CN103373908A - 9,9-bis[4-(2-hydroxyethoxy) phenyl] fluorene crystal polymorph and synthetic process thereof - Google Patents
9,9-bis[4-(2-hydroxyethoxy) phenyl] fluorene crystal polymorph and synthetic process thereof Download PDFInfo
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- CN103373908A CN103373908A CN2012103301637A CN201210330163A CN103373908A CN 103373908 A CN103373908 A CN 103373908A CN 2012103301637 A CN2012103301637 A CN 2012103301637A CN 201210330163 A CN201210330163 A CN 201210330163A CN 103373908 A CN103373908 A CN 103373908A
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Abstract
The invention researches and develops a 9,9-bis[4-(2-hydroxyethoxy) phenyl] fluorene crystal polymorph and a synthetic process thereof, and particularly provides a synthetic process for obtaining a 9,9-bis[4-(2-hydroxyethoxy) phenyl] fluorene crystal polymorph of which the maximum melting endothermic peak is positioned at a 100-150 DEG C part and the volume density is greater than 0.4g/cm<3> through differential scanning calorimetry. The 9,9-bis[4-(2-hydroxyethoxy) phenyl] fluorene which is synthesized by adopting the synthesis process has the advantages of low melting point, high stacking density and good fluidity, and is in industrial popularization and application well.
Description
Technical field
The present invention relates to a kind of 9, two [4-(2-hydroxy ethoxy) phenyl] fluorenes crystalline polymorph and the synthesis techniques thereof of 9-.
Background technology
Fluorenone is important organic synthesis raw material, can be for the synthesis of anticarcinogen, sympathetic inhibitor and convulsion relieving agent etc. in medicine industry; In agricultural for the synthesis of weedicide and agrochemical; In fuel industry, be used as synthetic aroma two amine fuels; In the xerox industry, be used for making sensitive materials; But Fluorenone bisphenol synthesis series products in plastics industry is made stablizer and the softening agent of polymerization process and is produced functional high molecule material.As far back as the 30-50 age, Fluorenone is used existing research at aspects such as fuel, medicine, agricultural chemicals, plastics and functional high molecule materials abroad, just there is the reagent product seventies in China, at present tangible on a large scale manufacture not yet.Therefore for the synthetic and performance study of Fluorenone and derivative thereof, not only have important theory significance, and for fully exploiting natural resources, increasing economic efficiency is with a wide range of applications.9, the derivative of the Fluorenones such as two [4-(2-hydroxy ethoxy) phenyl] fluorenes of 9-is outstanding at aspects such as thermotolerance, light transmissions, become the raw material for the manufacture of the polymkeric substance with high refractive index such as Resins, epoxy, polyester, polyethers, polycarbonate etc., remain to be become the raw material of optical lens, film, plastic optical fiber, heat-resistant resin or engineering plastics etc.
The Japanese Patent (speciallyying permit No. 4140975) of two [4-(2-hydroxy ethoxy) phenyl] fluorenes of 9,9-points out 1) this product divides polymorph A, and two kinds of crystalline forms of polymorph B.2) because the low and poor fluidity of volume density of polymorph A is not suitable for suitability for industrialized production; The volume density of polymorph B is high and mobile excellent, is fit to suitability for industrialized production.3) principal character of polymorph A is: locate volume density 0.2-0.4g/cm by the maximum melting endotherm(ic)peak that differential scanning calorimetric analysis obtains at 100-130 ℃
34) principal character of polymorph B is: locate at 150-180 ℃ by the maximum melting endotherm(ic)peak that differential scanning calorimetric analysis obtains, volume amasss density 0.5g/cm
3More than.
At non-patent literature Journal of Applied Polymer Science, 1995, vol.58 among the 1189-1197, is recited as 126-128 ℃ to two [4-(2-hydroxy ethoxy) phenyl] the fluorenes fusing points of 9,9-.
And for 9, whether two [4-(2-hydroxy ethoxy) phenyl] fluorenes of 9-exist the maximum melting endotherm(ic)peak that obtains by differential scanning calorimetric analysis to locate at 100-150 ℃, and volume density is greater than 0.4g/cm
3, then not record.
Summary of the invention
The present invention is directed to above-mentioned deficiency, researched and developed a kind of 9, two [4-(2-hydroxy ethoxy) phenyl] fluorenes crystalline polymorph and the synthesis techniques thereof of 9-, purpose is: provide a kind of maximum melting endotherm(ic)peak that obtains by differential scanning calorimetric analysis to locate at 100-150 ℃, volume density is greater than 0.4g/cm
3, and the synthesis technique of good fluidity.
