CN102795970B - Clean, environmentally-friendly and economical bisphenol fluorene synthesizing method - Google Patents
Clean, environmentally-friendly and economical bisphenol fluorene synthesizing method Download PDFInfo
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- CN102795970B CN102795970B CN201210238197.3A CN201210238197A CN102795970B CN 102795970 B CN102795970 B CN 102795970B CN 201210238197 A CN201210238197 A CN 201210238197A CN 102795970 B CN102795970 B CN 102795970B
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 23
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims abstract description 26
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000003377 acid catalyst Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000012074 organic phase Substances 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 14
- 238000010189 synthetic method Methods 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical group [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 8
- 239000002798 polar solvent Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000007171 acid catalysis Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 230000006837 decompression Effects 0.000 description 6
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- -1 mercaptan carboxylic acid Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phenol Chemical class C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 description 1
- IAKOSEFINWXRLC-UHFFFAOYSA-N 9H-fluorene methoxymethane phenol Chemical compound C1=CC=CC=2C3=CC=CC=C3CC12.C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.COC IAKOSEFINWXRLC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- ZXRCAYWYTOIRQS-UHFFFAOYSA-N hydron;phenol;chloride Chemical compound Cl.OC1=CC=CC=C1 ZXRCAYWYTOIRQS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a clean, environmentally-friendly and economic bisphenol fluorene synthesizing method, and relates to the field of preparation and organic synthesis of bisphenol fluorene monomers. The method comprises the following steps of: (1) preparation: synthesizing bisphenol fluorene by using cheap 9-fluorenone serving as a starting raw material and phenol in the presence of an acid catalyst and a thiohydracrylic acid cocatalyst; and (2) post treatment: adding a weak base salt to neutralize the catalyst, adding an organic solvent for dissolving, filtering, collecting an organic phase, and reclaiming the solvent and the redundant phenol under reduced pressure. The method is few in reaction steps and easy to operate, the reaction time is shortened, the production efficiency is greatly improved, and industrialized production is facilitated.
Description
Technical field
The present invention relates to the preparation of bisphenol fluorene monomer and organic synthesis field, be specifically related to a kind of bisphenol fluorene synthetic method of clean environment firendly economy.
Background technology
Bisphenol fluorene i.e. two (4-hydroxyphenyl) fluorenes of 9,9-, are a kind of fluorenyl compounds that contains phenolic hydroxyl structure, dissolve in the organic solvents such as monocycle and double ring arene, acetonitrile, toluene, methyl alcohol, methylene dichloride and ethylene dichloride.The preparation of bisphenol fluorene is that Fluorenone and phenol obtain through condensation reaction by under catalyst action.In modern polymerization process industry, bisphenol fluorene is by a large number for condensation reaction, and it is synthetic important monomer or the properties-correcting agent with polycondensation products such as high heat resistance, good optical, high flame retardant epoxy resin, polycarbonate, polyester.Bisphenol fluorene is widely used at the military affairs such as aircraft construction material, engine nozzle, space flight and aviation, electronics, automotive field.
The preparation method of at present existing patent literature is as follows:
(1) synthetic method of report in U.S. Pat. No. 4,675,458
Take 9-Fluorenone as starting raw material and phenol are under sulphuric acid catalysis condition, bisphenol fluorene synthesizing, wherein the vitriol oil accounts for 27% of total raw material weight, after reaction finishes, adopt dissolve with methanol, washing is separated out product, productive rate is about 85%, the method temperature is low, the time is short, productive rate is high, but phenol do not reclaim, and a large amount of phenolic wastewater and acid catalyst environmental pollution are serious; The seriously corroded of strong acid to equipment, causes cost to increase simultaneously.Large trouble.
(2) synthetic method in U.S. Pat. No. 5,387,725 A
Take 9-Fluorenone as starting raw material and methyl-phenoxide are at acetic acid, first synthetic methyl ether bisphenol fluorene under sulfuric acid catalysis condition, then take boron tribromide catalytic pyrolysis and obtain bisphenol fluorene yield as 59%, this method condition is harsh, and yield is low, complex operation, cost is high.
(3) synthetic method in U.S. Pat. No. 5,149,886
Using 9-Fluorenone as starting raw material and phenol hydrogen chloride gas as catalyst condition under bisphenol fluorene synthesizing, productive rate is in 85% left and right, the advantage of hydrogen chloride is that technology is comparatively ripe, raw material consumption is low, but hydrogen chloride gas corrodibility is strong, large to damage of facilities, and production operation is loaded down with trivial details, and potential safety hazard is large.
