 20-79wt%, silane 0.1-1.0wt%.
Preferably, a kind of cast uses modified phenolic furane resins binder, is according to mass percent：Modified phenolic furan
Furane resins 30-50wt%, furfuryl alcohol 49.9-69wt%, silane 0.1-1.0wt%.
Preferably, a kind of cast uses modified phenolic furane resins binder, is according to mass percent：Modified phenolic furan
Furane resins 30wt%, furfuryl alcohol 69wt%, silane 1wt%.
Preferably, a kind of cast uses modified phenolic furane resins binder, is according to mass percent：Modified phenolic furan
Furane resins 50wt%, furfuryl alcohol 49.9wt%, silane 0.1-1.0wt%.
The furane resins of solution in compared with the prior art, present invention gained have good hot deformability
Can, it is suitable for the production of steel-casting.The plasticity of sand mold obtained by the present invention also increases, and improves deformability.This is just significantly
Reduce the hot cracking tendency with Furan Resin-Bonded Sand casting.
Description of the drawings
Fig. 1 is that figure is compared in the thermal deformation of the Castings Produce with Furan Resin of furane resins of the present invention and the prior art.
Specific implementation mode
Said program is described further below in conjunction with specific embodiment.It should be understood that these embodiments are for illustrating
The present invention and be not limited to limit the scope of the invention.The implementation condition used in embodiment can be done according to the condition of specific producer
Further adjustment, the implementation condition being not specified is usually the condition in routine experiment.
Embodiment 1
The preparation of modified furan resin：100 gram of 37% formaldehyde will be added, 77.8 grams of phenol has blender, a reflux
The four-hole boiling flask of condenser and thermometer is placed in the oil bath pan of temperature-adjustable, stirring is opened, with appropriate 10% sodium hydroxide
Between solution tune pH value 8~10, temperature rising reflux 1~2 hour is cooled to 60 DEG C hereinafter, vacuum removal moisture content.Second two is added in cooling
15 grams of amine, 25 grams of anacardol, 20 grams of glucose, temperature rising reflux 0.5~1 hour；Cooling plus 114 grams of furfuryl alcohols, with 10% hydrochloric acid solution
Adjust pH4.5~5.0, temperature rising reflux 1~2 hour；Cooling is neutralized to pH=7 ± 0.7, that is, the base resin for producing of the invention.
Embodiment 2-1
Modified phenolic furane resins binder is according to mass percent：The resin 30wt% that embodiment 1 is prepared,
Furfuryl alcohol 69.7wt%, silane 0.3wt%, stirring at normal temperature is uniform, and finished product is made.
Embodiment 2-2
Modified phenolic furane resins binder is according to mass percent：The resin 50wt% that embodiment 1 obtains, furfuryl alcohol
49.7wt%, silane 0.3wt%, stirring at normal temperature is uniform, and finished product is made.
Illustrate that its heat distortion amount of sample made from the furane resins with the present invention is remote according to the test of heat distortion amount below
Less than the heat distortion amount of general furane resins (nitrogen-free).The data tested from thermal deformation can be seen that general furane resins (nothing
Nitrogen) heat distortion amount be 2.58mm, with the present invention base resin (embodiment 2-1) be 1.54mm, (embodiment 2-2), thermal change
Shape amount just only has 1.01mm, is only original 39%.It is seen by the shape of thermomechanical curve, the plasticity of sand mold obtained by the present invention
It also increases, improves deformability.This is greatly lowered the hot cracking tendency with Furan Resin-Bonded Sand casting.
1 binder of table forms and its thermal deformation test
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow the person skilled in the art to be
It cans understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention.It is all smart according to the present invention
The equivalent transformation or modification that refreshing essence is done, should be covered by the protection scope of the present invention.
Claims (3)
1. modified phenolic furane resins are made by the steps to obtain：
(1) formaldehyde, phenol are stirred by the molar ratio 1.4~2.5 of aldehyde/phenol, pH value 8~10, adds under basic catalyst
Heat heat preservation, dehydration；
(2) in the reaction system be added polyhydric amine compounds carry out addition reaction, addition be reaction system total weight 0.5wt~
8wt%；Be added long chain type molecule as chain extension plasticized modifier simultaneously, addition be reaction system total weight 1wt~
20wt% reacts 0.5-1.5 hours；
Polyhydric amine compounds are selected from：One or more of diethylentriamine, triethylenetetramine, ethylenediamine, toluenediamine；
Long chain type molecule is selected from：One or more of anacardol, glucose, galactolipin；
(3) furfuryl alcohol is added, furfuryl alcohol addition is 40wt~70wt% of reaction system total weight, and it is 4.5~5.0 to adjust pH,
Temperature rising reflux 1~2 hour；Cooling is neutralized to pH=7 ± 0.7, up to resin product.
2. modified phenolic furane resins according to claim 1, which is characterized in that formaldehyde, phenol in the step (1)
Molar ratio be preferably 1.7~2.0.
3. a kind of modified phenolic furane resins binder, which is characterized in that it is according to mass percent：Such as claims 1 or 2
Modified phenolic the furane resins 30-50wt%, furfuryl alcohol 49.9-69wt%, silane 0.1-1.0wt%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510683510.8A CN105273151B (en) | 2015-10-20 | 2015-10-20 | Modified phenolic furane resins and its binder |
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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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| CN105273151A CN105273151A (en) | 2016-01-27 |
| CN105273151B true CN105273151B (en) | 2018-08-03 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| CN113414344B (en) * | 2021-06-23 | 2023-04-25 | 共享新材料(山东)有限公司 | Preparation method of low-moisture self-hardening furan resin for casting |
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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 |
| CN103242500B (en) * | 2013-05-24 | 2015-06-17 | 山东圣泉新材料股份有限公司 | 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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