CN105111049A - Preparation method of 2, 2'-dihydroxybiphenyl - Google Patents
Preparation method of 2, 2'-dihydroxybiphenyl Download PDFInfo
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- CN105111049A CN105111049A CN201510616326.1A CN201510616326A CN105111049A CN 105111049 A CN105111049 A CN 105111049A CN 201510616326 A CN201510616326 A CN 201510616326A CN 105111049 A CN105111049 A CN 105111049A
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- dibenzofuran
- dihydroxybiphenyl
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- 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
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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- 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
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
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- 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
Abstract
The invention relates to preparation of polymer monomers, in particular to a preparation method of 2, 2'-dihydroxybiphenyl. The preparation method includes: adding dibenzofuran, potassium hydroxide and a cyclic compound containing active hydrogen into an alkali-melting vessel, heating the vessel to melt all materials, allowing uniform temperature rise to 240-290 DEG C in 1-4 hours, and allowing reaction for 1-6 hours; cooling an obtained material to 180-270 DEG C, adding water, maintaining the temperature to 80-120 DEG C, performing cooling and filtering after dispersing, adding activated carbon and an antioxidant, and performing cooling and filtering after heating and decoking; heating filtrate to 60-100 DEG C, adjusting pH, performing mixing to crystallize the filtrate, and performing filtering and washing until neutrality to obtain a crude product; adding the crude product into recrystallized solvent water, and performing heating, stirring, cooling and filtering to obtain the 2, 2'-dihydroxybiphenyl. The material, dibenzofuran, used in the method is resourceful in China, the purity of the dibenzofuran used in the method being higher than 80% is just required for use, and cost of the dibenzofuran is greatly decreased.
Description
Technical field
The present invention relates to the preparation of high polymer monomer, specifically one 2, the preparation method of 2 '-dihydroxybiphenyl.
Background technology
2,2 '-dihydroxybiphenyl and derivative thereof are important Organic chemical products, can be used as the intermediate of liquid crystalline polymers.In synthetic high polymer, because its resistance toheat is splendid, therefore the modified monomer of the macromolecular materials such as polyester, urethane, polycarbonate, polysulfones and epoxy resin can be used as, be used for making excellent engineering plastics and matrix material.It can also be used as the stablizer of rubber anti-ageing agent, plastic antioxidants and dyestuff intermediate or petroleum product.
US Patent No. 2244244 reports with dibenzofuran to be that starting raw material prepares 2,2 '-dihydroxybiphenyl, this patent simply describe with dibenzofuran, potassium hydroxide and containing the ring compound of reactive hydrogen after 250 ~ 270 DEG C of pyroreactions terminate, reaction mass is down to room temperature, mechanically reaction mass is pulverized.Material water dissolution after pulverizing, filter, acidifying obtains 2,2 '-dihydroxybiphenyl.The discharge method of the material grinding introduced in patent is only applicable to laboratory preparation, inapplicable suitability for industrialized production.Preparation 2, the temperature of reaction required for 2 '-dihydroxybiphenyl is higher, easily produces carbonizing matter, affects purity and the outward appearance of product, and do not introduce carbonizing matter removing mode in patent, patent does not introduce process for purification in addition.
English Patent GB922679 introduces with dibenzofuran and sodium hydroxide for raw material prepares 2,2 '-dihydroxybiphenyl, but temperature of reaction is 350 DEG C, and power consumption increases, and the amount that carbonizing matter produces increases greatly, be not suitable for industrialization, and yield is lower, only has 36%.
Japanese Patent JP57209241 once reported and reacted preparation 2,2 '-dihydroxybiphenyl with dibenzofuran and potassium hydroxide or mixture (comprising potassium hydroxide and sodium hydroxide).The dibenzofuran that material choice content is greater than 99%, reacts and carries out at 250 ~ 350 DEG C, and needs certain pressure, and manufacture changes into originally higher.
Summary of the invention
The object of the invention is to provide a kind of 2, the preparation method of 2 '-dihydroxybiphenyl.
