CN102659576A - Refining method for 2-hydroxyl-6-naphthoic acid - Google Patents
Refining method for 2-hydroxyl-6-naphthoic acid Download PDFInfo
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- CN102659576A CN102659576A CN2012101310326A CN201210131032A CN102659576A CN 102659576 A CN102659576 A CN 102659576A CN 2012101310326 A CN2012101310326 A CN 2012101310326A CN 201210131032 A CN201210131032 A CN 201210131032A CN 102659576 A CN102659576 A CN 102659576A
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Abstract
The invention discloses a refining method for 2-hydroxyl-6-naphthoic acid. The refining method mainly comprises the following five steps: dissolving an organic solvent and filtering a crude product; recrystallizing, centrifuging and purifying a filtrate; recycling the filtrate after being centrifuged; adsorbing the secondary filtrate by resins, and then distilling and recycling the organic solvent; and performing alkaline elution on the resins and recycling the crude product. The industrial refining is performed while the lost organic solvent is recycled. The defects of the present refining technology are overcome by industrially purifying and refining the 2-hydroxyl-6-naphthoic acid by adopting the refining method provided by the invention; a refining technical method, which is low in cost, high in product quality and comprehensive in resource utilization, is obtained; according to the refining method, the solvent loss is less; fully crystallizing is realized, without adding a seed crystal; in order to solve the loss problem of a common recrystallizing method, the lost materials during the refining process are recycled; and the refining method is convenient for industrial production and is beneficial to environmental protection.
Description
Technical field
The present invention relates to the working method of organic chemical industry's midbody, the process for refining and purifying of particularly a kind of midbody 2-hydroxyl-6-naphthoic acid.
Background technology
2-hydroxyl-6-naphthoic acid has another name called 2,6 acid, normally obtains through Peter-Michael Kolbe-Schmidt reation with beta naphthal.It is as the liquid crystal material raw material or produce the high molecular polymerization raw material; Account for the II type polyester liquid crystal Vectra of thermotropic liquid crystal high polymer (TLCP) most important part at present; Be exactly the copolymerization of PHB and 2-hydroxyl-6-naphthoic acid, the naphthalene nucleus that 2-hydroxyl-6-naphthoic acid is introduced has brought the side step effect, has destroyed the segmental regularity; Avoided insoluble, the not molten and unmanageable defective of PHB homopolymerization product; And naphthalene nucleus itself is again rigid structure, and intensity and thermotolerance are all better, so the over-all properties of Vectra is best in the thermotropic liquid crystal high polymer.But be used to produce the 2-hydroxyl-6-naphthoic acid of liquid crystal, purity requirement is higher.
2-hydroxyl-6-naphthoic acid mainly obtains through Peter-Michael Kolbe-Schmidt reation, contains principal reaction and a plurality of side reaction, and reaction equation is following.
Other side reactions:, possibly generate 1-hydroxyl-2-naphthoic acid with this understanding owing to also possibly contain the 1-naphthols of trace in the beta naphthal.
2-hydroxyl-6-the naphthoic acid that obtains through Peter-Michael Kolbe-Schmidt reation contains plurality of impurities, also has some content higher, can not directly be used for the sub product of liquid crystal material.Therefore just need make with extra care 2-hydroxyl-6-naphthoic acid bullion that Peter-Michael Kolbe-Schmidt reation obtains.
At present, the 2-hydroxyl-6-naphthoic acid bullion carries out the purified method has following method.
1, patent CN1181371A mentions a 2-hydroxyl-6-naphthoic acid bullion and is dissolved in basic soln, obtains purified 2-hydroxyl-6-naphthoic acid through the method for regulating pH then, though purity increases, it also has certain difference as the polymerizable mesogenic monomer.
2, patent US4916257 utilizes the verivate aqueous solution such as higher alcohols and ether thereof to carry out recrystallization, obtain better products, but loss is bigger, and is merely lab scenario, and productivity is not strong.
3, patent CN1335832A utilizes the aqueous solution of lower alcohols such as methyl alcohol, ethanol, Virahol to carry out recrystallization, obtains the polymerization-grade product.But in treating process 2-hydroxyl-6-naphthoic acid easily and lower alcohol produce corresponding ester, and loss is bigger in treating process.And this patent is in order to obtain the quality better products, must plus seed, under comparatively high temps and pressure, carry out crystallization, and be unfavorable for production.
Summary of the invention
Seeing that to 2-hydroxyl-6-naphthoic acid high-precision requirement and the deficiency of prior art on this midbody is refining, the object of the invention is intended to propose the process for purification of a kind of 2-hydroxyl-6-naphthoic acid, solves the problem of polymerizable mesogenic monomer purity problem and minimizing loss.
