CN105669927B - A kind of preparation method of the high intensity furane resins of low furfuryl alcohol content - Google Patents
A kind of preparation method of the high intensity furane resins of low furfuryl alcohol content Download PDFInfo
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- CN105669927B CN105669927B CN201610126957.XA CN201610126957A CN105669927B CN 105669927 B CN105669927 B CN 105669927B CN 201610126957 A CN201610126957 A CN 201610126957A CN 105669927 B CN105669927 B CN 105669927B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
Abstract
The present invention provides a kind of preparation methods of the high intensity furane resins of low furfuryl alcohol content, including：After furfuryl alcohol and coupling agent are mixed evenly, reaction at a certain temperature at the first time, generates furfuryl alcohol small molecule just polymers；In the reaction vessel, urea and formaldehyde carry out addition reaction；After addition reaction, the first polymers of furfuryl alcohol small molecule for accounting for furfuryl alcohol total amount one third is added, carries out pyroreaction；After pyroreaction, the first polymers of furfuryl alcohol small molecule for accounting for furfuryl alcohol total amount one third is added, turns off steam, stirring the second time of cooling；It is cooled down, remaining furfuryl alcohol small molecule just polymers is added, stirs evenly；And solvent dilution is added, it is cooled to room temperature, is discharged.The present invention, by special process, keeps naval stores normal temperature strength constant in the case where reducing furane resins furfuryl alcohol content, it is possible to reduce casting cost, while promoting resin bonded sand mould high temperature collapsibility.
Description
Technical field
The invention belongs to cast auxiliary material field, more particularly, to a kind of high intensity furane resins of low furfuryl alcohol content
Preparation method.
Background technology
Furane resins are domestic and international common casting resins, are generally passed through by furfuryl alcohol and urea, formaldehyde, phenol etc. poly-
Reaction is closed to synthesize.The intensity of furane resins is improved with the increase of furfuryl alcohol content, and heavy castings need the resin of high intensity,
Many Foundry Works require the 24 hours intensity of standard of furane resins that cannot be less than 2.0Mpa, to reach this intensity, in resin
Furfuryl alcohol content will at least reach 70%.
Furfuryl alcohol not only provides normal temperature strength, since its molecular structure contains furan nucleus, has high-temperature stability, therefore furfuryl alcohol
It plays a major role in resin elevated temperature strength, furfuryl alcohol content is higher, and resin elevated temperature strength is higher.But in actual production, increasingly
Advanced coating system can bring the heat-resisting quantity for the mould surface become better and better, the high-temperature behavior of resin itself not only increasingly rich
It is remaining, and start to occur extra, because excessively high elevated temperature strength is unfavorable for the defeated and dispersed of sand mold, cause regeneration difficult.
Normal temperature strength requires high furfuryl alcohol content, low collapsibility to require alap furfuryl alcohol content again, this is conventional furan
The big contradiction that resin occurs in use instantly.
Invention content
In order to solve above-described contradiction, needs to realize in the case where furfuryl alcohol content reduces, still can guarantee resin
Normal temperature strength.
Atlas analysis is carried out by the furane resins to 70% furfuryl alcohol content, detects that furans ring content only has 50% left side
It is right.It deeply excavates the production of furane resins and uses process, it has been found that in production due to violent reaction condition, part
Furan nucleus ruptures the polymer for producing low activity in process of production, this part low activity polymer in the curing process cannot
Further cross-linking reaction has lost its intensity having.Therefore, it if the loss of this part furan nucleus can be reduced, that is, prevents low
The generation of active macromolecules polymer makes furan nucleus synthesize the furfuryl alcohol polymer of small molecule, resin by other chemical bonded refractories
Intensity can get a promotion, and be become easy to reduce furfuryl alcohol content.
The present invention provides a kind of preparation methods of the high intensity furane resins of low furfuryl alcohol content, including：By furfuryl alcohol and idol
After connection agent is mixed evenly, reaction at a certain temperature at the first time, generates furfuryl alcohol small molecule just polymers；In reaction vessel
In, urea and formaldehyde carry out addition reaction；After the addition reaction, the furfuryl alcohol that addition accounts for furfuryl alcohol total amount one third is small
The first polymers of molecule, carries out pyroreaction；After the pyroreaction, small point of furfuryl alcohol for accounting for furfuryl alcohol total amount one third is added
Sub just polymers, turns off steam, stirring the second time of cooling；It is cooled down, remaining furfuryl alcohol small molecule just polymers is added, stirring is equal
It is even；And solvent dilution is added, it is cooled to room temperature, is discharged.
In the above-mentioned methods, wherein the coupling agent is silane KH-550 or silane KH-620.
In the above-mentioned methods, wherein the solvent is water and/or methanol.
In the above-mentioned methods, wherein the amount of the furfuryl alcohol used in the step of generating polymers at the beginning of furfuryl alcohol small molecule is 40-60
Parts by weight, the coupling agent account for the 0.4%-0.6% of furfuryl alcohol weight.