For achieving the above object, the technical solution used in the present invention is:
A kind of 2, the preparation method of 2 '-dihydroxybiphenyl,
(1) dibenzofuran, potassium hydroxide and the ring compound containing reactive hydrogen are joined in alkali-melting vessel, be first warming up to 80 ~ 130 DEG C, material is all melted, in then 1 ~ 4 hour, be at the uniform velocity warming up to 240 ~ 290 DEG C, reaction 1 ~ 6 hour after heating up;
(2) material that step (1) obtains is cooled to 180 ~ 270 DEG C, under stirring, water is added in alkali-melting vessel, after adding water, make alkali fusion temperature in the kettle maintain 80 ~ 120 DEG C, fully stir and within 1 ~ 4 hour, make material be dispersed in water, after dispersion, be cooled to 10 ~ 50 DEG C again, filter, stand-by;
(3) in filtrate after above-mentioned filtration, add gac and antioxidant, carry out decoking at being warming up to 40 ~ 100 DEG C 1 ~ 5 hour, after decoking, be cooled to 10 ~ 50 DEG C, filter;
(4) filtrate after above-mentioned filtration is warming up to 60 ~ 100 DEG C, regulates filtrate pH value to 2 ~ 5, then stirring makes its sufficient crystallising in 1 ~ 3 hour at 10 ~ 50 DEG C, filter, be washed to neutrality, obtain crude product;
(5) crude product is joined in recrystallization solvent water, stir 1 ~ 4 hour at being warming up to 60 ~ 100 DEG C, be cooled to 10 ~ 50 DEG C, filter, obtain 2,2 '-dihydroxybiphenyl.
Ring compound containing reactive hydrogen in described step (1) is fluorenes, carbazole or indoles; Charging capacity containing the ring compound of reactive hydrogen is dibenzofuran weight charging capacity 0 ~ 100%; The purity of dibenzofuran is 80 ~ 100%; Dibenzofuran and potassium hydroxide mol ratio=0.32 ~ 2:1, potassium hydroxide purity is 80 ~ 100%; Temperature of reaction is 240 ~ 290 DEG C.
Ring compound containing reactive hydrogen in described step (1) is fluorenes; Charging capacity containing the ring compound of reactive hydrogen is dibenzofuran weight charging capacity 0 ~ 40%; The purity of dibenzofuran is 89 ~ 99%; Dibenzofuran and potassium hydroxide mol ratio=0.32 ~ 0.98:1, potassium hydroxide purity is 90 ~ 95%; Temperature of reaction is 260 ~ 280 DEG C.
Wherein, the purity of dibenzofuran low containing active hydrogen compounds time, when feeding intake, can not active hydrogen compounds be added, but preferably add active hydrogen compounds again, because active hydrogen compounds not only can promote to react, the coking speed of raw material dibenzofuran can also be slowed down.
Described step (2) is that the material that step (1) obtains is cooled to 180 ~ 270 DEG C; The add-on of water is 1 ~ 20 times of dibenzofuran weight.
Described step (2) is that the material that step (1) obtains is cooled to 200 ~ 240 DEG C; The add-on of water is 2-5 times of dibenzofuran weight.
Described step (3) antioxidant comprises S-WAT, sodium bisulfite, tin protochloride or vat powder; Antioxidant usage quantity is 0.5 ~ 30% of dibenzofuran weight; Decoking temperature in described step (3) is 40 ~ 100 DEG C; The usage quantity of described gac is 0.5 ~ 30% of dibenzofuran weight.
Described step (3) antioxidant is S-WAT or sodium bisulfite; Antioxidant usage quantity is 1 ~ 3% of dibenzofuran weight; Decoking temperature in described step (3) is 75 ~ 95 DEG C; The usage quantity of described gac is 10 ~ 20% of dibenzofuran weight.
Acid is adopted to regulate filtrate in described step (4); Wherein, acid is hydrochloric acid, sulfuric acid or nitric acid.Preferred hydrochloric acid or sulfuric acid.
In described step (5), the usage quantity of water is crude product weight 5 ~ 30 times, preferably 10 ~ 15 times; Described recrystallization temperature is 60 ~ 100 DEG C, preferably 85 ~ 95 DEG C.
The middle filtration of described step (5) obtains phenolic wastewater and can apply mechanically after solvent extraction, described extraction solvent is toluene, o-Xylol, p-Xylol, m-xylene, xylol, chlorobenzene or mixed dichlorobenzene, preferred toluene or xylol.The consumption of extraction solvent is 10 ~ 100% of wastewater flow rate volume, preferably 20 ~ 40%.