To achieve these goals; The present invention is achieved through following technical measures: the process for purification of 2-hydroxyl-6-naphthoic acid; It is characterized in that may further comprise the steps: I: 2-hydroxyl-6-naphthoic acid bullion that Peter-Michael Kolbe-Schmidt reation is obtained is dissolved in the organic solvent of alcohol or ether and the mixture of water; Add gac and heating for dissolving bullion, be incubated 30 minutes～60 minutes down, cross then and filter filtrating at 80～120 ℃; II: the reaction kettle of the filtrating of step I being put into the tool pure water; The pure water relatively volume ratio of filtrating is 1～10:1, heats up then and 90～99 ℃ of insulations 30 minutes～200 minutes down, then through cooling; Centrifugal, the washing, the oven dry, obtain centrate and 2-hydroxyl-6-naphthoic acid elaboration; III:, obtain moisture recovery article and the secondary filtrating that to utilize step II recrystallization to refine with centrate cool to room temperature and filtration; IV: secondary filtrating is adopted resin absorption, and organic solvent is reclaimed in the adsorbed solution distillation; V: after resin absorption is saturated, utilize alkaline solution and water to carry out wash-out successively, desorption liquid is merged the back wherein can be used for refining 2-hydroxyl-6-naphthoic acid bullion of applying mechanically with dilute sulphuric acid adjusting pH4.5-4.8 recovery.
Further, the organic solvent of alcohol or ether is terepthaloyl moietie and ether derivants thereof in the step I, is at least Diethylene Glycol, triethylene glycol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether; Ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether and 1, one or more in the 4-dioxane.And the organic solvent of said alcohol or ether is calculated as 2～10 times of 2-hydroxyl-6-naphthoic acid bullion by mass ratio, and the quality of blended water is 1～10 times relatively.
Further preferably, the mass ratio of the relative 2-hydroxyl of the organic solvent of said alcohol or ether-6-naphthoic acid bullion or water is 2～3.
Further, pure water described in the step II mass ratio of filtrating relatively is 1～10, and the preferred mass ratio is 2～3.
Further, carry out again after being cooled to 40～60 ℃ in the step II centrifugal.
Further, resin described in the step IV is the homopolymerization or the copolymerization product of vinylbenzene or divinylbenzene or vinylformic acid or ester derivative.
Further, alkaline solution described in the step IV is 3～10% the sodium hydroxide or the aqueous solution of other oxyhydroxide.
Use process for purification of the present invention and carry out the industriallization exquisite 2-hydroxyl-6-naphthoic acid of purifying, overcome many shortcomings of existing process for refining, obtain that a kind of cost is low, quality product is high, the refining technique of comprehensive utilization of resources; This method solvent loss is few; It is crystallizable abundant need not to add in addition crystal seed, and is directed against the loss problem of general recrystallization method, has reclaimed the material of treating process loss; Be convenient to suitability for industrialized production, the environmentally friendly advantage of tool.
Embodiment
The present invention describes through following examples, can further understand the present invention, but embodiment of the present invention do not limit to therewith, and all technical schemes of taking equivalents or equivalent transformation to form are all among the protection domain that the present invention requires.
Embodiment 1:In reaction kettle, add 2-hydroxyl-6-naphthoic acid bullion (water cut about 20%) 200kg that Peter-Michael Kolbe-Schmidt reation obtains, 400L terepthaloyl moietie, 300L pure water; Add a small amount of activated carbon, be warmed up to 80～120 ℃ (preferably 93～95 ℃) then, this temperature insulation 30 minutes～60 minutes; Filter then, filtrating entering is accepted still (accept still and add the 500L pure water in advance), and filtration finishes; Be warmed up to 90～99 ℃ (preferably 95～98 ℃); Promote crystal growth in this temperature maintenance 60 minutes (generally 30 minutes～200 minutes all can), cool to 50 ℃ (40～60 ℃ all can) then, centrifuging; Washing, dry 165kg refined prod and the centrate of getting.
Centrate is reduced to room temperature, filters, and gets secondary filtrating and the moisture recovery article of 4.5kg, and this moisture recovery article can be used for refining applying mechanically.
Secondary filtrating is adopted resin column absorption, and the adsorbed solution distillation can be reclaimed organic solvent or be used for recrystallization and applied mechanically.Wherein the resin of resin column is the homopolymerization or the copolymerization product of vinylbenzene or divinylbenzene or vinylformic acid or ester derivative.The macroporous adsorbent resin that obtains of copolymerization particularly.The volume of this secondary filtrating is 8 times of resin column volume.