(4) synthetic method in C.N. Pat. No. 1,617,845
Under the coexisting of thio-alcohol and hydrochloric acid water, make Fluorenone and phenols condensation reaction, manufacture fluorene derivatives.The ratio of Fluorenone and thio-alcohol (weight ratio) is Fluorenone/thio-alcohol=approximately 1/0.01～1/0.5, and the ratio (weight ratio) of the hydrochloric acid in thio-alcohol and hydrochloric acid water (HCl) is thio-alcohol/hydrochloric acid=approximately 1/0.1～1/3.As thio-alcohol, can use mercaptan carboxylic acid's (β-mercaptopropionic acid).The method is marked down and manufacture easily the high purity fluorene derivatives that the transparency is excellent, and does not use the hydrogen chloride gas that is difficult to processing.But in reaction process, use hydrochloric acid, large to equipment corrosion, a large amount of waste water of generation are difficult for processing.
(5) synthetic method in C.N. Pat. No. 101,003,466
Reaction under 9-Fluorenone, phenol, storng-acid cation exchange resin and thiohydracrylic acid exist, prepare bisphenol fluorene, the ratio of Fluorenone and phenol (mol ratio) is 1:(6～15), Zeo-karb accounts for 5%～30% of reaction total mass, and the mass ratio of mercaptan carboxylic acid and 9-Fluorenone is (0.021～0.50): 1.Reaction is stirred 4～15h at 80～120 ℃, and this method is little to equipment corrosion, and catalyzer is reusable, but temperature of reaction is high, and the time is long, and catalyzer cost is high.
summary of the invention:
In order to overcome deficiency of the prior art, the invention provides that a kind of yield is high, cost is low, convenient post-treatment, environmental pollution are little, the low preparation method of being convenient to suitability for industrialized production of processing requirement.
Concrete grammar is as follows:
(1) preparation: take cheap 9-Fluorenone as starting raw material, at acid catalyst, thiohydracrylic acid is under promotor condition, bisphenol fluorene synthesizing with phenol;
(2) aftertreatment: add weak base salt catalyst neutralisation, add organic solvent dissolution, filter, collect organic phase, decompression and solvent recovery and unnecessary phenol.
The bisphenol fluorene synthetic method of clean environment firendly economy of the present invention, according to following step, carry out:
(1) by 9-Fluorenone and phenol 1:4～1:8 in molar ratio, promotor thiohydracrylic acid is pressed 4 ‰ of total raw material quality～9 ‰ and is dropped in reactor, and within 60 ℃, heated and stirred is dissolved;
(2) by acid catalyst, by itself and Fluorenone mol ratio, be that 0.4:1～0.8:1 is slowly added dropwise in the mixed reaction solution that step (1) obtains, dropping temperature within 60 ℃, after dripping under temperature is the condition of 55 ℃～70 ℃, reaction 2～9h;
(3) in the reaction solution finishing to step (2) reaction, add weak base salt, weak base salt and acid catalyst mol ratio are (1.05～2.15): 1, continue to stir 0.5～2h, and then add organic polar solvent in reaction solution, the weight of organic polar solvent and reaction solution weight ratio are 0.5:1～1.5:1(mL:g), standing, separate out salt, collect organic phase;
(4) organic phase step (3) being obtained is carried out underpressure distillation and is collected organic solvent and phenol cut, and distill complete obtaining slightly and produce, through recrystallization, the dry bisphenol fluorene that to obtain;
Wherein the described phenol of step (1) is both as reactant, again as reaction solvent, and the preferred 1:4～1:6 of the mol ratio of 9-Fluorenone and phenol;
Wherein the described thiohydracrylic acid of step (1) is promotor, when thiohydracrylic acid feeds intake by 6 ‰ of total raw material quality, and the catalytic effect of raising acid catalyst that can be larger, Reaction time shorten;
Wherein the described acid catalyst of step (2) can be the vitriol oil, methylsulphonic acid, tosic acid, when take methylsulphonic acid catalysis: methylsulphonic acid by itself and Fluorenone mol ratio when 0.4:1～0.5:1 feeds intake, time for adding is 0.5～1h, dropping temperature is 55～60 ℃, after dripping at 60～70 ℃, reaction times 3～5h, catalytic effect is better like this, and methylsulphonic acid consumption is few;
Step (3) wherein, weak base salt can be anhydrous sodium acetate, anhydrous sodium carbonate, sodium bicarbonate etc.; Preferred anhydrous sodium acetate;
Step (3) wherein, organic polar solvent can be the conventional organic solvents such as ethylene dichloride, methylene dichloride, toluene, cyclohexane, preferably ethylene dichloride is made solvent;
Step (4) wherein, described underpressure distillation, different by the organic solvent of selecting, under vacuum tightness (0.08Mp ~ 0.1Mp), reclaim respectively cut;
Step (4) wherein, described recrystallization solvent can be toluene, methyl alcohol, Virahol, acetone etc., preferably toluene is as recrystallization solvent.