The advantage that the present invention has:
The raw material dibenzofuran Domestic Resources that the inventive method uses enriches, and the purity of the dibenzofuran used in technique only needs to be greater than 80% and just can use, and greatly reduces the cost of raw material dibenzofuran.The invention solves reaction mass discharge method, make technique meet the requirement of suitability for industrialized production, avoid occurring pulverizing material discharge method.For the carbonizing matter produced in high-temperature reaction process, the present invention finds decoking scheme.For acquisition crude product, the present invention finds the economic process for purification be applicable to, and the refining phenolic wastewater produced can directly be applied mechanically after solvent extraction, greatly reduces environmental protection pressure.
Embodiment
Embodiment 1
In alkali-melting vessel (material is stainless steel), adding the dibenzofuran of 10kg, (purity is 89.5%, containing the fluorenes of 3.5% in dibenzofuran), 2kg fluorenes (purity is 93.5%) and 5kg potassium hydroxide (purity is 90%), be heated to 118 ~ 120 DEG C, after material all melts, at the uniform velocity be warming up to 275 ~ 277 DEG C (controlling the heating-up time is 1.5 hours), at this temperature, be incubated 3 hours.
After insulation reaction terminates, cooling, when reaction mass is cooled to 240 DEG C, in alkali-melting vessel, slowly add the water of 20kg, along with adding of water, material is water-soluble, and temperature is also down to 80 DEG C by 240 DEG C, stirs normal operation.Stir 2 hours at material being warming up to 90 ~ 92 DEG C, stir 1 hour at being cooled to 30 DEG C, filter, and with 10kg water washing filter cake, filter cake is dark yellow.
In filtrate, add 1.2kg gac and 0.3kg S-WAT, be warming up to 78 ~ 80 DEG C of decokings 1 hour, be cooled to 40 DEG C, cross and filter gac.
At 70 DEG C, in filtrate, adding 30% dilute sulphuric acid neutralization filtrate to PH is 3 ~ 4, and required sulfuric acid amount is about about 13kg.Stir at 30 ~ 32 DEG C and make its sufficient crystallising in 1 hour.Filter and be washed to neutrality and obtain 2,2 '-dihydroxybiphenyl crude product, dry weight is 6.1kg, and crude product weight yield is 81.7%.
6.1kg crude product is joined in refining kettle, and 60kg water is added in still, stir 1 hour at being warming up to 90 ~ 92 DEG C, at being down to 30 ~ 32 DEG C, filtration obtains product, and be heavily 5.2kg after drying at 80 DEG C, outward appearance is white powder, content is 99.3% (GC normalizing content), and refining yield is 85.2%.
Join in extraction kettle by the toluene of the phenolic wastewater obtained after refining and 12kg, stirred at ambient temperature is after 3 hours, and stop stirring, leave standstill 30 minutes, point sub-cloud water layer, it is refining that the water obtained can directly apply to next time.
Embodiment 2
In alkali-melting vessel, adding the dibenzofuran of 10kg, (purity is 89.5%, containing the fluorenes of 3.5% in dibenzofuran) and 5kg potassium hydroxide (purity is 90%), be heated to 108 ~ 110 DEG C, after material all melts, at the uniform velocity be warming up to 268 ~ 270 DEG C (controlling the heating-up time is 2 hours), at this temperature, be incubated 5 hours.
After insulation reaction terminates, cooling, when reaction mass is cooled to 220 DEG C, in alkali-melting vessel, slowly add the water of 15kg, along with adding of water, material is water-soluble, and temperature is also down to 100 DEG C by 220 DEG C, stirs normal operation.Stir 2 hours at material being maintained 86 ~ 88 DEG C, stir 1 hour at being cooled to 30 DEG C, filter, and with 10kg water washing filter cake, filter cake is black, and coking is serious.
In filtrate, add 2kg gac and 0.5kg S-WAT, be warming up to 84 ~ 86 DEG C of decokings 1 hour, be cooled to 40 DEG C, cross and filter gac.
80 DEG C, lower in filtrate, to add 33% hydrochloric acid neutralization filtrate to PH be 3 ~ 4, and required hydrochloric acid content is about about 9.8kg.Stir at 38 ~ 40 DEG C and make its sufficient crystallising in 1 hour.Filter and be washed to neutrality and obtain 2,2 '-dihydroxybiphenyl crude product, dry weight is 5.6kg, and crude product weight yield is 75.0%.
