CN100497280C - Para phenyl phenol preparation method - Google Patents
Para phenyl phenol preparation method Download PDFInfo
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- CN100497280C CN100497280C CNB200610049123XA CN200610049123A CN100497280C CN 100497280 C CN100497280 C CN 100497280C CN B200610049123X A CNB200610049123X A CN B200610049123XA CN 200610049123 A CN200610049123 A CN 200610049123A CN 100497280 C CN100497280 C CN 100497280C
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- biphenyl
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- phenyl phenol
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Abstract
The present invention relates to a preparation method of p-phenylphenol, which belongs to the technical field of a compound preparation method. The present invention is characterized in that the prepaThe invention relates to a method for preparing phenyl phenol in the field of compound preparing method technology. It comprises the following steps: using sulfonyl chloride to do sulfonation biphenylration method has the following procedures: under the condition of 0DEG. C to 180DEG. C of the temperature, chlorosulfonic acid is used for sulfonating biphenyl in organic solvent, and biphenyl-4-sulf in the organic solution at the reacting temperature 0-180 deg., filtering and drying to obtain the biphenyl-4-sulfonation; mixing the biphenyl-4-sulfonation and the base mental hydroxide (1:2-30 moleonic acid is obtained though filtration and dryness; the prepared biphenyl-4-sulfonic acid and alkali metal hydroxide of which the molar ratio is 1: 2 to 30 are mixed in the organic solvent, and under rate) in the organic solution and preparing the phenyl phenol on the condition of PH value >=13; the temperature 160-340 deg.; the pressure 0-1.5 MPa; reclaiming the solvent form the base fusion matt the conditions that a pH value is not less than 13, temperature is 160DEG. C to 340DEG. C, and pressure is 0MPa to 1.5MPa, the p-phenylphenol is prepared through alkali fusion; solvent is reclaimed fer and separating the phenyl phenol and other fenol compounds during the course. rom prepared alkali fusion substances, and the p-phenylphenol and other phenolic compounds are separated during the process. The preparation method has a simple manufacturing process, and little pollution; side products which are generated in the preparation method are far less than the side products which are generated by using sulfuric acid sulfonation; the purity of a sulphonation product is so high that the highly-purified p-phenylphenol can be directly prepared through the alkali fusion without refining, and the present invention has low cost.
Description
Technical field
The invention belongs to the compounds process for production thereof technical field, be specially a kind of preparation method's technical field of p-phenyl phenol.
Background technology
The p-phenyl phenol purposes is very extensive, is mainly used in: the preparation heat sensitive dye; Preparation hot melt ink, classified papers impact paper; Synthetic have extremely strong weather resistance and weather resisteant resin, coating; Synthesizing hydrophobic fiber promotor can be improved dyeing kinetics and colour fastness greatly; Synthetic red, green sensitizing dye; Be widely used in novel pesticide, the new pharmaceutical of preparation high-efficiency low-toxicity; Can synthesize various monomers.General biphenyl and the sulfuric acid of adopting carries out sulfonation reaction in the prior art, preparation biphenyl-4-sulfonic acid, then hydro-oxidation sodium at high temperature and under the condition of long-time reaction alkali fusion prepare p-phenyl phenol.Also have by replacing sodium hydroxide to reduce the technology of alkali fusion temperature with potassium hydroxide.All these methods all produce a large amount of acid waste water in the processing of sulfonated bodies, the purity of sulfonated bodies is not high, and temperature of reaction is higher during alkali fusion.The inertia organic medium or the water that also will add high boiling point sometimes carry out alkali fusion.The easy contaminate environment of acid waste water that produces must can be discharged through handling, and has increased production cost.
Summary of the invention
The present invention is for overcoming the above-mentioned problems in the prior art, design provides a kind of preparation method's of new p-phenyl phenol technical scheme, the by product that its reaction generates is few, sulfonated bodies purity height, and just not needing to make with extra care directly, alkali fusion prepares highly purified p-phenyl phenol.