The present invention and traditional technology comparison tool have the following advantages:
1: reaction step number is few, simple to operate, has shortened the reaction times, has greatly improved production efficiency, is easy to suitability for industrialized production.
2: a small amount of acid catalyst is only used in reaction, little to the corrodibility of equipment.
3: adopt in weak base and the post processing mode phenol recovery rate of decompression can reach more than 90%, and whole reaction process almost do not make water, significantly reduced the discharge of wastewater containing phenol and an acidic catalyst, environmental pollution is little; Make up the product loss that washing aftertreatment is shone simultaneously, improved productive rate, to suitability for industrialized production, brought larger economic interests.
embodiment:
embodiment 1
In being housed, the 100ml four-hole boiling flask of magnetic agitation adds 5.40g Fluorenone, 11.29g phenol, 0.10g thiohydracrylic acid, mix and blend, and at 55 ℃, drip the 1.48g vitriol oil, drip about 0.5h, after dripping, be warming up to 60 ℃, reaction 3h, stopped reaction, add 2.60g anhydrous sodium acetate, stir 1h, add 20mL ethylene dichloride to dissolve, filter, filtrate decompression distillation, 40-50 ℃ of (vacuum tightness: 0.08Mp) the lower ethylene dichloride cut of collecting, 85-100 ℃ of (vacuum tightness: 0.09Mp) the lower acetic acid cut of collecting, 125-150 ℃ of (vacuum tightness: 0.09Mp ~ 0.1Mp) the lower phenol cut of collecting, distill complete, claim to obtain the about 5.13g of phenol cut, phenol recovery rate reaches 90.96%, thick product recrystallizing methanol, vacuum-drying obtains 10.08g white solid, yield: 95.89%, purity: 99.68%.
1h NMR(CDCl
3, 500MHz, ppm): δ: 4.95(2H, s, OH), 6.65 ~ 7.75(16H, m, ArH); IR (KBr), v/cm
-1: 3480 (O-H), 3063,3031 (Ar C-H), 1608,1593,1508,1445 (Ar C-C), 1253,1171 (C-O); 223.0～223.9 ℃ of fusing points.
Select the reaction yield of different feed ratio in Table 1.
The reaction result of the different feed ratio of table 1
| Experiment | Catalyzer | Temperature (℃) | Ketone: phenol: catalyzer (mol ratio) | Yield |
| Experiment 1 | The vitriol oil | 60 | 1：4∶0.4 | 94.23% |
| Experiment 2 | The vitriol oil | 60 | 1：4∶0.5 | 95.89% |
| Experiment 3 | The vitriol oil | 60 | 1：4∶0.8 | 95.01% |
| Experiment 4 | The vitriol oil | 60 | 1：6∶0.4 | 94.85% |
| Experiment 5 | The vitriol oil | 60 | 1：6∶0.5 | 96.37% |
| Experiment 6 | The vitriol oil | 60 | 1：6∶0.8 | 96.42% |
| Experiment 7 | The vitriol oil | 60 | 1：8∶0.4 | 95.93% |
| Experiment 8 | The vitriol oil | 60 | 1：8∶0.5 | 96.58% |
| Experiment 9 | The vitriol oil | 60 | 1：8∶0.8 | 96.33% |
embodiment 2
To being equipped with in the 100mL four-hole boiling flask of magnetic agitation, add respectively 5.40g Fluorenone, 16.90g phenol, 0.15g thiohydracrylic acid, mix and blend, and at 55 ℃, drip 1.15g methylsulphonic acid, drip about 0.5h, after dripping, be warming up to 60 ℃, reaction 3h, stopped reaction, add 1.20g anhydrous sodium acetate, stir 1h, add 20mL ethylene dichloride to dissolve, filter, filtrate decompression distillation, 40-50 ℃ of (vacuum tightness: 0.08Mp) the lower ethylene dichloride cut of collecting, 85-100 ℃ of (vacuum tightness: 0.09Mp) the lower acetic acid cut of collecting, 125-150 ℃ of (vacuum tightness: 0.09Mp ~ 0.1Mp) the lower phenol cut of collecting, distill complete, claim to obtain the about 9.68g of phenol cut, phenol recovery rate reaches 86.04%, thick product toluene recrystallization, vacuum-drying obtains 10.17g white solid, yield: 96.75%, purity: 99.53%.
