CN104447217A - Synthesis method of 4,4-bisphenol F - Google Patents
Synthesis method of 4,4-bisphenol F Download PDFInfo
- Publication number
- CN104447217A CN104447217A CN201410737057.XA CN201410737057A CN104447217A CN 104447217 A CN104447217 A CN 104447217A CN 201410737057 A CN201410737057 A CN 201410737057A CN 104447217 A CN104447217 A CN 104447217A
- Authority
- CN
- China
- Prior art keywords
- bisphenol
- mass parts
- filter cake
- distilled water
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
Abstract
The invention discloses a synthesis method of 4,4-bisphenol F. The synthesis method of 4,4-bisphenol F is characterized by comprising the following steps: pouring 150 parts (by weight) of phenol, 60-90 parts of 85% phosphoric acid and 60-90 parts of solvent in a reactor, stirring for 1-3 hours at 45-65 DEG C, dripping 22-33 parts of 37% formaldehyde, keeping the reaction temperature at 45-65 DEG C, controlling the dripping time to be 2-8 hours, then reacting for 0.5-2 hours at 45-75 DEG C, standing for layering, removing lower-layer colourless and transparent liquid, and then filtering upper-layer white and turbid liquid; washing a filter cake by the solvent, then washing the filter cake to be neutral by distilled water, drying, then mixing and dissolving with 40-78 parts of absolute methanol, then adding the obtained methanol solution in 66-128 parts of distilled water and mixing, separating out solid substances, filtering and drying to prepare 4,4-bisphenol F. According to the synthesis method disclosed by the invention, 4,4-bisphenol F is prepared by a pure phosphoric acid catalysis method, and the synthesis method is suitable for industrial production and high in practicability.
Description
Technical field
The invention belongs to the preparation of organic bisphenol compounds.Relate to a kind of synthetic method of 4,4-Bisphenol F, 4,4-Bisphenol F prepared by the present invention are applicable to the field such as epoxy resin, polycarbonate.
Background technology
4,4-Bisphenol F, as a kind of fine chemical product, due to the structure of its uniqueness, is considered to the excellent substitute of dihydroxyphenyl propane in epoxy resin field and polycarbonate field.
Document (synthesis and characteries of bisphenol F epoxy resin, Shi Ning, thermosetting resin, 1995,3:13 ~ 17) is reported, the viscosity of 4,4-bisphenol F epoxy resins of ideal structure is about 1/5 of bisphenol A epoxide resin.Document (the study on the synthesis of wind electricity blade material bisphenol F epoxy resin, Liao Yongyong, University Of Xiangtan, master thesis, 2009) also point out bisphenol F epoxy resin have that viscosity is low, solvent resistance is strong, impact resistance is high, to fiber impregnation and and the advantage such as glass reinforced plastic composite performance is good, use cost is low, the basic material-wind electricity blade of emerging wind-powered electricity generation energy wind-power electricity generation can be adapted to the viscosity of epoxy resin, the requirement to fiber impregnability, impact resistance and toughness.And the viscosity of bisphenol A type epoxy resin universal is at present high, shock-resistance and weathering resistance poor, paint film out of doors easily efflorescence loss of gloss owe again plentiful, outdoor coating and tackiness agent should not be made.
Polycarbonate is as one of five large-engineering plastics, be widely used in glazing, automotive industry and electronics, electrical equipment industry, secondly also have office equipment, medical treatment and health care, film, leisure and the protective equipments etc. such as industrial machinery part, CD, packaging, computer.The polycarbonate of current industrial application mainly refers to the aromatic copolycarbonate based on dihydroxyphenyl propane synthesis, and dihydroxyphenyl propane is as a kind of industrial chemicals, on April 18th, 2008 is formally regarded as toxic substance by federal government of Canada, and forbids to add in food product pack.European Union is thought can bring out sexual prematurity containing dihydroxyphenyl propane feeding bottle, from 2 days March in 2011, forbids the baby bottles containing production chemical substance dihydroxyphenyl propane (BPA).The departments such as ministry of Health of China issue to announce and claim, and play the infant feeding bottle that import prohibition and sale polycarbonate infant feeding bottle and other contain dihydroxyphenyl propane on September 1st, 2011, are responsible for recalling by manufacturing enterprise or importor.Therefore there are 4, the 4-position Bisphenol F alternatively product with dihydroxyphenyl propane analog structure, in polycarbonate synthesis, show huge potentiality.