Technical solution of the present invention:
A kind of 9, the synthesis technique of two [4-(2-hydroxy ethoxy) phenyl] the fluorenes crystalline polymorphs of 9-:
The first step adds 9-Fluorenone and ethylene glycol phenyl ether in reactor, stirring and dissolving after 9-Fluorenone is entirely molten, adds promotor 3-thiohydracrylic acid;
Second step is kept 20 ℃, begins to drip 98% the vitriol oil, keeps 50 ~ 90 ℃ of insulation 10h after dropping finishes;
In the 3rd step, insulation adds water and toluene and is warming up to 80 ℃ of washings after finishing;
The 4th step, add successively again water, sodium carbonate solution, water agitator treating respectively once, by the organic phase concentrating under reduced pressure being reclaimed toluene and superfluous Phenoxyethanol, add methyl alcohol temperature rising reflux recrystallization in the mixing solutions that obtains, cool to 0 ~ 20 ℃ of filtration and obtain two [4-(2-hydroxy ethoxy) phenyl] the fluorenes crude products of white 9,9-;
In the 5th step, the 4th step product is obtained the white granular solid with ethyl acetate and alkane solvent recrystallization.
Described 9, the synthesis technique of two [4-(2-hydroxy ethoxy) phenyl] the fluorenes crystalline polymorphs of 9-is characterized in that: the selected solvent of described synthesis technique the 5th step recrystallization is ethyl acetate and two kinds of solvents of alkanes.
Described 9, the synthesis technique of two [4-(2-hydroxy ethoxy) phenyl] the fluorenes crystalline polymorphs of 9-, it is characterized in that: alkane solvents is normal hexane, hexanaphthene, heptane or sherwood oil.
A kind of 9, two [4-(2-hydroxy ethoxy) phenyl] the fluorenes crystalline polymorphs of 9-, it is characterized in that: locate at 100-150 ℃ by the maximum melting endotherm(ic)peak that differential scanning calorimetric analysis obtains, volume density is greater than 0.40g/cm
3
Beneficial effect of the present invention:
Adopt this technique synthetic 9, two [4-(2-hydroxy ethoxy) phenyl] fluorenes of 9-have that fusing point is low, tap density is high, the advantage of good fluidity, are beneficial to industrial application.
Description of drawings
Fig. 1 is differential scanning calorimetric analysis of the present invention (DSC) figure.
Embodiment
Embodiment 1
In the 1L four neck flasks with water-cooled tube, stirring, constant pressure funnel, thermometer, drop into the 9-Fluorenone of 36g (0.2mol), ethylene glycol phenyl ether and the 1mL 3-thiohydracrylic acid of 165.6g (1.2mol), stirring is warmed up to 20 ℃, begin to drip the 30g vitriol oil, maintain 60 ~ 70 ℃ of insulation 12h after dropping finishes.Insulation finishes to add water 100g, and toluene 240g is warming up to 80 ℃, after tell water, organic phase is water respectively, aqueous sodium carbonate, water washs respectively.By the organic phase concentrating under reduced pressure being reclaimed toluene and superfluous Phenoxyethanol.Add methyl alcohol 400g temperature rising reflux recrystallization in the mixing solutions that obtains, cool to 5 spend the filter obtain white 9, two [4-(2-hydroxy ethoxy) phenyl] the fluorenes crude products of 9-, again with adding 200 gram sherwood oil cooling crystallizations after the clarification of 200g acetic acid ethyl dissolution, obtain sterling 54.3g, its yield is 61.9%, and fusing point is 108-162 ℃, HPLC:99.23%, volume density is 0.48g/cm
3
Embodiment 2
In the 1L four neck flasks with water-cooled tube, stirring, constant pressure funnel, thermometer, drop into the 9-Fluorenone of 36g (0.2mol), ethylene glycol phenyl ether and the 1mL 3-thiohydracrylic acid of 110.4g (0.8mol), stirring is warmed up to 20 ℃, begin to drip the 30g vitriol oil, the dropping end is rear to be incubated 10h below 70 ℃.Insulation finishes to add water 100g, and toluene 240g is warming up to 80 ℃, after tell water, organic phase is water respectively, aqueous sodium carbonate, water washs respectively.By the organic phase concentrating under reduced pressure being reclaimed toluene and superfluous Phenoxyethanol.It is heavy to add methyl alcohol 400g temperature rising reflux in the mixing solutions that obtains, cool to 5 spend the filter obtain white 9, two [4-(2-hydroxy ethoxy) phenyl] the fluorenes crude products of 9-, again with adding 200 gram sherwood oil cooling crystallizations after the clarification of 200g acetic acid ethyl dissolution, obtain sterling 58.6g, its yield is 66.8%, and fusing point is 108-162 ℃, HPLC:99.08%, volume density is 0.44g/cm
3
The purpose that the above embodiment of the invention is described is in order to give an example and explanation.They and not exclusively and its do not limit the invention to the clear and definite form that discloses.According to top example, many distortion and variation may be arranged.The embodiment that more than selects and describe is in order to explain best principle of the present invention and practical application thereof, thereby makes others skilled in the art can understand better the different embodiment of the present invention and various distortion.The present invention is not limited to above-mentioned specific implementation method, and is every a kind of 9, and two [4-(2-hydroxy ethoxy) phenyl] the fluorenes polymorphs of 9-are located at 100-150 ℃ by the maximum melting endotherm(ic)peak that differential scanning calorimetric analysis obtains, and volume density is greater than 0.40g/cm
3, no matter which kind of method it adopts obtain, all should list protection scope of the present invention in.