embodiment 3
In being housed, the 100ml four-hole boiling flask of magnetic agitation adds 5.40g Fluorenone, 16.94g phenol, 0.15g thiohydracrylic acid, 2.28g tosic acid, mix and blend, 70 ℃, reaction 5h, stopped reaction, add 1.10g anhydrous sodium acetate, stir 1h, add 20mL ethylene dichloride to dissolve, filter, filtrate decompression distillation, 40-50 ℃ of (vacuum tightness: 0.08Mp) the lower ethylene dichloride cut of collecting, 85-100 ℃ of (vacuum tightness: 0.09Mp) the lower acetic acid cut of collecting, 125-150 ℃ of (vacuum tightness: 0.09Mp ~ 0.1Mp) the lower phenol cut of collecting, distill complete, claim to obtain the about 9.75g of phenol cut, phenol recovery rate reaches 86.35%, thick product ethyl alcohol recrystallization, vacuum-drying obtains 9.97g white solid, yield: 94.95%, purity: 99.17%.
embodiment 4
In being housed, churned mechanically 250ml four-hole boiling flask adds 27.05g Fluorenone, 56.51g phenol, 0.35g thiohydracrylic acid, mix and blend, and at 55 ℃, drip the 7.36g vitriol oil, drip about 2h, after dripping, be warming up to 60 ℃, reaction 3h, stopped reaction, add 12.63g anhydrous sodium acetate, continue to stir 2.5h, add 80mL ethylene dichloride to dissolve, suction filtration, filtrate decompression distillation, 40-50 ℃ of (vacuum tightness: 0.08Mp) the lower ethylene dichloride cut of collecting, 85-100 ℃ of (vacuum tightness: 0.09Mp) the lower acetic acid cut of collecting, 125-150 ℃ of (vacuum tightness: 0.09Mp ~ 0.1Mp) the lower phenol cut of collecting, distill complete, claim to obtain the about 24.72g of phenol cut, phenol recovery rate reaches 87.50%, thick product toluene recrystallization, vacuum-drying obtains 50.24g white solid, yield: 95.59%, purity: 99.04%.
comparative example
In being housed, churned mechanically 250ml four-hole boiling flask adds 45g Fluorenone, 94g phenol, 0.2mL thiohydracrylic acid, mix and blend at 30 ℃, then drips the 40mL vitriol oil (96%), and temperature control is at 30 ℃-70 ℃, thin-layer chromatography is followed the tracks of, after 15min, Fluorenone is changed completely, uses 100mL dissolve with methanol, and solution is poured in 1L water, product is separated out, suction filtration, filtrate extracts with ethylene dichloride, reclaims to obtain phenol 20.46g, phenol recovery rate is 43.53%, filter cake obtains 75.69g white solid through vacuum-drying, yield 86.50%, purity: 98.72%.
Comparative example adopts the synthetic target product of patent U.S. Pat. No. 4,675,458 methods
Comparative example and embodiment comparison, both can react at low temperatures, and the reaction times is short, but comparative example yield is starkly lower than the yield of the synthetic target product of the present invention; Comparative example has been used a large amount of easy volatile solvent and has produced a large amount of waste water, has caused the wasting of resources and environmental pollution." directly phenol is reclaimed in washing+extraction " comparative example and " phenol is reclaimed in weak base salt neutralization+underpressure distillation " example the results are shown in Table 1 to the impact of product yield and phenol recovery
The impact of the different post processing modes of table 1 on yield
| ? | Product yield % | Phenol recovery % |
| Embodiment 1 | 95.89 | 90.96 |
| Embodiment 2 | 96.75 | 86.04 |
| Embodiment 3 | 94.95 | 86.35 |
| Embodiment 4 | 95.59 | 87.50 |
| Comparative example | 86.50 | 43.53 |
Preparation method of the present invention has that few, the simple to operate safety of synthesis step, yield are high in sum, environmental friendliness, clean economy easily realize the advantages such as suitability for industrialized production.
