CN101235126B - Integrated utilization method for byproduct of vanillin production - Google Patents
Integrated utilization method for byproduct of vanillin production Download PDFInfo
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- CN101235126B CN101235126B CN2007100605095A CN200710060509A CN101235126B CN 101235126 B CN101235126 B CN 101235126B CN 2007100605095 A CN2007100605095 A CN 2007100605095A CN 200710060509 A CN200710060509 A CN 200710060509A CN 101235126 B CN101235126 B CN 101235126B
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Abstract
The invention relates to a comprehensive utilization method for the byproduct of vanillin production, which comprises effectively separating 3-methoxy-4-hydroxy benzene glycollic acid dimmer from the product to replace part or the total phenol, to be condensed with formaldehyde to prepare a modified phenol resin, replace part or total bisphenol A to be condensed with epichlorohydrin to prepare modified epoxy resin, or optionally replace part or total benzene dicarboxylic acid to be condensed with maleic anhydride and propylene glycol to prepare unsaturated alkide resin. The modified resin has wide application in paint, adhesive and plastic to reduce vanillin production cost and eliminate waste liquid pollution in production.
Description
Technical field
The present invention relates to a kind of byproduct of vanillin production method of comprehensive utilization; Particularly replace the method for raw material synthesis modification resins such as phthalic acid, phenol and dihydroxyphenyl propane, belong to macromolecule chemical industry and polymeric material field with oxoethanoic acid and methyl catechol byproduct of reaction 3-methoxyl group-4 hydroxylphenylethyl alcohol acid dimer.
Background technology
Oxoethanoic acid and phenolic cpd carry out condensation reaction and generate p-hydroxybenzene oxyacetic acid verivate, can synthesize a series of fine chemicals simply efficiently through it, have extensive use aspect medicine, agricultural chemicals and the daily-use chemical industry.The principal item of suitability for industrialized production is summarized as follows both at home and abroad:
With oxoethanoic acid and methyl catechol prepare vanillin food grade,1000.000000ine mesh technology at present heavy industrialization use, basic craft course contriver is at " Jiangsu chemical industry ", 1993, (3): 13-16 has more in detail and introduces.The subject matter that exists in the production is that the yield of oxoethanoic acid and methyl catechol condensation reaction is not ideal enough, is generally 60%-80%.Major cause is that product 3-methoxyl group-4 hydroxymandelic acid polymerization reaction take place has generated a large amount of dipolymers.The generation of these dipolymers has not only increased raw material consumption, and has increased the production treatment cost of waste liquor.Past hopes to reduce the dipolymer generation and improve yield through improving the condensation process condition, but effective income is little.Chinese patent CN1847216 proposes that vanillin food grade,1000.000000ine mesh is produced waste liquid and solidifies the treatment process that acts as a fuel, but processing cost is higher.With the byproduct of reaction comprehensive utilization is the effective way that reduces vanillin food grade,1000.000000ine mesh production cost and liquid waste disposal pressure.
Summary of the invention
The objective of the invention is to solve oxoethanoic acid and methyl catechol byproduct of reaction problem of complex utilization.At first propose a kind of method 3-methoxyl group-4 hydroxymandelic acid dipolymer is effectively separated with product, replace the resin synthesis material to prepare modified resin with it again.Modified resin can be widely used in aspects such as coating, tamanori, plastics, thereby has reduced the vanillin food grade,1000.000000ine mesh production cost and eliminated waste water pollution problem in the production process.
It is open that oxoethanoic acid and methyl catechol carry out the existing patent of condensation reaction; Promptly earlier methyl catechol is dissolved in and obtains the methyl catechol sodium solution in the sodium hydroxide solution; Again sodium carbonate solution is added glyoxylic acid solution and obtain the oxoethanoic acid sodium solution; Then the oxoethanoic acid sodium solution is added drop-wise to and makes 3-methoxyl group-4-p-hydroxyphenylethanol acid sodium in the methyl catechol sodium solution, generate 3-methoxyl group-4-p-hydroxyphenylethanol acid oligomer by product simultaneously.The final vacuum concentration of reaction solution is accomplished in reaction, cooling, crystallization, separation 3-methoxyl group-4-p-hydroxyphenylethanol acid sodium product.With the further vacuum concentration of mother liquor to the dried 3-methoxyl group-4-p-hydroxyphenylethanol acid oligomer by product that obtains.