Existing Bisphenol F technology of preparing mainly adopts phenol and formaldehyde to be raw material, carries out synthesizing (JP08198790, JP08268943, JP09067287, CN102992964A, CN103936562A) under an acidic catalyst (example hydrochloric acid, phosphoric acid, oxalic acid, solid acid etc.) effect.But due to the character of reaction raw materials, product is generally the mixture of three kinds of isomer of Bisphenol F, namely 4,4-dihydroxydiphenyl methane (4,4-position Bisphenol F), 2,4-dihydroxydiphenyl methane and 2,2-dihydroxydiphenyl methane, and wherein the content of 4,4-Bisphenol F is general lower.By the improvement to synthetic method, the situation that 4,4-Bisphenol F content is lower obtains certain improvement, and 4,4-Bisphenol F content is brought up to about 60%, US4400554 and 4,4-Bisphenol F content is increased to about 55 ~ 75% by CN101440022A.It is preferable that patent CN102491879A is by 4,4-Bisphenol F content brings up to 93.5%, CN103319314A is by 4,4-Bisphenol F content brings up to 96%, but the product that these two kinds of methods obtain is still the mixture of three kinds of isomer, and (the former is 7 ~ 12:1 to have employed very high phenolic aldehyde mol ratio, the latter is 10 ~ 17:1), still cannot synthesize 4,4-pure Bisphenol F, and the recovery of high magnification phenol makes production energy consumption very large.Have not yet to see the bibliographical information that pure phosphoric acid catalysis method prepares 4,4-pure Bisphenol F.
Summary of the invention
Object of the present invention is intended to overcome above-mentioned deficiency of the prior art; solve pure phosphoric acid catalysis method for a long time and cannot obtain pure 4; the technical barrier of 4-Bisphenol F; there is provided a kind of with phenol and formaldehyde for raw material; lower phenol formaldehyde ratio, be catalyzer with phosphoric acid effect under prepare pure 4; the method of 4-Bisphenol F, thus provide a kind of proper scale to prepare the method for 4,4-pure position Bisphenol F.
Content of the present invention is: a kind of 4, the synthetic method of 4-Bisphenol F, it is characterized in that: the phosphate aqueous solution being 85% by 150 mass parts phenol and 60 ~ 90 mass parts mass percent concentrations drops in reactor, add 60 ~ 90 mass parts solvents, 1 ~ 3h is stirred at the temperature of 45 DEG C ~ 65 DEG C, after stirring, dripping 22 ~ 33 mass parts mass percent concentrations is the formalin of 37%, keep temperature of reaction at 45 DEG C ~ 65 DEG C in dropping process, dropwise at 2 ~ 8h, and then reaction 0.5 ~ 2h is continued at 45 ~ 75 DEG C, stratification, be separated except after sub-cloud colourless transparent liquid, again the white opacity liquid on upper strata is filtered, gained filter cake solvent wash 2 times, all filters with after 60 ~ 90 mass parts solvents and filter cake mix and blend 1h at every turn, again with distilled water by after filter cake washing to neutral (pH can be any point in 6.5 ~ 7), dry, methanol solution is obtained again with 40 ~ 78 mass parts anhydrous methanol mixed dissolutions, then the methanol solution obtained is joined mixing in the distilled water (or deionized water) of 66 ~ 128 mass parts, solids is separated out, and filters, solids drying, i.e. obtained (pure) 4,4-Bisphenol F.
In content of the present invention: described solvent can be one or both the mixture in dimethylbenzene, toluene, ethylbenzene, benzene, 1，3，5-trimethyl-benzene, propyl benzene.。
Compared with prior art, the present invention has features and beneficial effect:
(1) the present invention adopts traditional phosphoric acid as catalyzer, solves the technical barrier that pure phosphoric acid catalysis method for a long time cannot obtain 4,4-pure Bisphenol F; Under lower phenol formaldehyde ratio (mol ratio is 4 ~ 6:1) condition under achieve the preparation method of 4,4-pure Bisphenol F compounds; Embodiment result shows that the purity of its 4,4-Bisphenol F reaches 99.0% ~ 99.4%, and yield reaches 45.6% ~ 75.3%, and product quality is good, and yield is high;
(2) the present invention breaches and cheap mass-producing can not prepare pure 4 in the past, the technical bottleneck of 4-Bisphenol F, thus make to adopt pure 4 in commercialization, 4-Bisphenol F substitutes dihydroxyphenyl propane and comprehensive 4 of the synthesizing new that is widely used in, 4-bisphenol F epoxy resin and the poly-contour performance materials of 4,4-bisphenol-f type carbonic ether become possibility;
(3) preparation technology of the present invention is simple, and operation is easy, easily operates, and low production cost very easily realizes industrialization, is appropriate to the scale of chemical production, practical.
