CN109627146A - A kind of preparation method of styrylphenol - Google Patents
A kind of preparation method of styrylphenol Download PDFInfo
- Publication number
- CN109627146A CN109627146A CN201811491446.3A CN201811491446A CN109627146A CN 109627146 A CN109627146 A CN 109627146A CN 201811491446 A CN201811491446 A CN 201811491446A CN 109627146 A CN109627146 A CN 109627146A
- Authority
- CN
- China
- Prior art keywords
- styrylphenol
- preparation
- reaction
- added
- acid
- 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
- C07C37/18—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 by condensation involving halogen atoms of halogenated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation methods of styrylphenol, belong to field of fine chemical.A kind of preparation method of styrylphenol of the present invention includes the following steps: that (1) is added catalyst, 2 phenylethyl alcohol and partially halogenated phenol in a kettle, is bubbled back flow reaction for a period of time with nitrogen under certain temperature；(2) it is then bubbled with a small amount of nitrogen, while vacuumizing the small molecule that certain time removing generates；(3) under nitrogen protection control reaction temperature be slowly added to remaining halogenation phenol, and the reaction was continued a period of time；(4) then cooling to 60-70 DEG C is obtained by filtration crude product, and crude product is obtained finished product after purification.The present invention provides one kind can obtain low color, high-purity styrylphenol product the method for preparing styrylphenol.
Description
Technical field
The present invention relates to a kind of preparation methods of styrylphenol, belong to field of fine chemical.
Technical background
Styrylphenol is added in product usually as antioxidant, to improve the oxidation-stabilized performance of product, in phenol
In kind antioxidant, styrylphenol has excellent thermal stability, and does not dye, is non-discolouring, not migrating, will not be to product
It pollutes.Styrylphenol can further be reacted with ethylene oxide, propylene oxide, and non-ionic surface active is prepared
Agent, and a kind of important raw material have excellent emulsibility, temperature viscosity and bactericidal properties, and volatility is low, and performance is stablized,
Be pesticide, paint emulsification agent, rinse product important component, especially apply the liquid in colored filter and thin film transistor (TFT)
In crystal panel, domestic every annual requirement is at ten thousand tons or more.
The Study of synthesis method of domestic styrylphenol starts from nineteen sixties mid-term, most start using
Liquid acid, such as the concentrated sulfuric acid, phosphoric acid, polyphosphoric acid, hydrochloric acid etc., but they react more violent, and product color is deeper, to equipment corruption
Erosion is serious.Also useful later that inorganic acid synthesizing styrene base is replaced using minerals, atlapulgite, ion exchange resin, zeolite
Phenol, currently, P-TOLUENE SULFO ACID 99 and phosphoric acid composite catalyst, atlapulgite catalyze and synthesize the method use of styrylphenol compared with
It is more.
Styrene is prepared using large hole cation exchanger resin as patent CN103880603A, CN101412795 describes
The process of base phenol, patent CN1280994A describe a kind of technique side that inorganic acid catalysis prepares styrylphenol
Method.Patent CN107141465A describes the method for preparing diphenylethyllene phenol with methane sulfonic acid.
Such methods are to be synthesized using styrene and phenol under acidic catalyst effect by alkylated reaction.
But determined by reaction mechanism, this method inevitably generates consecutive reaction, therefore main production during the reaction
Product are the mixtures of single styrylphenol, diphenylethyllene phenol and triphenyl vinyl phenol, since product boiling point is high, property
Matter is close, it is difficult to obtain pure styrylphenol product.And product appearance described in the report of existing document is equal
It is yellow or brown product, is unable to satisfy high-end quality requirements.
Then open source literature (chemical industry is in progress the 12nd phase of volume 36 in 2017) is made by first synthesizing diphenylethyllene phenol
It is standby to obtain diphenylethyllene phenol polyoxyethylene ether.Author uses acid catalysis styrene and the method for phenol reactant prepares hexichol
Vinylphenol not can avoid the consecutive reaction in reaction, therefore inevitably poly- containing a styrene in final product
Ethylene oxide ether, diphenylethyllene phenol polyoxyethylene ether and tristyrylphenol polyoxyethylene ether, wherein diphenylethyllene
Phenol polyoxyethylene ether is only 52.7%.
Single, low color styrylphenol product, the lack of checks on power of technology is prepared currently, not having been reported that also
The application of such product.
Summary of the invention
In order to obtain the styrylphenol product of low color, high-purity, styryl is prepared the present invention provides a kind of
The method of phenol, the shortcomings that overcome existing preparation method that can only obtain a variety of styrylphenol mixtures in dark pool.
