CN103351455A - Low furfuralcohol furan resin preparation method - Google Patents
Low furfuralcohol furan resin preparation method Download PDFInfo
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- CN103351455A CN103351455A CN2013102965175A CN201310296517A CN103351455A CN 103351455 A CN103351455 A CN 103351455A CN 2013102965175 A CN2013102965175 A CN 2013102965175A CN 201310296517 A CN201310296517 A CN 201310296517A CN 103351455 A CN103351455 A CN 103351455A
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Abstract
The invention discloses a low furfuralcohol furan resin preparation method and relates to a resin preparation method, which comprises the following steps: adopting furfuralcohol and formaldehyde as the raw materials and preparing 2,5-hydroxymethyl; during preparing adhesive, adding the hydroxymethyl as an intermediate body into an adhesive formula; performing polycondensation under the action of an activator; preparing adhesive resin under the heating condition, wherein the mole ratio of the furfuralcohol and the formaldehyde is 1:0.6-1:1, the reaction temperature is 80-100 DEG C, the reaction time is 2-18 hours, and the pH value is 1-6.5. The low furfuralcohol furan resin preparation method solves the discharge problem of noxious gases in adhesive industry, lowers production cost, further improves process performance, and also solves the problem of purification of impurity in the product.
Description
Technical field
The present invention relates to a kind of process for preparing resins, particularly relate to a kind of low furfuryl alcohol furane resin preparation method.
Background technology
Arrival along with energy dilemma; constantly riseing of the continuous minimizing of oil supply amount and price; the severization of the concern of people's environmental pollution and National Environmental rules particularly; more strict to the toxic gas Permissible limit that the resene binding agent discharges in process of setting, the demand that replaces petroleum product with botanical derivative grows to even greater heights.Because the market scale that casting, furniture, timber, coating and synthetical resin products are larger and the importance in national economy thereof, the also low furfuryl alcohol furan no-bake resin of this novel environment-friendly of requirement exploitation.
Casting mainly is made of furfuryl alcohol and plant base derivative with the low furfuryl alcohol furan no-bake resin of novel environment-friendly.Wherein furfuryl alcohol also is a kind of very important starting material on North America and international economy and trade market, therefore, adopt replace in the furan no-bake resin and minimizing furfuryl alcohol content various organic addings with inorganic materials, and the processing performance of further improving the furan no-bake resin, showing great attention to of people caused.
In the near future, along with the high speed development of world economy and the increase of various countries' furfuryl alcohol usage quantity, furfuryl alcohol is supplied with may be more restricted.Therefore, seek all or part of replacement furfuryl alcohol surrogate and seem more urgent.
As everyone knows, polycondensation can occur in furfuryl alcohol and formaldehyde under suitable catalyst action, and still, the shortcoming that its polymerization is produced is that reaction process is slow, and inefficiency needs a large amount of an acidic catalysts, and not easily separated.Free phenol in original resin technique or free formaldehyde pollute Working environment, serious harm the workman physically and mentally healthy.Simultaneously, a large amount of addings of furfuryl alcohol have improved production cost greatly, affect applying of product.Furfuryl alcohol is listed in the toxic substance category, but when containing free furfuryl alcohol＜25% in the furane resin, not only has the characteristics of low toxicity, and, can keep the concentration＜40mg/m of free furfuryl alcohol in the Active workings
3. this has protected the healthy of workman, has also guaranteed the environment that manufacturing enterprise is good.
Therefore be necessary to study a kind of resin that substitutes, it is joined in the sizing agent prescription as intermediate, replacement or part replace the usage quantity of furfuryl alcohol, and eliminate its Free-formaldehyde.Itself production unit requires low, and technique is simple, is easy to produce.
Summary of the invention
The object of the present invention is to provide a kind of low furfuryl alcohol furane resin preparation method, the method proposes 2, the synthetic method of 5-dihydroxymethyl furans, solve the problem of toxic gas discharging in the sizing agent industry, reduce production costs, further improve processing performance, the resin of preparation is widely used in casting, furniture, timber, coating and synthetic resins field.
The objective of the invention is to be achieved through the following technical solutions:
A kind of low furfuryl alcohol furane resin preparation method, described method comprises following process: adopting furfuryl alcohol and formaldehyde is raw material, preparation 2,5-dihydroxymethyl furans in preparation sizing agent process, joins the dihydroxymethyl furans in the sizing agent prescription as intermediate; Polycondensation under catalyst action is made tackifying resin under the condition of heating; Wherein the mol ratio of furfuryl alcohol and formaldehyde is 1:0.6 ~ 1:1; Its temperature of reaction is 80 ℃ ~ 100 ℃, and the reaction times is 2-18 hour, and pH value is between 1 ~ 6.5.