Embodiment
The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1:
The phosphoric acid being 85% by 150 ㎏ phenol and 75 ㎏ mass percent concentrations drops in reactor, add 75 ㎏ toluene, at 45 DEG C, stir 1.5h, to be mixed evenly after, starting to drip 33 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise in 8h, and then at 45 DEG C, continue reaction 1h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 75 ㎏ toluene/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, with 40 ㎏ anhydrous methanols dissolve, then add distilled water chromatography (that is: filter cake anhydrous methanol dissolve after mixture in add again distilled water, solids separate out; Described in embodiment below, " chromatography " is identical), filter, dry, obtain 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.2%, yield (in formaldehyde, lower same) 75.3%.
Embodiment 2:
The phosphoric acid being 85% by 150 ㎏ phenol and 90 ㎏ mass percent concentrations drops in reactor, add 90 ㎏ dimethylbenzene, at 45 DEG C, stir 1h, to be mixed evenly after, starting to drip 30 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise in 6h, and then at 65 DEG C, continue reaction 0.5h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 90 ㎏ dimethylbenzene/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 50 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.1%, yield 65.2%.
Embodiment 3:
The phosphoric acid being 85% by 150 ㎏ phenol and 60 ㎏ mass percent concentrations drops in reactor, add 60 ㎏ ethylbenzene, at 45 DEG C, stir 1h, to be mixed evenly after, starting to drip 22 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise in 4h, and then at 75 DEG C, continue reaction 0.5h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 60 ㎏ ethylbenzene/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 68 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.0%, yield 61.7%.
Embodiment 4:
The phosphoric acid being 85% by 150 ㎏ phenol and 70 ㎏ mass percent concentrations drops in reactor, add 60 ㎏ propyl benzene, at 45 DEG C, stir 3h, to be mixed evenly after, starting to drip 24 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise at 4.5h, and then at 60 DEG C, continue reaction 1.5h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 80 ㎏ propyl benzene/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 50 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.2%, yield 52.4%.
Embodiment 5:
The phosphoric acid being 85% by 150 ㎏ phenol and 80 ㎏ mass percent concentrations drops in reactor, adds 75 ㎏ 1,3,5-Three methyl Benzene, at 45 DEG C, stir 2h, to be mixed evenly after, starting to drip 27 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise at 3.5h, and then at 55 DEG C, continue reaction 1h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 60 ㎏ 1，3，5-trimethyl-benzene/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 62 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.1%, yield 46.5%.
Embodiment 6:
The phosphoric acid being 85% by 150 ㎏ phenol and 65 ㎏ mass percent concentrations drops in reactor, add 85 ㎏ benzene, at 45 DEG C, stir 2.5h, to be mixed evenly after, starting to drip 30 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise at 2h, and then at 75 DEG C, continue reaction 2h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 76 ㎏ benzene/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 44 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.0%, yield 48.8%.
Embodiment 7:
The phosphoric acid being 85% by 150 ㎏ phenol and 85 ㎏ mass percent concentrations drops in reactor, add 80 ㎏ solvents (dimethylbenzene: the mass ratio of toluene=1:8), 1h is stirred at 45 DEG C, to be mixed evenly after, starting to drip 29 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise at 3h, and then at 45 DEG C, continue reaction 1h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 80 ㎏ solvents (dimethylbenzene: the mass ratio of toluene=1:8)/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 58 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.4%, yield 55.9%.
Embodiment 8:
The phosphoric acid being 85% by 150 ㎏ phenol and 90 ㎏ mass percent concentrations drops in reactor, add 90 ㎏ solvents (toluene: the mass ratio of propyl benzene=5:1), 1.5h is stirred at 45 DEG C, to be mixed evenly after, starting to drip 23 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise at 6h, and then at 55 DEG C, continue reaction 2h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 90 ㎏ solvents (toluene: the mass ratio of propyl benzene=5:1)/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 50 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.3%, yield 50.6%.