5.6kg crude product is joined in refining kettle, and 50kg water is added in still, stir 1 hour at being warming up to 95 ~ 97 DEG C, at being down to 30 ~ 40 DEG C, filtration obtains product, and be heavily 4.9kg after drying at 80 DEG C, outward appearance is white powder, content is 99.1% (GC normalizing content), and refining yield is 87.7%.
Join in extraction kettle by the toluene of the phenolic wastewater obtained after refining and 15kg, stirred at ambient temperature is after 2 hours, and stop stirring, leave standstill 30 minutes, point sub-cloud water layer, it is refining that the water obtained can directly apply to next time.
Embodiment 3
In alkali-melting vessel, adding the dibenzofuran of 10kg, (purity is 89.5%, containing the fluorenes of 3.5% in dibenzofuran), 2kg carbazole (purity is 95.4%) and 5kg potassium hydroxide (purity is 95%), be heated to 120 ~ 122 DEG C, after normal operation to be mixed, at the uniform velocity be warming up to 280 ~ 282 DEG C (controlling the heating-up time is 2 hours), at this temperature, be incubated 2 hours.
After insulation reaction terminates, cooling, when reaction mass is cooled to 200 DEG C, in alkali-melting vessel, slowly add the water of 30kg, along with adding of water, material is water-soluble, and temperature is also down to 20 DEG C by 190 DEG C, stirs normal operation.Stir 2 hours at material being maintained 88 ~ 90 DEG C, stir 1 hour at being cooled to 30 DEG C, filter, and with 10kg water washing filter cake, filter cake is dark yellow.
In filtrate, add 3kg gac and 1kg S-WAT, be warming up to 88 ~ 90 DEG C of decokings 1 hour, be cooled to 40 DEG C, cross and filter gac.
At 70 DEG C, in filtrate, adding 30% nitric acid neutralization filtrate to PH is 3 ~ 4, and required nitric acid amount is about about 19.5kg.Stir at 28 ~ 30 DEG C and make its sufficient crystallising in 1 hour.Filter and be washed to neutrality and obtain 2,2 '-dihydroxybiphenyl crude product, dry weight is 6.3kg, and crude product weight yield is 79.9%.
6.3kg crude product is joined in refining kettle, and 120kg water is added in still, stir 1 hour at being warming up to 94 ~ 96 DEG C, at being down to 25 ~ 27 DEG C, filtration obtains product, and be heavily 4.8kg after drying at 80 DEG C, outward appearance is white powder, content is 99.5% (GC normalizing content), and refining yield is 76.2%.Phenolic wastewater is reusable after 30kg xylene extraction.
Join in extraction kettle by the dimethylbenzene of the phenolic wastewater obtained after refining and 30kg, stirred at ambient temperature is after 4 hours, and stop stirring, leave standstill 1 hour, point sub-cloud water layer, it is refining that the water obtained can directly apply to next time.
Embodiment 4
In alkali-melting vessel, adding the dibenzofuran of 15kg, (purity is 98%, containing the ripple hydrogen compound of living), 2kg indoles (purity is 96.8%) and 5kg potassium hydroxide (purity is 90%), be heated to 98 ~ 100 DEG C, after material all melts, at the uniform velocity be warming up to 273 ~ 275 DEG C (controlling the heating-up time is 1 hour), at this temperature, be incubated 4 hours.
After insulation reaction terminates, cooling, when reaction mass is cooled to 190 DEG C, in alkali-melting vessel, slowly add the water of 20kg, along with adding of water, material is water-soluble, and temperature is also down to 70 DEG C by 190 DEG C, stirs normal operation.Stir 2 hours at material being maintained 98 ~ 100 DEG C, stir 1 hour at being cooled to 30 DEG C, filter, and with 10kg water washing filter cake, filter cake is dark yellow.
In filtrate, add 1kg gac and 0.2kg sodium bisulfite, be warming up to 80 ~ 82 DEG C of decokings 2 hours, be cooled to 30 DEG C, cross and filter gac.
At 85 DEG C, in filtrate, adding 33% hydrochloric acid neutralization filtrate to PH is 3 ~ 4, and required hydrochloric acid content is about about 9.8kg.Stir at 20 ~ 22 DEG C and make its sufficient crystallising in 1 hour.Filter and be washed to neutrality and obtain 2,2 '-dihydroxybiphenyl crude product, dry weight is 6.0kg, and crude product weight yield is 80.5%.