The technical solution that the present invention solves disadvantages mentioned above is as follows:
A kind of preparation method of styrylphenol, includes the following steps:
(1) catalyst, 2 phenylethyl alcohol and partially halogenated phenol are added in a kettle, is bubbled and is flowed back with nitrogen under certain temperature
Reaction a period of time；
(2) it is then bubbled with a small amount of nitrogen, while vacuumizing the small molecule that certain time removing generates；
(3) under nitrogen protection control reaction temperature be slowly added to remaining halogenation phenol, and the reaction was continued a period of time；
(4) then cooling to 60-70 DEG C is obtained by filtration crude product, and crude product is obtained finished product after purification.
Catalyst in the step (1) is one of alkali metal, alkali metal alcoholates or alkali metal hydroxide or several
Kind mixture.
The alkali metal is Na, K, and the alkali metal alcoholates refer to the C of Na or K1-C4Alkoxide, the alkali metal hydrogen
Oxide is sodium hydroxide or potassium hydroxide.
The molar ratio of catalyst charge and 2 phenylethyl alcohol is 1 ~ 1.1:1 in the step (1), is added in the step (1)
The amount of the partially halogenated phenol entered is the 1/3-1/2 of halogenation phenol total amount.
Halogenation phenol in the step (1) or (3) has structure below:
Wherein R is halogen.
Halogenation phenol in the step (1) or (3) is that have structure below:Or,
Middle R is halogen, such as Cl, Br, I.
Halogenation phenol in the step (1) or (3) is that have structure below:
Wherein R is halogen, such as Cl, Br, I.
Certain temperature in the step (1) is 70-120 DEG C, what the back flow reaction in the step (1) referred to for a period of time
It is back flow reaction 1-5 h, the small molecule that the abjection of vacuum certain time generates in the step (2) refers to vacuum 2-5h abjection life
At small molecule, the case where vacuum is finger pressure≤- 0.098Mpa in the step (2).
Reaction temperature in the step (3) is 80-140 DEG C, and reaction a period of time refers to reaction in the step (3)
1-6 h。
Molar ratio 1:1 ~ 3 of halogenation phenol total amount and 2 phenylethyl alcohol that the step (1) and step (3) are added.
Purification in the step (4) includes the following steps: that neutralizer, which is added, to be neutralized, water, adsorbent is added at 60-70 DEG C
2 h of adsorption bleaching, then vacuum distillation removing moisture, is obtained by filtration finished product.
The neutralizer refers to that the substance for neutralizing alkali, the neutralizer refer to the substance for neutralizing alkali, can
It is acetic acid, phosphoric acid, sulfuric acid, oxalic acid, citric acid, formic acid, nitric acid, hydrochloric acid, sulfamic acid, the neutralizer with the neutralizer
Additional amount be by system pH adjust to 5-6, the additional amount of the water is the 3-5% of crude product quality, and the adsorbent is silicon
Sour magnesium, the additional amount of the adsorbent are the 0.2-0.5% of crude product quality.
Of the invention has the advantage that
1, using halogenation phenol and 2 phenylethyl alcohol as raw material, styryl benzene is prepared in reaction in the presence of basic catalyst
Phenol.By selecting different halogenation starting phenols to react with 2 phenylethyl alcohol, the styrene of high-purity, low color can be prepared
Base phenol product.
2, the key of this method is the alcohol salinization fully reacting of 2 phenylethyl alcohol and base catalyst, could obtain high conversion
Product.It is reacted due to needing catalyst to carry out alcohol salinization with benzyl carbinol, to generate a large amount of benzyl carbinol salt, substantially increases body
The viscosity of system.When adding the mode of halogenation phenol using small molecule is first removed, since system viscosity becomes larger quickly, stirring is equal
Even just to become difficult, alcohol salinization reaction is difficult to carry out thoroughly.It is unexpected, partially halogenated phenol is added in the ban, in nitrogen
The lower reaction of gas bell reflux, the small molecule then generated with vacuum removal, being eventually adding remaining halogenation phenol, the reaction was continued, can
To obtain satisfied effect.This is because the small molecule that initial reaction stage generates is not removed, the work of solvent is played in system
With reducing viscosity, make to react easy progress, while the partially halogenated phenol being added participates in the work for also playing solvent after reaction
With the later period can remove the small molecule of generation completely in such a way that drum nitrogen adds vacuum, so that alcohol salinization reaction progress is thorough
Bottom makes conversion ratio be guaranteed.