Embodiment 9:
The phosphoric acid being 85% by 150 ㎏ phenol and 70 ㎏ mass percent concentrations drops in reactor, add 85 ㎏ solvents (toluene: the mass ratio of ethylbenzene=3:2), 3h is stirred at 45 DEG C, to be mixed evenly after, starting to drip 25 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise at 5h, and then at 65 DEG C, continue reaction 1.5h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 60 ㎏ solvents (toluene: the mass ratio of ethylbenzene=3:2)/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 60 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.2%, yield 53.6%.
Embodiment 10:
The phosphoric acid being 85% by 150 ㎏ phenol and 75 ㎏ mass percent concentrations drops in reactor, add 75 ㎏ solvent (ethylbenzene: 1,3, the mass ratio of 5-Three methyl Benzene=5:2), 2h is stirred at 45 DEG C, to be mixed evenly after, starting to drip 32 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise at 3h, and then at 50 DEG C, continue reaction 1.5h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 69 ㎏ solvents (ethylbenzene: the mass ratio of 1，3，5-trimethyl-benzene=5:2)/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 66 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.0%, yield 47.1%.
Embodiment 11:
The phosphoric acid being 85% by 150 ㎏ phenol and 60 ㎏ mass percent concentrations drops in reactor, add 65 ㎏ solvent (toluene: 1,3, the mass ratio of 5-Three methyl Benzene=3:1), 2.5h is stirred at 45 DEG C, to be mixed evenly after, starting to drip 33 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise at 4h, and then at 70 DEG C, continue reaction 1h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 84 ㎏ solvents (toluene: the mass ratio of 1，3，5-trimethyl-benzene=3:1)/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 72 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.1%, yield 45.6%.
Embodiment 12:
The phosphoric acid being 85% by 150 ㎏ phenol and 68 ㎏ mass percent concentrations drops in reactor, add 60 ㎏ solvents (1,3,5-Three methyl Benzene: the mass ratio of propyl benzene=1:4), 3h is stirred at 45 DEG C, to be mixed evenly after, starting to drip 30 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise at 5h, and then at 60 DEG C, continue reaction 0.5h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 75 ㎏ solvents (1，3，5-trimethyl-benzene: the mass ratio of propyl benzene=1:4)/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 40 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.3%, yield 51.3%.
Embodiment 13:
The phosphoric acid being 85% by 150 ㎏ phenol and 78 ㎏ mass percent concentrations drops in reactor, add 70 ㎏ solvents (toluene: the mass ratio of propyl benzene=6:1), 1h is stirred at 45 DEG C, to be mixed evenly after, starting to drip 28 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise at 7h, and then at 50 DEG C, continue reaction 1h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 90 ㎏ solvents (toluene: the mass ratio of propyl benzene=6:1)/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 48 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.1%, yield 47.7%.
Embodiment 14:
The phosphoric acid being 85% by 150 ㎏ phenol and 88 ㎏ mass percent concentrations drops in reactor, add 80 ㎏ solvents (ethylbenzene: the mass ratio of propyl benzene=1:1), 1.5h is stirred at 45 DEG C, to be mixed evenly after, starting to drip 25 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise at 8h, and then at 68 DEG C, continue reaction 2h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 60 ㎏ solvents (ethylbenzene: the mass ratio of propyl benzene=1:1)/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 54 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.3%, yield 52.8%.
Embodiment 15:
The phosphoric acid being 85% by 150 ㎏ phenol and 90 ㎏ mass percent concentrations drops in reactor, add 90 ㎏ solvents (dimethylbenzene: the mass ratio of benzene=2:1), 2h is stirred at 45 DEG C, to be mixed evenly after, starting to drip 22 ㎏ mass percent concentrations is the formaldehyde solution of 37%, keep temperature of reaction 45 DEG C constant in dropping process, dropwise at 6h, and then at 53 DEG C, continue reaction 1.5h, stratification, be separated except after sub-cloud colourless transparent liquid, then the white opacity liquid on upper strata is filtered; Filter after gained filter cake 67 ㎏ solvents (dimethylbenzene: the mass ratio of benzene=2:1)/time carry out twice agitator treating 1h, with distilled water, filter cake is washed till neutrality again, drying, dissolves with 65 ㎏ anhydrous methanols, then adds distilled water chromatography, filter, drying, obtains 4,4-pure Bisphenol F, liquid chromatography (HPLC) purity 99.0%, yield 57.4%.