6.0kg crude product is joined in refining kettle, and in still, add 50kg water (water obtained after toluene extraction in embodiment 2), stir 2 hours at being warming up to 98 ~ 100 DEG C, at being down to 28 ~ 30 DEG C, filtration obtains product, and be heavily 5.1kg after drying at 80 DEG C, outward appearance is white powder, content is 99.3% (GC normalizing content), and refining yield is 85%.Phenolic wastewater can be applied mechanically after the extraction of 20kg toluene.
Join in extraction kettle by the toluene of the phenolic wastewater obtained after refining and 20kg, stirred at ambient temperature is after 3 hours, and stop stirring, leave standstill 30 minutes, point sub-cloud water layer, it is refining that the water obtained can directly apply to next time.
Claims (10)
1. one kind 2, the preparation method of 2 '-dihydroxybiphenyl, is characterized in that:
(1) dibenzofuran, potassium hydroxide and the ring compound containing reactive hydrogen are joined in alkali-melting vessel, be first warming up to 80 ~ 130 DEG C, material is all melted, in then 1 ~ 4 hour, be at the uniform velocity warming up to 240 ~ 290 DEG C, reaction 1 ~ 6 hour after heating up;
(2) material that step (1) obtains is cooled to 180 ~ 270 DEG C, under stirring, water is added in alkali-melting vessel, after adding water, make alkali fusion temperature in the kettle maintain 80 ~ 120 DEG C, fully stir and within 1 ~ 4 hour, make material be dispersed in water, after dispersion, be cooled to 10 ~ 50 DEG C again, filter, stand-by;
(3) in filtrate after above-mentioned filtration, add gac and antioxidant, carry out decoking at being warming up to 40 ~ 100 DEG C 1 ~ 5 hour, after decoking, be cooled to 10 ~ 50 DEG C, filter;
(4) filtrate after above-mentioned filtration is warming up to 60 ~ 100 DEG C, regulates filtrate pH value to 2 ~ 5, then stirring makes its sufficient crystallising in 1 ~ 3 hour at 10 ~ 50 DEG C, filter, be washed to neutrality, obtain crude product;
(5) crude product is joined in recrystallization solvent water, stir 1 ~ 4 hour at being warming up to 60 ~ 100 DEG C, be cooled to 10 ~ 50 DEG C, filter, obtain 2,2 '-dihydroxybiphenyl.
2. by according to claim 12, the preparation method of 2 '-dihydroxybiphenyl, is characterized in that: the ring compound containing reactive hydrogen in described step (1) is fluorenes, carbazole or indoles;
Charging capacity containing the ring compound of reactive hydrogen is dibenzofuran weight charging capacity 0 ~ 100%; The purity of dibenzofuran is 80 ~ 100%; Dibenzofuran and potassium hydroxide mol ratio=0.32 ~ 2:1, potassium hydroxide purity is 80 ~ 100%; Temperature of reaction is 240 ~ 290 DEG C.
3. by according to claim 22, the preparation method of 2 '-dihydroxybiphenyl, is characterized in that: the ring compound containing reactive hydrogen in described step (1) is fluorenes; Charging capacity containing the ring compound of reactive hydrogen is dibenzofuran weight charging capacity 0 ~ 40%; The purity of dibenzofuran is 89 ~ 99%; Dibenzofuran and potassium hydroxide mol ratio=0.32 ~ 0.98:1, potassium hydroxide purity is 90 ~ 95%; Temperature of reaction is 260 ~ 280 DEG C.
4., by according to claim 12, the preparation method of 2 '-dihydroxybiphenyl, is characterized in that: described step (2) is that the material that step (1) obtains is cooled to 180 ~ 270 DEG C; The add-on of water is 1 ~ 20 times of dibenzofuran weight.
5., by according to claim 42,2 '-dihydroxybiphenyl industrialized process for preparing, is characterized in that: described step (2) is that the material that step (1) obtains is cooled to 200 ~ 240 DEG C; The add-on of water is 2-5 times of dibenzofuran weight.