The preparation method of described a kind of p-phenyl phenol is characterized in that comprising the steps:
1) biphenyl is dissolved in the organic solvent, adds chlorsulfonic acid and carry out sulfonation reaction, temperature of reaction is 0～180 ℃, and reaction finishes after-filtration, drying, makes biphenyl-4-sulfonic acid;
2) biphenyl-4-sulfonic acid that makes is mixed with alkali metal hydroxide, organic solvent, under 160～340 ℃ of temperature, carry out the alkali fusion reaction;
3) after reaction finished, with the water diluted reaction mixture, separating suspension reclaimed solvent, and reaction solution carries out neutralization reaction with mineral acid, to pH be 4～6.5, filtration, cleaning, dry p-phenyl phenol.
The preparation method of described a kind of p-phenyl phenol is characterized in that the described organic solvent of step 1) is a kind of in the straight-chain paraffin (n 〉=2) of o-nitroethylbenzene, Ortho Nitro Toluene, tetracol phenixin, chloroform, chloride atom.
The preparation method of described a kind of p-phenyl phenol is characterized in that step 2) described organic solvent is a kind of in hydrogenated terphenyl or the straight chain alcohol compounds, described straight chain alcohol compounds is methyl alcohol, ethanol, butanols, Virahol etc.
The preparation method of described a kind of p-phenyl phenol is characterized in that the temperature of reaction described in the step 1) is: 10～80 ℃.
The preparation method of described a kind of p-phenyl phenol is characterized in that step 2) described in temperature of reaction be 280～320 ℃.
The preparation method of described a kind of p-phenyl phenol is characterized in that step 2) described in biphenyl-40-sulfonic acid and the mol ratio of alkali metal hydroxide be 1:6～12.
The preparation method of described a kind of p-phenyl phenol is characterized in that mineral acid described in the step 3) is sulfuric acid or hydrochloric acid.
The preparation method of described a kind of p-phenyl phenol is characterized in that the described drying process of step 3) is 100 ℃ of following vacuum-dryings, and then the purification that distils.
Among the above-mentioned preparation method, step 1) also can adopt the segmentation reaction, as: reacted 10-20 minute down at 30～50 ℃, be warming up to 60～80 ℃ then, kept 0.5-4 hour, be generally 1-3 hour, be preferably 2-3 hour.
Among the above-mentioned preparation method, step 2) the insulation reaction time is 5-20 hour, is generally 12-18 hour, is preferably 14-16 hour, and reaction finishes postcooling and enters down step process to 180-220 ℃.
Alkali fusion is reflected in the Inconel(nickel alloys) autoclave and carries out among the above-mentioned preparation method, and when reacting under air-tight state, the pressure-controlling that reaction mass self produces generally is controlled at 0.2-1.5Mpa below 5.0Mpa, be preferably 0.5-1.5Mpa.
The preparation method of above-mentioned a kind of p-phenyl phenol, technology is simple, and the by product that reaction generates is few; sulfonated bodies purity height does not need the direct alkali fusion of refining just energy prepare highly purified p-phenyl phenol, has reduced production cost; can not produce a large amount of acid waste water, help environment protection.
Embodiment
Below by embodiment the present invention is described in further detail.
31.2 gram (0.2 mole) biphenyl are dissolved in 200 milliliters of o-nitroethylbenzenes, and temperature is controlled at 30～40 ℃, slow Dropwise 35 gram chlorsulfonic acid, and this thermotonus 10 to 15 minutes, then reaction mixture is heated to 80 ℃ and kept 2 hours.Be cooled to room temperature, filter, dry that dry product weighs 49.2 gram biphenyl-4-sulfonic acid content 98.5%.In the Inconel(nickel alloys) autoclave, add 100 milliliters of above-mentioned sulfonation material and hydrogenated terphenyls, 96% sodium hydroxide 167 grams (4 moles), airtight autoclave.Start stirring and be warming up to 280 ℃, insulation reaction 15 hours, pressure rises to 0.8～1.5MPa.After insulation was finished, reaction mixture was cooled to 200 ℃, pumps into 300 ml waters, and suspended substance shifts out from autoclave, and water flushing autoclave.Reactant and wash water cumulative volume are told hydrogenated terphenyl with separating funnel for 1600 milliliters and are applied mechanically next time, the water of telling with in 30% sulfuric acid and the pH value be 4.5～6.0.Sedimentary product filters with B, and with the clear water washing, wet product 100 ℃ of dryings under vacuum are used the pure system of subliming method again.Product yield 83% (in biphenyl), p-phenyl phenol purity 99.9%.The used organic solvent of the present invention leaches the later recycled for a long time of product, does not have the waste water output.