Claims (4)
1. one kind 9, the synthesis technique of two [4-(2-hydroxy ethoxy) phenyl] the fluorenes crystalline polymorphs of 9-:
The first step adds 9-Fluorenone and ethylene glycol phenyl ether in reactor, stirring and dissolving after 9-Fluorenone is entirely molten, adds promotor 3-thiohydracrylic acid;
Second step is kept 20 ℃, begins to drip 98% the vitriol oil, keeps 50 ~ 90 ℃ of insulation 10h after dropping finishes;
In the 3rd step, insulation adds water and toluene and is warming up to 80 ℃ of washings after finishing;
The 4th step, add successively again water, sodium carbonate solution, water agitator treating respectively once, by the organic phase concentrating under reduced pressure being reclaimed toluene and superfluous Phenoxyethanol, add methyl alcohol temperature rising reflux recrystallization in the mixing solutions that obtains, cool to 0 ~ 20 ℃ of filtration and obtain two [4-(2-hydroxy ethoxy) phenyl] the fluorenes crude products of white 9,9-;
In the 5th step, the 4th step product is obtained the white granular solid with ethyl acetate and alkane solvent recrystallization.
2. according to claim 19, the synthesis technique of two [4-(2-hydroxy ethoxy) phenyl] the fluorenes crystalline polymorphs of 9-is characterized in that: the selected solvent of described synthesis technique the 5th step recrystallization is ethyl acetate and two kinds of solvents of alkanes.
3. according to claim 29, the synthesis technique of two [4-(2-hydroxy ethoxy) phenyl] the fluorenes crystalline polymorphs of 9-, it is characterized in that: alkane solvents is normal hexane, hexanaphthene, heptane or sherwood oil.
4. one kind 9, two [4-(2-hydroxy ethoxy) phenyl] the fluorenes crystalline polymorphs of 9-, it is characterized in that: locate at 100-150 ℃ by the maximum melting endotherm(ic)peak that differential scanning calorimetric analysis obtains, volume density is greater than 0.40g/cm
3
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| CN2012103301637A CN103373908A (en) | 2012-04-23 | 2012-09-10 | 9,9-bis[4-(2-hydroxyethoxy) phenyl] fluorene crystal polymorph and synthetic process thereof |
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| CN201210118294.9 | 2012-04-23 | ||
| CN2012101182949A CN102659535A (en) | 2012-04-23 | 2012-04-23 | Synthesizing process for fluorenone derivatives |
| CN2012103301637A CN103373908A (en) | 2012-04-23 | 2012-09-10 | 9,9-bis[4-(2-hydroxyethoxy) phenyl] fluorene crystal polymorph and synthetic process thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935827A (en) * | 2017-12-04 | 2018-04-20 | 江苏永星化工股份有限公司 | Graininess 9,9 2 [3 phenyl 4 (2 hydroxyl-oxethyl) phenyl] fluorenes and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191577A (en) * | 1998-12-25 | 2000-07-11 | Osaka Gas Co Ltd | Production of fluorene derivative |
| CN101724159A (en) * | 2008-10-27 | 2010-06-09 | 三菱瓦斯化学株式会社 | Method for producing thermoplastic resin, polyester resin and polycarbonate resin, and their applications |
| CN102388012A (en) * | 2009-04-13 | 2012-03-21 | 田冈化学工业株式会社 | Method for producing fluorene derivative |
| JP2012077266A (en) * | 2010-10-06 | 2012-04-19 | Teijin Chem Ltd | Thermoplastic resin comprising fluorene derivative, and melt polymerization method thereof |
-
2012
- 2012-04-23 CN CN2012101182949A patent/CN102659535A/en active Pending
- 2012-09-10 CN CN2012103301637A patent/CN103373908A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191577A (en) * | 1998-12-25 | 2000-07-11 | Osaka Gas Co Ltd | Production of fluorene derivative |
| CN101724159A (en) * | 2008-10-27 | 2010-06-09 | 三菱瓦斯化学株式会社 | Method for producing thermoplastic resin, polyester resin and polycarbonate resin, and their applications |
| CN102388012A (en) * | 2009-04-13 | 2012-03-21 | 田冈化学工业株式会社 | Method for producing fluorene derivative |
| JP2012077266A (en) * | 2010-10-06 | 2012-04-19 | Teijin Chem Ltd | Thermoplastic resin comprising fluorene derivative, and melt polymerization method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935827A (en) * | 2017-12-04 | 2018-04-20 | 江苏永星化工股份有限公司 | Graininess 9,9 2 [3 phenyl 4 (2 hydroxyl-oxethyl) phenyl] fluorenes and preparation method thereof |
| CN107935827B (en) * | 2017-12-04 | 2022-04-12 | 江苏永星化工股份有限公司 | Granular 9, 9-di [ 3-phenyl-4- (2-hydroxyethoxy) phenyl ] fluorene and preparation method thereof |
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| CN102659535A (en) | 2012-09-12 |
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Application publication date: 20131030 |