Embodiment 16:
A kind of 4, the synthetic method of 4-Bisphenol F, step is: the phosphate aqueous solution being 85% by 150 mass parts phenol and 60 mass parts mass percent concentrations drops in reactor, add 60 mass parts solvents, 1h is stirred at the temperature of 45 DEG C ~ 50 DEG C, after stirring, dripping 22 mass parts mass percent concentrations is the formalin of 37%, keep temperature of reaction at 45 DEG C ~ 50 DEG C in dropping process, dropwise at 2 ~ 8h, and then at 45 ~ 55 DEG C, continue reaction 0.5h, stratification, be separated except after sub-cloud colourless transparent liquid, again the white opacity liquid on upper strata is filtered, gained filter cake solvent wash 2 times, all filters with after 60 mass parts solvents and filter cake mix and blend 1h at every turn, again with distilled water by after filter cake washing to neutral (pH can be any point in 6.5 ~ 7), dry, methanol solution is obtained again with 40 mass parts anhydrous methanol mixed dissolutions, then the methanol solution obtained is joined mixing in the distilled water (or deionized water) of 66 mass parts, solids is separated out, and filters, solids drying, i.e. obtained (pure) 4,4-Bisphenol F.
Embodiment 17:
A kind of 4, the synthetic method of 4-Bisphenol F, step is: the phosphate aqueous solution being 85% by 150 mass parts phenol and 90 mass parts mass percent concentrations drops in reactor, add 90 mass parts solvents, 3h is stirred at the temperature of 55 DEG C ~ 65 DEG C, after stirring, dripping 33 mass parts mass percent concentrations is the formalin of 37%, keep temperature of reaction at 55 DEG C ~ 65 DEG C in dropping process, dropwise at 8h, and then at 65 ~ 75 DEG C, continue reaction 2h, stratification, be separated except after sub-cloud colourless transparent liquid, again the white opacity liquid on upper strata is filtered, gained filter cake solvent wash 2 times, all filters with after 90 mass parts solvents and filter cake mix and blend 1h at every turn, again with distilled water by after filter cake washing to neutral (pH can be any point in 6.5 ~ 7), dry, methanol solution is obtained again with 78 mass parts anhydrous methanol mixed dissolutions, then the methanol solution obtained is joined mixing in the distilled water (or deionized water) of 128 mass parts, solids is separated out, and filters, solids drying, i.e. obtained (pure) 4,4-Bisphenol F.
Embodiment 18:
A kind of 4, the synthetic method of 4-Bisphenol F, step is: the phosphate aqueous solution being 85% by 150 mass parts phenol and 75 mass parts mass percent concentrations drops in reactor, add 75 mass parts solvents, 2h is stirred at the temperature of 45 DEG C ~ 50 DEG C, after stirring, dripping 28 mass parts mass percent concentrations is the formalin of 37%, keep temperature of reaction at 45 DEG C ~ 5 DEG C in dropping process, dropwise at 5h, and then at 65 ~ 70 DEG C, continue reaction 1.2h, stratification, be separated except after sub-cloud colourless transparent liquid, again the white opacity liquid on upper strata is filtered, gained filter cake solvent wash 2 times, all filters with after 80 mass parts solvents and filter cake mix and blend 1h at every turn, again with distilled water by after filter cake washing to neutral (pH can be any point in 6.5 ~ 7), dry, methanol solution is obtained again with 60 mass parts anhydrous methanol mixed dissolutions, then the methanol solution obtained is joined mixing in the distilled water (or deionized water) of 100 mass parts, solids is separated out, and filters, solids drying, i.e. obtained (pure) 4,4-Bisphenol F.