The condensation reaction by product is formed more complicated, discovers the ortho position active sites that has two carboxyls, two phenolic hydroxyl groups and a phenolic hydroxyl group in the by-product oligomer structure unit at least.Infer that it is formed mainly is 3-methoxy-4-hydroxyphenyle-thanol acid dipolymer, molecular structural formula is expressed as:
This by product has the diprotic acid structure, can partly or entirely replace phthalic acid and MALEIC ANHYDRIDE and Ucar 35 to carry out polyreaction synthesis modification unsaturated alkyd resin.This by product has the dihydric phenol structure, and it can partly or entirely replace dihydroxyphenyl propane and epoxy chloropropane to carry out polyreaction synthesis modification epoxy resin.Also can partly or entirely replace phenol and formaldehyde to carry out polyreaction synthesis modification resol.
Embodiment
The objective of the invention is to adopt following mode to realize, specify below in conjunction with embodiment:
Embodiment 1
The industrial methyl catechol (1.2mol) of 156.6g content 95% is dissolved in obtains light red methyl catechol sodium solution in 1200ml 4% sodium hydroxide solution.1000ml 10% sodium carbonate solution under agitation added obtain faint yellow oxoethanoic acid sodium solution in 222g content 40% glyoxylic acid solution (1.2mol).3000ml four-hole bottle so that whisking appliance, TM and tap funnel to be housed is done reactor drum; Add the methyl catechol sodium solution earlier; Drip the oxoethanoic acid sodium solution in 15-25 ℃ with stirring down, added in about 8 hours, continue stirring reaction then aldehyde in solution acid sodium is all transformed.The about 2400ml of reaction mother liquor TV, liquid-phase chromatographic analysis wherein contain 3-methoxyl group-4-p-hydroxyphenylethanol acid 190g (0.96mol), 3-methoxyl group-4-p-hydroxyphenylethanol acid dipolymer 45.4g (0.12mol).The vacuum concentration reaction solution is cooled to 15 ℃ the 3-methoxyl group-4-p-hydroxyphenylethanol acid sodium of generation is crystallized out to 800ml, and the filtering separation crystallization obtains 3-methoxyl group-4-p-hydroxyphenylethanol acid dipolymer behind the further vacuum concentration of mother liquor, subsequent use.
Embodiment 2
3-methoxyl group-4-p-hydroxyphenylethanol acid dipolymer 45.4g (0.12mol) adding will be equipped with in the 250ml four-hole bottle of whisking appliance, TM and tap funnel, under agitation add 37% formaldehyde solution 19.5g (0.24mol).Be heated to 65 ℃ with electric mantle, drip 10% hydrochloric acid soln, control pH value of solution 1.5-2.5 stops condensation reaction behind the reaction 3h.Vacuum concentration, cooling back branch removes upper water, obtains modified phenolic resins 48.1g.
Embodiment 3
3-methoxyl group-4-p-hydroxyphenylethanol acid dipolymer 45.4g (0.12mol) adding will be equipped with in the 250ml four-hole bottle of whisking appliance, TM and tap funnel, under agitation add epoxy chloropropane 33.6g (0.36mol).Substep drips 30% sodium hydroxide solution 25ml, 75 ℃ of controlled temperature.Alkali lye is added dropwise to complete continued back flow reaction 1.5h, and cooling stops condensation reaction then.Divide the extracting and separating organic phase three times with 150ml benzene, wash organic phase with warm water.Excessive epoxy chloropropane is reclaimed in distillation, obtains modified epoxy 50.1g.
Embodiment 4
In the 500ml four-hole bottle that whisking appliance, TM and still head are housed, add MALEIC ANHYDRIDE 9.8g (0.10mol), 3-methoxyl group-4-p-hydroxyphenylethanol acid 37.7g (0.10mol) and Ucar 35 9.2g (0.12mol) successively.Heat to 80 ℃ with electric mantle, fully stirring reaction 1.5h is warmed up to 160 ℃ of reaction 0.5h down, the sampling and measuring acid number then.Be warmed up to 190-200 ℃ gradually, about acid number reaches 40, stop condensation.When treating that material cools to 100 ℃, add vinylbenzene 25g, fully stir and obtain modified unsaturated polyester resin 77.4g.