6., by according to claim 12, the preparation method of 2 '-dihydroxybiphenyl, is characterized in that: described step (3) antioxidant comprises S-WAT, sodium bisulfite, tin protochloride or vat powder; Antioxidant usage quantity is 0.5 ~ 30% of dibenzofuran weight; Decoking temperature in described step (3) is 40 ~ 100 DEG C; The usage quantity of described gac is 0.5 ~ 30% of dibenzofuran weight.
7., by according to claim 62, the preparation method of 2 '-dihydroxybiphenyl, is characterized in that: described step (3) antioxidant is S-WAT or sodium bisulfite; Antioxidant usage quantity is 1 ~ 3% of dibenzofuran weight; Decoking temperature in described step (3) is 75 ~ 95 DEG C; The usage quantity of described gac is 10 ~ 20% of dibenzofuran weight.
8. by according to claim 12, the preparation method of 2 '-dihydroxybiphenyl, is characterized in that: adopt acid to regulate filtrate in described step (4); Wherein, acid is hydrochloric acid, sulfuric acid or nitric acid.
9., by according to claim 12, the preparation method of 2 '-dihydroxybiphenyl, is characterized in that; In described step (5), the usage quantity of water is crude product weight 5 ~ 30 times; Described recrystallization temperature is 60 ~ 100 DEG C.
10. by according to claim 12, the preparation method of 2 '-dihydroxybiphenyl, it is characterized in that: the middle filtration of described step (5) obtains phenolic wastewater and can apply mechanically after solvent extraction, and described extraction solvent is toluene, o-Xylol, p-Xylol, m-xylene, xylol, chlorobenzene or mixed dichlorobenzene; The consumption of extraction solvent is 10 ~ 100% of wastewater flow rate volume.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107805185A (en) * | 2017-11-22 | 2018-03-16 | 安庆三喜医药化工有限公司 | 2,2 ' the dihydroxybiphenyls using 9 fluorenes ketone compounds as waste |
| CN107903151A (en) * | 2017-11-22 | 2018-04-13 | 安庆三喜医药化工有限公司 | A kind of purification process of 2,2 ' dihydroxybiphenyls |
| CN112341316A (en) * | 2020-10-23 | 2021-02-09 | 河北中化鑫宝化工科技有限公司 | Method for preparing 2, 2' -dihydroxybiphenyl by using dibenzofuran fraction as raw material |
| CN114805035A (en) * | 2022-06-08 | 2022-07-29 | 四川圣效科技股份有限公司 | Method for purifying 4, 4' -biphenol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2244244A (en) * | 1938-06-22 | 1941-06-03 | Firm Ruetgerswerke Ag | Process for producing o, o'-dihydroxydiphenyl |
| GB922679A (en) * | 1960-10-03 | 1963-04-03 | Ici Ltd | Improvements in and relating to the preparation of 2:2- dihydroxydiphenyls |
| JPS57209241A (en) * | 1981-06-19 | 1982-12-22 | Sanko Kagaku Kk | Preparation of 2,2'-dihydroxydiphenyl |
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2015
- 2015-09-24 CN CN201510616326.1A patent/CN105111049B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2244244A (en) * | 1938-06-22 | 1941-06-03 | Firm Ruetgerswerke Ag | Process for producing o, o'-dihydroxydiphenyl |
| GB922679A (en) * | 1960-10-03 | 1963-04-03 | Ici Ltd | Improvements in and relating to the preparation of 2:2- dihydroxydiphenyls |
| JPS57209241A (en) * | 1981-06-19 | 1982-12-22 | Sanko Kagaku Kk | Preparation of 2,2'-dihydroxydiphenyl |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107805185A (en) * | 2017-11-22 | 2018-03-16 | 安庆三喜医药化工有限公司 | 2,2 ' the dihydroxybiphenyls using 9 fluorenes ketone compounds as waste |
| CN107903151A (en) * | 2017-11-22 | 2018-04-13 | 安庆三喜医药化工有限公司 | A kind of purification process of 2,2 ' dihydroxybiphenyls |
| CN112341316A (en) * | 2020-10-23 | 2021-02-09 | 河北中化鑫宝化工科技有限公司 | Method for preparing 2, 2' -dihydroxybiphenyl by using dibenzofuran fraction as raw material |
| CN114805035A (en) * | 2022-06-08 | 2022-07-29 | 四川圣效科技股份有限公司 | Method for purifying 4, 4' -biphenol |
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| CN105111049B (en) | 2017-04-12 |
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