After the resin column absorption; Earlier with monoploid long-pending 5% (3～10% all can) sodium hydroxide solution wash-out; With the long-pending hot water elution of monoploid, twice desorption liquid merged again, regulate pH to 7 with dilute sulphuric acid and carry out coarse filtration earlier; The solution of coarse filtration is continued to regulate pH to 4.6 (pH4.5-4.8 all can), filter once more, wash and obtain 15.2kg and can be used for refining 2-hydroxyl-6-naphthoic acid bullion of applying mechanically.
Embodiment 2:Be different from embodiment 1, wherein organic solvent is changed to Diethylene Glycol, and other process for purification and consumption are identical, obtains the 171kg refined prod, reclaims the moisture recovery article of 3.2kg in the centrate, and desorption liquid reclaims 2-hydroxyl-6-naphthoic acid bullion of 13.2kg.
Embodiment 3:Be different from embodiment 1, wherein organic solvent is changed to ethylene glycol monomethyl ether, and other process for purification and consumption are identical, obtains the 168kg refined prod, reclaims the moisture recovery article of 4.7kg in the centrate, and desorption liquid reclaims 2-hydroxyl-6-naphthoic acid bullion of 14.7kg.
Embodiment 4:200kg after the 2-hydroxyl-6-naphthoic acid bullion (or containing the moisture recovery article that centrate reclaims) that utilizes the desorption liquid among the embodiment 2 to reclaim is given money as a gift; Solvent is the mixed solution through (it is 0.652 that the karl Fischer method is analyzed water cut) 460L of the refinement mother liquor after the absorption and Diethylene Glycol 240L; Other process for purification is identical; Obtain the 170kg refined prod, reclaim the moisture recovery article of 4.1kg in the centrate again, desorption liquid reclaims 2-hydroxyl-6-naphthoic acid bullion of 14.5kg again.
Below just analyze difference and advantage between the existing process for purification of introducing above-mentioned four relative background technologies of embodiment process for purification products obtained therefrom from empirical value, as shown in the table
Annotate: go up 2-hydroxyl-3 in the table, 6-naphthalic acid, 6-hydroxyl-2,7-naphthalic acid, 3-hydroxyl-2, the 7-naphthalic acid is a same substance, the position that begins when just naming is different.
Except that the foregoing description, the organic solvent of alcohol or ether refers in particular to terepthaloyl moietie and ether derivants thereof described in the step I, is at least Diethylene Glycol, triethylene glycol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether; Ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether and 1, one or more in the 4-dioxane.And the organic solvent of alcohol or ether is calculated as 2～10 times of 2-hydroxyl-6-naphthoic acid bullion by mass ratio, and the quality of blended water is 1～10 times relatively.The preferred mass ratio is 2～3.
In addition, pure water described in the step II mass ratio of filtrating relatively is 1～10, but the general better quality ratio of implementing is 2～3.
To sum up a plurality of embodiment introductions and data comparative analysis are visible; Use process for purification of the present invention and carry out the industriallization exquisite 2-hydroxyl-6-naphthoic acid of purifying, overcome many shortcomings of existing process for refining, obtain that a kind of cost is low, quality product is high, the refining technique of comprehensive utilization of resources; This method solvent loss is few; It is crystallizable abundant need not to add in addition crystal seed, and is directed against the loss problem of general recrystallization method, has reclaimed the material of treating process loss; Be convenient to suitability for industrialized production, the environmentally friendly advantage of tool.
Claims (9)
1.2-the process for purification of hydroxyl-6-naphthoic acid is characterized in that may further comprise the steps:
I: 2-hydroxyl-6-naphthoic acid bullion that Peter-Michael Kolbe-Schmidt reation is obtained is dissolved in the organic solvent of alcohol or ether and the mixture of water, adds gac and heating for dissolving bullion, is incubated 30 minutes～60 minutes down at 80～120 ℃, crosses then and filters filtrating;
II: the reaction kettle of the filtrating of step I being put into the tool pure water; The pure water relatively volume ratio of filtrating is 1～10:1, heats up then and 90～99 ℃ of insulations 30 minutes～200 minutes down, then through cooling; Centrifugal, the washing, the oven dry, obtain centrate and 2-hydroxyl-6-naphthoic acid elaboration;
III:, obtain moisture recovery article and the secondary filtrating that to utilize step II recrystallization to refine with centrate cool to room temperature and filtration;
IV: secondary filtrating is adopted resin absorption, and organic solvent is reclaimed in the adsorbed solution distillation;
V: after resin absorption is saturated, utilize alkaline solution and water to carry out wash-out successively, desorption liquid is merged the back wherein can be used for refining 2-hydroxyl-6-naphthoic acid bullion of applying mechanically with dilute sulphuric acid adjusting pH4.5-4.8 recovery.