Described a kind of low furfuryl alcohol furane resin preparation method, acid catalyzed polymerisation is adopted in described polycondensation.
Described a kind of low furfuryl alcohol furane resin preparation method, described catalyzer comprises: sulfuric acid, boric acid, zinc acetate, aluminosilicate-type catalyzer (ZSM-23).
Advantage of the present invention and effect are:
The present invention prepares the method for dihydroxymethyl furans; will reduce in the sizing agent preparation process; the consumption of furfuryl alcohol and the adding of formaldehyde monomers; the release that solves significantly toxic gas in the production process is arranged; be conducive to protect the cleaning of production site environment and workman's physical and mental health, and greatly reduce production cost.Adopt the dihydroxymethyl furane resin as intermediate, add in the sizing agent prescription, be conducive to improve the processing performance of resin.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
The present invention mainly develops the synthetic method of dihydroxymethyl furane resin, in preparation sizing agent process, the dihydroxymethyl furans is joined in the sizing agent prescription as intermediate, replace the use of part furfuryl alcohol and the use of formaldehyde, thereby play the saving cost, eliminate the effect of free formaldehyde.Prepare a kind of low furfuryl alcohol furane resin, wherein the mol ratio of furfuryl alcohol and formaldehyde should be 1:0.6 ~ 1:1.Its temperature of reaction should be 80 ℃ ~ 100 ℃.PH value should be between 1 ~ 3.5.Adopt acid catalyzed polymerisation.Wherein catalyzer comprises: sulfuric acid, boric acid, zinc acetate, ZSM-23.
Preparation 2,5-dihydroxymethyl furans:
(1) in preparation sizing agent process, the dihydroxymethyl furans is joined in the sizing agent prescription as intermediate, replace the use of part furfuryl alcohol and the use of formaldehyde, thereby play the saving cost, eliminate the effect of free formaldehyde.
(2) mol ratio
Proportioning raw materials is the key factor that affects resin property. experiment showed, when the formaldehyde consumption is too small, is difficult to generate resin, and too much when the formaldehyde consumption, cause on the one hand the waste of environmental pollution and material; Also can reduce on the other hand the water tolerance after the curing.
(3) catalyzer
In the polycondensation stage, pH value major effect speed of response, the larger then reaction of pH value is slower, thereby affects the production cycle, cause raw-material waste, if the pH value is too small, then speed of response is too fast, moment generates larger molecule, makes speed of response be difficult to control, gelatin phenomenon can occur.So, need to control pH value by catalyzer.
(4) temperature-time
Temperature of reaction also has larger impact to speed of response, quality product. and temperature is higher, and speed of response is faster, easily generates on the one hand derivative, can cause gel on the other hand, and production can not normally be carried out; On the contrary, temperature is excessively low, and speed of response is excessively slow, will greatly extend manufacture cycle, and increases cost.
It is raw material that the method mainly adopts furfuryl alcohol and formaldehyde, under catalyst action, makes tackifying resin under the condition of heating.This resin can reduce furfuryl alcohol and the usage quantity of formaldehyde in the sizing agent prescription, thereby eliminates the harm of monomer formaldehyde in traditional sizing agent.Wherein the mol ratio of furfuryl alcohol and formaldehyde should be 1:0.6 ~ 1:1.Its temperature of reaction should be 80 ℃ ~ 100 ℃, and the reaction times is 2-18 hour, and pH value should be between 1 ~ 6.5.Adopt acid catalyzed polymerisation.Wherein catalyzer comprises: sulfuric acid, boric acid, zinc acetate, aluminosilicate-type catalyzer (ZSM-23).
Embodiment 1
Measure the mixed solution of 500ml furfuryl alcohol and 250-500ml formaldehyde, it is moved in the there-necked flask with reflux condensate device, add 20-100g ZSM-23 catalyzer, at the uniform velocity stir, be heated to 80-100 ℃ and be incubated 2-18h.After the product cooling, by vacuum filtration, remove catalyst Z SM-23.Then residual moisture content is removed in underpressure distillation.Can prepare furfuryl alcohol-formal resin.
Embodiment 2
Measure the mixed solution of 50ml furfuryl alcohol and 30-30ml formaldehyde, it is moved in the there-necked flask with reflux condensate device, add the 5g alumina silicate catalyst, at the uniform velocity stir, be heated to 90-100 ℃ and be incubated 6-15h.After the product cooling, by vacuum filtration, remove catalyst Z SM-23.Then residual moisture content is removed in underpressure distillation.Make furfuryl alcohol-formal resin.