Claims (3)
1. the bisphenol fluorene synthetic method of clean environment firendly economy, is characterized in that carrying out according to following step:
(1) by 9-Fluorenone and phenol 1:4～1:8 in molar ratio, promotor thiohydracrylic acid is pressed 4 ‰ of total raw material quality～9 ‰ and is dropped in reactor, and within 60 ℃, heated and stirred is dissolved;
(2) by acid catalyst, by itself and Fluorenone mol ratio, be that 0.4:1～0.8:1 is slowly added dropwise in the mixed reaction solution that step (1) obtains, dropping temperature within 60 ℃, after dripping under temperature is the condition of 55 ℃～70 ℃, reaction 2～9h;
(3) in the reaction solution finishing to step (2) reaction, add weak base salt, weak base salt and acid catalyst mol ratio are 1.05:1～2.15:1, continue to stir 0.5～2h, and then add organic polar solvent in reaction solution, the weight of organic polar solvent and reaction solution weight ratio are 0.5:1～1.5:1(mL:g), standing, separate out salt, collect organic phase;
(4) organic phase step (3) being obtained is carried out underpressure distillation and is collected organic solvent and phenol cut, and distill complete obtaining slightly and produce, through recrystallization, the dry bisphenol fluorene that to obtain;
The bisphenol fluorene synthetic method of clean environment firendly economy according to claim 1, is characterized in that the described phenol of step (1) is wherein both as reactant, again as reaction solvent, and the mol ratio 1:4～1:6 of 9-Fluorenone and phenol;
Wherein the described thiohydracrylic acid of step (1) accounts for 6 ‰ of total raw material quality;
Wherein the described acid catalyst of step (2) is the vitriol oil, methylsulphonic acid, tosic acid, while take methylsulphonic acid catalysis: methylsulphonic acid by itself and Fluorenone mol ratio when 0.4:1～0.5:1 feeds intake, time for adding is 0.5～1h, dropping temperature is 55～60 ℃, after dripping at 60～70 ℃, reaction times 3～5h;
=wherein in step (3), weak base salt is anhydrous sodium acetate, anhydrous sodium carbonate, sodium bicarbonate;
Wherein in step (3), organic polar solvent is ethylene dichloride, methylene dichloride, toluene, cyclohexane;
The wherein described underpressure distillation of step (4), different by the organic solvent of selecting, under vacuum tightness 0.08Mp ~ 0.1Mp, reclaim respectively cut;
Wherein the described recrystallization solvent of step (4) is toluene, methyl alcohol, Virahol, acetone.
2. the bisphenol fluorene synthetic method of clean environment firendly economy according to claim 1, is characterized in that wherein the middle weak base salt of step (3) is anhydrous sodium acetate;
Wherein in step (3), organic polar solvent is ethylene dichloride.
3. the bisphenol fluorene synthetic method of clean environment firendly economy according to claim 1, is characterized in that wherein the recrystallization solvent described in step (4) is toluene.
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| CN103804149B (en) * | 2014-02-20 | 2015-09-02 | 常州市正锋光电新材料有限公司 | The preparation method of bisphenol fluorene |
| CN105693475B (en) * | 2016-03-15 | 2018-04-17 | 辽宁大学 | A kind of solid acid H2SO4‑SiO2Catalysis prepares the process of bisphenol fluorene |
| CN106478381B (en) * | 2016-10-16 | 2019-06-21 | 武汉轻工大学 | A method of bis ether fluorenes is prepared by catalyzing epoxyethane |
| TWI675822B (en) * | 2018-09-12 | 2019-11-01 | 中國石油化學工業開發股份有限公司 | Methods for producing bisphenol fluorene compound |
| CN114591148A (en) * | 2022-04-07 | 2022-06-07 | 南京邮电大学 | Method for synthesizing bisphenol fluorene based on microreactor |
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