2. the process for purification of 2-hydroxyl according to claim 1-6-naphthoic acid, it is characterized in that: the organic solvent of alcohol or ether is terepthaloyl moietie and ether derivants thereof in the step I, is at least Diethylene Glycol, triethylene glycol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether; Ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether and 1, one or more in the 4-dioxane.
3. the process for purification of 2-hydroxyl according to claim 1-6-naphthoic acid; It is characterized in that: the organic solvent of alcohol or ether described in the step I is calculated as 2～10 times of 2-hydroxyl-6-naphthoic acid bullion by mass ratio, and the quality of blended water is 1～10 times relatively.
4. the process for purification of 2-hydroxyl according to claim 3-6-naphthoic acid is characterized in that: the mass ratio of the relative 2-hydroxyl of the organic solvent of alcohol or ether described in the step I-6-naphthoic acid bullion or water is 2～3.
5. the process for purification of 2-hydroxyl according to claim 1-6-naphthoic acid is characterized in that: pure water described in the step II mass ratio of filtrating relatively is 1～10.
6. the process for purification of 2-hydroxyl according to claim 5-6-naphthoic acid is characterized in that: the mass ratio of the relative aluminium liquid of pure water described in the step II is 2～3.
7. the process for purification of 2-hydroxyl according to claim 1-6-naphthoic acid is characterized in that: carry out centrifugal after being cooled to 40～60 ℃ in the step II again.
8. the process for purification of 2-hydroxyl according to claim 1-6-naphthoic acid is characterized in that: resin described in the step IV is the homopolymerization or the copolymerization product of vinylbenzene or divinylbenzene or vinylformic acid or ester derivative.
9. the process for purification of 2-hydroxyl according to claim 1-6-naphthoic acid is characterized in that: alkaline solution described in the step IV is 3～10% sodium hydroxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776411A (en) * | 2019-11-07 | 2020-02-11 | 北京师范大学 | Simple and efficient method for preparing 2, 7-dihydroxy-3, 6-naphthalene diacid |
| CN114057566A (en) * | 2021-12-09 | 2022-02-18 | 宁夏清研高分子新材料有限公司 | Preparation method of 2-hydroxy-6-naphthoic acid |
| CN114524723A (en) * | 2022-01-29 | 2022-05-24 | 宿迁思睿屹新材料有限公司 | 2-hydroxy-6-naphthoic acid preparation process capable of continuous production and control device thereof |
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| US4916257A (en) * | 1988-01-15 | 1990-04-10 | Hoechst Aktiengesellschaft | Process for the purification of 2-hydroxynaphthalene-6-carboxylic acid |
| CN1335832A (en) * | 1999-08-24 | 2002-02-13 | 株式会社上野制药应用研究所 | Columnar crystals of 6-hydroxy-Naphthoic acid and process for the production thereof |
| CN1844072A (en) * | 2006-04-30 | 2006-10-11 | 中国科学院成都有机化学有限公司 | Method for synthesizing 6-hydroxy-2-naphthoic acid |
| CN102092875A (en) * | 2010-12-09 | 2011-06-15 | 苏州林通新材料科技有限公司 | Wastewater treatment method |
| CN102173988A (en) * | 2011-03-25 | 2011-09-07 | 衢州英特高分子材料有限公司 | Purification method of 6-hydroxyl-2-naphthoic acid |
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2012
- 2012-05-02 CN CN2012101310326A patent/CN102659576A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4916257A (en) * | 1988-01-15 | 1990-04-10 | Hoechst Aktiengesellschaft | Process for the purification of 2-hydroxynaphthalene-6-carboxylic acid |
| CN1335832A (en) * | 1999-08-24 | 2002-02-13 | 株式会社上野制药应用研究所 | Columnar crystals of 6-hydroxy-Naphthoic acid and process for the production thereof |
| CN1844072A (en) * | 2006-04-30 | 2006-10-11 | 中国科学院成都有机化学有限公司 | Method for synthesizing 6-hydroxy-2-naphthoic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776411A (en) * | 2019-11-07 | 2020-02-11 | 北京师范大学 | Simple and efficient method for preparing 2, 7-dihydroxy-3, 6-naphthalene diacid |
| CN114057566A (en) * | 2021-12-09 | 2022-02-18 | 宁夏清研高分子新材料有限公司 | Preparation method of 2-hydroxy-6-naphthoic acid |
| CN114524723A (en) * | 2022-01-29 | 2022-05-24 | 宿迁思睿屹新材料有限公司 | 2-hydroxy-6-naphthoic acid preparation process capable of continuous production and control device thereof |
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Application publication date: 20120912 |