Embodiment 3
Measure the mixed solution of 500ml furfuryl alcohol and 250-500ml formaldehyde, it is moved in the there-necked flask with reflux condensate device, add the 20-100g zinc acetate catalyst, at the uniform velocity stir, be heated to 80-100 ℃ and be incubated 2-18h.After the product cooling, by vacuum filtration, remove gel.Then residual moisture content is removed in underpressure distillation.
Embodiment 4
Measure the mixed solution of 500ml furfuryl alcohol and 250-500ml formaldehyde, it is moved in the there-necked flask with reflux condensate device, add 20-100g boric acid, at the uniform velocity stir, be heated to 80-100 ℃ and be incubated 2-18h.After the product cooling, by vacuum filtration, remove gel.Then residual moisture content is removed in underpressure distillation.
Embodiment 5
Measuring 2-10 ml sulfuric acid joins in the 300-500 ml formaldehyde solution, produce the high concentrated acid mixture of pH 1-6.5, it is moved in the there-necked flask of reflux condensate device, fluid temperature is stabilized in 80-100 ℃, at the uniform velocity stir, dropwise add subsequently the 500ml furfuryl alcohol.Keep heating in the reaction process and make liquidus temperature keep constant.
Introduce completely when furfuryl alcohol, continue heating 5 minutes and react completely guaranteeing.After the product cooling, by vacuum filtration, remove gel.Then residual moisture content is removed in underpressure distillation.
Claims (3)
1. one kind low furfuryl alcohol furane resin preparation method is characterized in that, described method comprises following process: adopting furfuryl alcohol and formaldehyde is raw material, preparation 2,5-dihydroxymethyl furans in preparation sizing agent process, joins the dihydroxymethyl furans in the sizing agent prescription as intermediate; Polycondensation under catalyst action is made tackifying resin under the condition of heating; Wherein the mol ratio of furfuryl alcohol and formaldehyde is 1:0.6 ~ 1:1; Its temperature of reaction is 80 ℃ ~ 100 ℃, and the reaction times is 2-18 hour, and pH value is between 1 ~ 6.5.
2. a kind of low furfuryl alcohol furane resin preparation method according to claim 1 is characterized in that, acid catalyzed polymerisation is adopted in described polycondensation.
3. a kind of low furfuryl alcohol furane resin preparation method according to claim 2 is characterized in that, described catalyzer comprises: sulfuric acid, boric acid, zinc acetate, aluminosilicate-type catalyzer (ZSM-23).
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| CN2013102965175A CN103351455A (en) | 2013-07-16 | 2013-07-16 | Low furfuralcohol furan resin preparation method |
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| CN2013102965175A CN103351455A (en) | 2013-07-16 | 2013-07-16 | Low furfuralcohol furan resin preparation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109224A (en) * | 2014-07-04 | 2014-10-22 | 沈阳化工大学 | Method for synthesizing furfuryl alcohol formaldehyde resin at low temperature |
| WO2015128070A1 (en) * | 2014-02-28 | 2015-09-03 | Hexion GmbH | Reaction product and use for the production of foundry molds and cores |
| CN105175669A (en) * | 2015-08-04 | 2015-12-23 | 宁夏共享化工有限公司 | Method for fast and integral hardening of furan resin |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117514A (en) * | 1993-12-27 | 1996-02-28 | 花王株式会社 | Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold |
| CN103058962A (en) * | 2013-01-24 | 2013-04-24 | 中国科学院青岛生物能源与过程研究所 | Method for preparing 2,5-furan methylene glycol dialkyl ether by furfuryl alcohol |
-
2013
- 2013-07-16 CN CN2013102965175A patent/CN103351455A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117514A (en) * | 1993-12-27 | 1996-02-28 | 花王株式会社 | Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold |
| CN103058962A (en) * | 2013-01-24 | 2013-04-24 | 中国科学院青岛生物能源与过程研究所 | Method for preparing 2,5-furan methylene glycol dialkyl ether by furfuryl alcohol |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015128070A1 (en) * | 2014-02-28 | 2015-09-03 | Hexion GmbH | Reaction product and use for the production of foundry molds and cores |
| CN104109224A (en) * | 2014-07-04 | 2014-10-22 | 沈阳化工大学 | Method for synthesizing furfuryl alcohol formaldehyde resin at low temperature |
| CN105175669A (en) * | 2015-08-04 | 2015-12-23 | 宁夏共享化工有限公司 | Method for fast and integral hardening of furan resin |
| 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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Application publication date: 20131016 |