Claims (3)
1, a kind of preparation method of p-phenyl phenol is characterized in that comprising the steps:
1) biphenyl is dissolved in the o-nitroethylbenzene, add chlorsulfonic acid and carry out sulfonation reaction, described sulfonation reaction was reacted 10-15 minute under 30～40 ℃ of conditions earlier, then reaction mixture was heated to 80 ℃ and kept 2 hours, reaction finishes after-filtration, drying, makes biphenyl-4-sulfonic acid;
2) biphenyl-4-sulfonic acid that makes is mixed with alkali metal hydroxide, organic solvent, under 160～340 ℃ of temperature, carry out the alkali fusion reaction, described organic solvent is a kind of in hydrogenated terphenyl or the straight chain alcohol compounds, and the mol ratio of described biphenyl-4-sulfonic acid and alkali metal hydroxide is 1:6～12;
3) after reaction finished, with the water diluted reaction mixture, separating suspension reclaimed solvent, and reaction solution carries out neutralization reaction with sulfuric acid or hydrochloric acid, to pH be 4～6.5, filtration, cleaning, dry p-phenyl phenol.
2, the preparation method of a kind of p-phenyl phenol as claimed in claim 1 is characterized in that step 2) described in temperature of reaction be 280～320 ℃.
3, the preparation method of a kind of p-phenyl phenol as claimed in claim 1 is characterized in that the described drying process of step 3) is 100 ℃ of following vacuum-dryings, and then the purification that distils.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610049123XA CN100497280C (en) | 2006-01-17 | 2006-01-17 | Para phenyl phenol preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610049123XA CN100497280C (en) | 2006-01-17 | 2006-01-17 | Para phenyl phenol preparation method |
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| CN1800126A CN1800126A (en) | 2006-07-12 |
| CN100497280C true CN100497280C (en) | 2009-06-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB200610049123XA Expired - Fee Related CN100497280C (en) | 2006-01-17 | 2006-01-17 | Para phenyl phenol preparation method |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103739449B (en) * | 2013-12-30 | 2016-05-04 | 青岛双桃精细化工（集团）有限公司 | A kind of preparation method of 1,5-dihydroxy naphthlene |
| CN114853575A (en) * | 2022-06-13 | 2022-08-05 | 连云港市三联化工有限公司 | Production process of p-phenylphenol for mother liquor recycling |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US424822A (en) * | 1890-04-01 | pokoeny | ||
| US4467123A (en) * | 1982-02-06 | 1984-08-21 | Bayer Aktiengesellschaft | Process for the preparation of alkali metal diphenylates and free hydroxydiphenyls |
| US4633024A (en) * | 1982-04-23 | 1986-12-30 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Process for producing aromatic hydroxy compound |
| CN1566053A (en) * | 2003-07-04 | 2005-01-19 | 江西麒麟化工有限公司 | Process for producing para phenyl phenol |
-
2006
- 2006-01-17 CN CNB200610049123XA patent/CN100497280C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US424822A (en) * | 1890-04-01 | pokoeny | ||
| US4467123A (en) * | 1982-02-06 | 1984-08-21 | Bayer Aktiengesellschaft | Process for the preparation of alkali metal diphenylates and free hydroxydiphenyls |
| US4633024A (en) * | 1982-04-23 | 1986-12-30 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Process for producing aromatic hydroxy compound |
| CN1566053A (en) * | 2003-07-04 | 2005-01-19 | 江西麒麟化工有限公司 | Process for producing para phenyl phenol |
Non-Patent Citations (2)
| Title |
|---|
| 联苯衍生物的磺化反应. 邹友思等.合成化学，第4卷第3期. 1996 |
| 联苯衍生物的磺化反应. 邹友思等.合成化学，第4卷第3期. 1996 * |
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| CN1800126A (en) | 2006-07-12 |
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Granted publication date: 20090610 Termination date: 20190117 |