Claims (1)
1. byproduct of vanillin production method of comprehensive utilization; It is characterized in that earlier methyl catechol being dissolved in obtaining the methyl catechol sodium solution in the sodium hydroxide solution; Again sodium carbonate solution is added glyoxylic acid solution and obtain the oxoethanoic acid sodium solution; Then the oxoethanoic acid sodium solution is added drop-wise to and makes 3-methoxyl group-4-p-hydroxyphenylethanol acid sodium in the methyl catechol sodium solution, generate 3-methoxyl group-4-p-hydroxyphenylethanol acid oligomer by product simultaneously; The final vacuum concentration of reaction solution is accomplished in reaction, cooling, crystallization, separation 3-methoxyl group-4-p-hydroxyphenylethanol acid sodium product; Mother liquor vacuum concentration to the dried 3-of the obtaining methoxyl group-4-p-hydroxyphenylethanol acid oligomer by product that will contain by product; This by product has the dihydric phenol structure; Replace phenol raw material and formaldehyde to carry out polyreaction synthesis modification resol with it, replace dihydroxyphenyl propane raw material and epoxy chloropropane to carry out polyreaction synthesis modification epoxy resin with it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100605095A CN101235126B (en) | 2007-12-28 | 2007-12-28 | Integrated utilization method for byproduct of vanillin production |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007100605095A CN101235126B (en) | 2007-12-28 | 2007-12-28 | Integrated utilization method for byproduct of vanillin production |
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| CN101235126A CN101235126A (en) | 2008-08-06 |
| CN101235126B true CN101235126B (en) | 2012-05-30 |
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| CN2007100605095A Expired - Fee Related CN101235126B (en) | 2007-12-28 | 2007-12-28 | Integrated utilization method for byproduct of vanillin production |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674179A (en) * | 2017-10-27 | 2018-02-09 | 天津市职业大学 | The method for preparing epoxy resin using D-pHPG production solid slag |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538354B (en) * | 2009-04-14 | 2012-08-22 | 天津市职业大学 | Method for utilizing synthesized aspirin waste liquid to prepare water soluble phenol resin |
| CN107759773A (en) * | 2017-10-27 | 2018-03-06 | 天津市职业大学 | The method for preparing glycolylurea epoxide resin using 4-Hydroxyphenyl hydantoin production solid slag |
| CN107540817A (en) * | 2017-10-29 | 2018-01-05 | 天津市职业大学 | Novolac epoxy resin method is prepared using vanillic aldehyde production waste liquid |
| CN108840336A (en) * | 2018-08-13 | 2018-11-20 | 天津市职业大学 | A method of high performance active carbon is prepared using vanillic aldehyde production waste liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2662871A (en) * | 1950-11-28 | 1953-12-15 | Rayonier Inc | Polyesters made from dibasic acids derived from vanillin |
| CN1847216A (en) * | 2006-04-25 | 2006-10-18 | 扬州大学 | Circular treating process of solid waste from vanillin synthesis |
-
2007
- 2007-12-28 CN CN2007100605095A patent/CN101235126B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2662871A (en) * | 1950-11-28 | 1953-12-15 | Rayonier Inc | Polyesters made from dibasic acids derived from vanillin |
| CN1847216A (en) * | 2006-04-25 | 2006-10-18 | 扬州大学 | Circular treating process of solid waste from vanillin synthesis |
Non-Patent Citations (2)
| Title |
|---|
| 高大维等."用生产香兰素的副产物合成N-[p-（二甲氨基）苯基]马来酰亚胺".《吉林大学自然科学学报》.1997,(第4期),103-105. |
| 高大维等."用生产香兰素的副产物合成N-[p-(二甲氨基)苯基]马来酰亚胺".《吉林大学自然科学学报》.1997,(第4期),103-105. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107674179A (en) * | 2017-10-27 | 2018-02-09 | 天津市职业大学 | The method for preparing epoxy resin using D-pHPG production solid slag |
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| CN101235126A (en) | 2008-08-06 |
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