In the above-mentioned methods, wherein the addition reaction carries out under alkaline condition.
In the above-mentioned methods, wherein the amount of urea and formaldehyde is 20-40 parts by weight.
In the above-mentioned methods, wherein the pyroreaction carries out in acid condition.
In the above-mentioned methods, wherein in the step of the cooling, be cooled to 60 DEG C -70 DEG C.
In the above-mentioned methods, wherein the amount of the solvent is 10-20 parts by weight.
In the above-mentioned methods, wherein the first time is 2-6h, and second time is 1-2h.
In the above-mentioned methods, wherein the certain temperature is 30-50 DEG C.
The present invention, by special process, keeps naval stores room temperature strong in the case where reducing furane resins furfuryl alcohol content
It spends constant, it is possible to reduce casting cost, while promoting resin bonded sand mould high temperature collapsibility.
Specific implementation mode
The following examples can make those skilled in the art that the present invention be more fully understood, but not limit in any way
The present invention.
Method provided by the invention mainly includes the following steps that：
I. in 30- after 40-60 parts by weight furfuryl alcohol being mixed evenly with the coupling agent for accounting for furfuryl alcohol weight 0.4%-0.6%
2-6h is reacted at 50 DEG C, is generated furfuryl alcohol small molecule just polymers, is released spare.Period is it is observed that furfuryl alcohol is converted to from yellow
Dark red, color are gradually being deepened, it was demonstrated that the association of intermolecular chemical bond has occurred；
In II, reaction vessels, urea-formaldehyde carries out addition reaction, urea and the total 20-40 weight of formaldehyde under alkaline condition
Part；
After III, addition reactions, the first polymers of furfuryl alcohol small molecule for accounting for furfuryl alcohol total amount one third is added, in acid condition
Lower carry out pyroreaction；
After IV, pyroreaction, the first polymers of furfuryl alcohol small molecule for accounting for furfuryl alcohol total amount one third is added, turns off steam,
Stirring cooling 1-2h；
V, cooling waters are cooled to 60 DEG C -70 DEG C, and remaining furfuryl alcohol small molecule just polymers is added, stirs evenly；
The solvent dilution of 10-20 parts by weight is added in VI, is cooled to room temperature, discharges.
In above step, coupling agent is silane KH-550 or silane KH-620；Solvent is water, one kind in methanol or two
Kind.It is illustrated below with specific embodiment.
Embodiment one：
I, reacts 6h after stirring evenly 500 kilograms of furfuryl alcohols in a stirring kettle with 2 kilograms of silane KH602 at 30 DEG C, instead
Furfuryl alcohol small molecule just polymers should be generated, is released spare；
165 kilograms of urea are added in 1 ton of resin reaction kettle in II, and 185 kilograms of formaldehyde are reacted under alkaline condition to complete
Entirely, about 2 hours；
III, after completion of the reaction, be added 150 kilograms of step I in furfuryl alcohol small molecule just polymers, react in acid condition to
Completely, about 2 hours；
After completion of the reaction, the first polymers of furfuryl alcohol small molecule being added in 150 kilograms of step I turns off steam, stirs 1h IV,；
V, cooling waters are cooled to 60 DEG C, and the first polymers of the furfuryl alcohol small molecule being added in 200 kilograms of step I stirs evenly；
75 kg of water and 75 kilograms of methanol are added in VI,.
By national standard《JBT 7526-2008 casting self-hardening furan resins》Product is detected, naval stores intensity can
Reach 1.8Mpa, higher than the 1.3Mpa of the traditional handicraft product of identical furfuryl alcohol content.
Embodiment two：
I, reacts 4h after stirring evenly 570 kilograms of furfuryl alcohols in a stirring kettle with 2.5 kilograms of silane KH550 at 40 DEG C,
Reaction generates furfuryl alcohol small molecule just polymers, releases spare；
170 kilograms of urea are added in 1 ton of resin reaction kettle in II, and 180 kilograms of formaldehyde are reacted under alkaline condition to complete
Entirely, about 2 hours；
III, after completion of the reaction, be added 190 kilograms of step I in furfuryl alcohol small molecule just polymers, react in acid condition to
Completely, about 2 hours；
After completion of the reaction, the first polymers of furfuryl alcohol small molecule being added in 190 kilograms of step I turns off steam, stirs 1.5h IV,；
V, cooling waters are cooled to 65 DEG C, and the first polymers of the furfuryl alcohol small molecule being added in 190 kilograms of step I stirs evenly；
50 kg of water and 30 kilograms of methanol are added in VI,.
By national standard《JBT 7526-2008 casting self-hardening furan resins》Product is detected, naval stores intensity can
Reach 2.0Mpa, higher than the 1.5Mpa of the traditional handicraft product of identical furfuryl alcohol content.