Embodiment 19:
A kind of 4, the synthetic method of 4-Bisphenol F, step is: the phosphate aqueous solution being 85% by 150 mass parts phenol and 60 ~ 90 mass parts mass percent concentrations drops in reactor, add 60 ~ 90 mass parts solvents, 1 ~ 3h is stirred at the temperature of 45 DEG C ~ 65 DEG C, after stirring, dripping 22 ~ 33 mass parts mass percent concentrations is the formalin of 37%, keep temperature of reaction at 45 DEG C ~ 65 DEG C in dropping process, dropwise at 2 ~ 8h, and then reaction 0.5 ~ 2h is continued at 45 ~ 75 DEG C, stratification, be separated except after sub-cloud colourless transparent liquid, again the white opacity liquid on upper strata is filtered, gained filter cake solvent wash 2 times, all filters with after 60 ~ 90 mass parts solvents and filter cake mix and blend 1h at every turn, again with distilled water by after filter cake washing to neutral (pH can be any point in 6.5 ~ 7), dry, methanol solution is obtained again with 40 ~ 78 mass parts anhydrous methanol mixed dissolutions, then the methanol solution obtained is joined mixing in the distilled water (or deionized water) of 66 ~ 128 mass parts, solids is separated out, and filters, solids drying, i.e. obtained (pure) 4,4-Bisphenol F,
The concrete mass parts consumption of each component in embodiment 19 ~ 25 (unit of mass parts: kilogram) see the following form:
In above-described embodiment 16 ~ 25: described solvent can be one or both the mixture in dimethylbenzene, toluene, ethylbenzene, benzene, 1，3，5-trimethyl-benzene, propyl benzene.
In above-described embodiment: in the percentage adopted, do not indicate especially, be quality (weight) percentage; In the ratio adopted, do not indicate especially, be quality (weight) ratio; Described quality (weight) part can be all gram or kilogram.
In above-described embodiment: the processing parameter (temperature, time, concentration etc.) in each step and each amounts of components numerical value etc. are scope, and any point is all applicable.
The concrete same prior art of technology contents described in content of the present invention and above-described embodiment, described starting material are commercially available prod.
The invention is not restricted to above-described embodiment, all can implement described in content of the present invention and there is described good result.
Claims (2)
1. one kind 4, the synthetic method of 4-Bisphenol F, it is characterized in that: the phosphate aqueous solution being 85% by 150 mass parts phenol and 60 ~ 90 mass parts mass percent concentrations drops in reactor, add 60 ~ 90 mass parts solvents, 1 ~ 3h is stirred at the temperature of 45 DEG C ~ 65 DEG C, after stirring, dripping 22 ~ 33 mass parts mass percent concentrations is the formalin of 37%, keep temperature of reaction at 45 DEG C ~ 65 DEG C in dropping process, dropwise at 2 ~ 8h, and then reaction 0.5 ~ 2h is continued at 45 ~ 75 DEG C, stratification, be separated except after sub-cloud colourless transparent liquid, again the white opacity liquid on upper strata is filtered, gained filter cake solvent wash 2 times, all filters with after 60 ~ 90 mass parts solvents and filter cake mix and blend 1h at every turn, again with distilled water by after filter cake washing to neutrality, dry, then obtain methanol solution with 40 ~ 78 mass parts anhydrous methanol mixed dissolutions, then joined by the methanol solution obtained in the distilled water of 66 ~ 128 mass parts and mix, solids is separated out, and filters, solids drying, i.e. obtained 4,4-Bisphenol F.