Embodiment three：
I, reacts 2h after stirring evenly 600 kilograms of furfuryl alcohols in a stirring kettle with 3 kilograms of silane KH602 at 50 DEG C, instead
Furfuryl alcohol small molecule just polymers should be generated, is released spare；
148 kilograms of urea are added in 1 ton of resin reaction kettle in II, and 152 kilograms of formaldehyde are reacted under alkaline condition to complete
Entirely, about 2 hours；
III, after completion of the reaction, be added 200 kilograms of step I in furfuryl alcohol small molecule just polymers, react in acid condition to
Completely, about 2 hours；
After completion of the reaction, the first polymers of furfuryl alcohol small molecule being added in 200 kilograms of step I turns off steam, stirs 2h IV,；
V, cooling waters are cooled to 70 DEG C, and the first polymers of the furfuryl alcohol small molecule being added in 200 kilograms of step I stirs evenly；
50 kg of water and 50 kilograms of methanol are added in VI,.
By national standard《JBT 7526-2008 casting self-hardening furan resins》Product is detected, naval stores intensity can
Reach 2.1Mpa, higher than the 1.6Mpa of the traditional handicraft product of identical furfuryl alcohol content.
It will be understood by those skilled in the art that above example is only exemplary embodiment, in the spirit without departing substantially from the present invention
In the case of range, a variety of variations can be carried out, replaced and changed.
Claims (7)
1. a kind of preparation method of the high intensity furane resins of low furfuryl alcohol content, including：
After furfuryl alcohol and coupling agent are mixed evenly, 2-6h is reacted at 30-50 DEG C, generates furfuryl alcohol small molecule just polymers；
In the reaction vessel, urea and formaldehyde carry out addition reaction；
After the addition reaction, the first polymers of furfuryl alcohol small molecule for accounting for furfuryl alcohol total amount one third is added, it is anti-to carry out high temperature
It answers；
After the pyroreaction, the first polymers of furfuryl alcohol small molecule for accounting for furfuryl alcohol total amount one third is added, turns off steam, stirs
Mix cooling 1-2h；
It is cooled down, remaining furfuryl alcohol small molecule just polymers is added, stirs evenly；And
Solvent dilution is added, is cooled to room temperature, discharges,
Wherein, the amount of the furfuryl alcohol used in the step of generating polymers at the beginning of furfuryl alcohol small molecule is 40-60 parts by weight, the coupling agent
Account for the 0.4%-0.6% of furfuryl alcohol weight；
The total amount of urea and formaldehyde is 20-40 parts by weight.
2. preparation method according to claim 1, wherein the coupling agent is silane KH-550 or silane KH-620.
3. preparation method according to claim 1, wherein the solvent is water and/or methanol.
4. preparation method according to claim 1, wherein the addition reaction carries out under alkaline condition.
5. preparation method according to claim 1, wherein the pyroreaction carries out in acid condition.
6. preparation method according to claim 1, wherein in the step of the cooling, be cooled to 60 DEG C -70 DEG C.
7. preparation method according to claim 1, wherein the amount of the solvent is 10-20 parts by weight.
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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 |
| CN108687301B (en) * | 2017-04-06 | 2020-01-10 | 济南圣泉集团股份有限公司 | Binder composition for casting and kit for preparing the same |
| CN110655628A (en) * | 2019-11-06 | 2020-01-07 | 徐州盛安化工科技有限公司 | Synthetic method of environment-friendly furan resin for cast iron |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102504157A (en) * | 2011-10-19 | 2012-06-20 | 珠海市斗门福联造型材料实业有限公司 | Non-dehydrated modified furan resin and production process thereof |
| CN104086733A (en) * | 2014-06-26 | 2014-10-08 | 宁夏共享装备有限公司 | Production method of furan resin without dehydration property |
| CN104193936A (en) * | 2014-08-29 | 2014-12-10 | 玉林市兰科铸造材料有限公司 | Hot box resin for casting and preparation method of hot box resin for casting |
| CN104497299A (en) * | 2014-11-20 | 2015-04-08 | 济南圣泉集团股份有限公司 | Method for preparing low dissociation furfuryl alcohol binder |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504157A (en) * | 2011-10-19 | 2012-06-20 | 珠海市斗门福联造型材料实业有限公司 | Non-dehydrated modified furan resin and production process thereof |
| CN104086733A (en) * | 2014-06-26 | 2014-10-08 | 宁夏共享装备有限公司 | Production method of furan resin without dehydration property |
| CN104193936A (en) * | 2014-08-29 | 2014-12-10 | 玉林市兰科铸造材料有限公司 | Hot box resin for casting and preparation method of hot box resin for casting |
| CN104497299A (en) * | 2014-11-20 | 2015-04-08 | 济南圣泉集团股份有限公司 | Method for preparing low dissociation furfuryl alcohol binder |
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