2., by the synthetic method of 4,4-Bisphenol F according to claim 1, it is characterized in that: described solvent is one or both the mixture in dimethylbenzene, toluene, ethylbenzene, benzene, 1，3，5-trimethyl-benzene, propyl benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410737057.XA CN104447217A (en) | 2014-12-05 | 2014-12-05 | Synthesis method of 4,4-bisphenol F |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410737057.XA CN104447217A (en) | 2014-12-05 | 2014-12-05 | Synthesis method of 4,4-bisphenol F |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104447217A true CN104447217A (en) | 2015-03-25 |
Family
ID=52894057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410737057.XA Pending CN104447217A (en) | 2014-12-05 | 2014-12-05 | Synthesis method of 4,4-bisphenol F |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104447217A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461519A (en) * | 2015-11-06 | 2016-04-06 | 江南大学 | Neo-epoxy resin proplastid bisphenol F |
| CN111579670A (en) * | 2020-05-26 | 2020-08-25 | 亿科检测认证有限公司 | Method for detecting bisphenol F in food contact plastic product |
| CN113101979A (en) * | 2021-04-22 | 2021-07-13 | 江南大学 | Lewis acid promoted compound protonic acid and catalytic application thereof |
| CN115215736A (en) * | 2022-08-11 | 2022-10-21 | 山东海科创新研究院有限公司 | Low-phenolic-ratio bisphenol F synthesis process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400554A (en) * | 1982-03-29 | 1983-08-23 | Monsanto Company | Process for making bis(hydroxyphenyl)methanes |
-
2014
- 2014-12-05 CN CN201410737057.XA patent/CN104447217A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400554A (en) * | 1982-03-29 | 1983-08-23 | Monsanto Company | Process for making bis(hydroxyphenyl)methanes |
Non-Patent Citations (2)
| Title |
|---|
| 张文雯 等: "改性阳离子交换树脂催化合成双酚F", 《化工进展》 * |
| 李月明: "双酚F合成新工艺，氧肟酸类聚合物及新烟碱类杀虫剂的制备", 《中国优秀硕士学位论文全文数据库-工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461519A (en) * | 2015-11-06 | 2016-04-06 | 江南大学 | Neo-epoxy resin proplastid bisphenol F |
| CN111579670A (en) * | 2020-05-26 | 2020-08-25 | 亿科检测认证有限公司 | Method for detecting bisphenol F in food contact plastic product |
| CN113101979A (en) * | 2021-04-22 | 2021-07-13 | 江南大学 | Lewis acid promoted compound protonic acid and catalytic application thereof |
| CN115215736A (en) * | 2022-08-11 | 2022-10-21 | 山东海科创新研究院有限公司 | Low-phenolic-ratio bisphenol F synthesis process |
| CN115215736B (en) * | 2022-08-11 | 2024-01-26 | 东营市赫邦化工有限公司 | Bisphenol F synthesis process with low phenolic ratio |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104447217A (en) | Synthesis method of 4,4-bisphenol F | |
| CN105860030B (en) | Glycidyl amine type epoxy resin of structure containing Cardo and preparation method thereof | |
| CN105503550A (en) | Green preparation method for compounding pinacolone | |
| CN104193961A (en) | Preparation method for hydrogenated bisphenol A epoxy resin | |
| CN102167658A (en) | Technology for complexing, crystallizing, separating and purifying metacresol | |
| CN103013682A (en) | Synthetic method for epoxy soybean oil acrylate | |
| CN107311868A (en) | A kind of method for preparing p-tert-butyl benzoic acid methyl esters | |
| CN104084089B (en) | The preparation method of rosin emulsifying agent | |
| US20200062888A1 (en) | Biomass-based epoxy resin and preparation method thereof | |
| CN102701985A (en) | Method for preparing epoxy resin curing agent by performing alcoholysis on PET (Polyethylene Terephthalate) polyester | |
| CN102311420B (en) | Method for synthesizing epsilon-caprolactone | |
| CN102838725A (en) | Preparation method of phenol-dicyclopentadiene epoxy resin | |
| CN103275302A (en) | Synthetic method for tri-functionality water-soluble epoxy resin | |
| CN103224837A (en) | Rapid and green preparation method of epoxidation soybean oil | |
| CN104557791B (en) | Method for preparing plant bisphenol glycidyl ether | |
| CN105536827A (en) | Composite acid supported catalyst and catalytic synthesis method of bisphenol F | |
| CN105085335A (en) | Method for preparing 3-mercapto-propionate | |
| CN105669384B (en) | The method that one kind catalyzes and synthesizes high 44 ' content of isomer Bisphenol F | |
| CN102875497A (en) | Soybean oil-based aliphatic epoxy resin and preparation method thereof | |
| CN102643517B (en) | Method for preparing composite material by blending PHQEP/montmorillonite and modified epoxy resin | |
| CN101838222B (en) | Preparation method of N-(4-ethoxycarbonylphenyl)-N'-ethyl-N'-phenylformamidine | |
| CN109721584B (en) | Method for preparing 1, 4-dioxane | |
| CN106243324A (en) | A kind of fire-retardant epoxy resin and preparation method thereof | |
| CN105541561A (en) | Method for synthesizing and purifying 1,1,1-tri(4-hydroxy phenyl) ethane | |
| CN107434761B (en) | Method for removing o-ethylphenol from m-cresol and p-cresol products of medium-temperature and low-temperature coal tar |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150325 |
|
| RJ01 | Rejection of invention patent application after publication |