3, phenol product easily changes colour in the presence of having air and alkaline matter, this by strong influence itself and
Quality, color and the application performance of downstream product, therefore, reaction must be oxygen barrier.Using continuous logical nitrogen come isolating oxygen in reaction
Gas avoids oxygen from influencing product color, and entire reaction carries out under the conditions of nitrogen protection, and the color of product obtains good protection,
Color≤30(platinum-cobalt colorimetric method), high-end product requirement can be reached
4, this method selectivity high (principal product selectivity >=98%), by-product few (by-product≤2%), product color≤30
(Pt-Co method), high conversion rate (in terms of benzyl carbinol >=99.5%), which has industrial application value.
Specific embodiment
In the present invention, product is detected using standard curve outside liquid phase, i.e., by configuring the sample of various concentration, then will
Sample concentration and liquid phase signal are fitted to standard curve, obtain sample concentration by the liquid phase signal of test sample.To selectivity
(X) it is defined as follows with conversion ratio (C):
Raw material used in the present invention can be adopted and is made with the conventional methods in the field, and commercial product can also be used.
Below by way of specific embodiment, the invention will be further described, but following embodiment should not be construed as to this hair
The limitation that bright scope of protection of the claims are made.
Embodiment 1
244g 2 phenylethyl alcohol, 46g metallic sodium, 220g are added in autoclave pressure to iodophenol, nitrogen is blasted by reactor bottom
Then gas slowly opens vacuum, turns down nitrogen, keep pressure≤- 0.098Mpa, deaerate at 80 DEG C in 70 DEG C of back flow reaction 1h
2h is then shut off vacuum, with nitrogen by force-displacement to normal pressure, and is slowly added to 220g under nitrogen protection to iodophenol, control
Reaction temperature processed is 80 DEG C of reaction 1h.
60 DEG C are cooled to, 377g crude product is obtained by filtration, 11.3g deionized water is added, phosphoric acid is added and is neutralized to pH=5-6, adds
Enter 0.75g magnesium silicate, in 60-70 DEG C of adsorption bleaching 2h, then slowly opens vacuum and risen to pressure≤0.099Mpa, while gradually
High-temperature carries out decompression dehydration to 105 DEG C, after cool to 50 DEG C colorless and transparent product be obtained by filtration.
Pass through detection, color 15, conversion ratio 99.9%, selectivity 99.5%.
Embodiment 2
244g 2 phenylethyl alcohol, 108g sodium methoxide, 65.2g 2 are added in autoclave pressure, 6- chlorophenesic acid passes through reactor bottom
Nitrogen is blasted, in 100 DEG C of 3 h of back flow reaction, vacuum is then slowly opened, turns down nitrogen, keep pressure≤- 0.098Mpa,
105 DEG C of 3 h of degassing, are then shut off vacuum, with nitrogen by force-displacement to normal pressure, and are slowly added to 97.8g under nitrogen protection
2,6- chlorophenesic acids, control reaction temperature are 110 DEG C of reaction 4h.
60 DEG C are cooled to, 291g crude product is obtained by filtration, 11.6g deionized water is added, phosphoric acid is added and is neutralized to pH=5-6, adds
Enter 0.87g magnesium silicate, in 60-70 DEG C of adsorption bleaching 2h, then slowly opens vacuum and risen to pressure≤0.099Mpa, while gradually
High-temperature carries out decompression dehydration to 105 DEG C, after cool to 50 DEG C colorless and transparent product be obtained by filtration.
Pass through detection, color 11, conversion ratio 99.7%, selectivity 99.2%.
Embodiment 3
Basic preparation method and embodiment 2 are consistent, and 2,6- chlorophenesic acid is only changed to 2,4- chlorophenesic acid.Pass through detection, color
Pool 19, conversion ratio 99.7%, selectivity 99.5%.
Embodiment 4
366g 2 phenylethyl alcohol, 184.8g potassium hydroxide, 110g 2,4 are added in autoclave pressure, 6- tribromophenol passes through reaction kettle bottom
Portion blasts nitrogen, in 120 DEG C of back flow reaction 5h, then slowly opens vacuum, turns down nitrogen, keep pressure≤- 0.098Mpa,
130 DEG C of 5 h of degassing, are then shut off vacuum, with nitrogen by force-displacement to normal pressure, and are slowly added to 220.8g under nitrogen protection
2,4,6- tribromophenols, control reaction temperature are 140 DEG C of 6 h of reaction.
60 DEG C are cooled to, 397g crude product is obtained by filtration, 19.9g deionized water is added, phosphoric acid is added and is neutralized to pH=5-6, adds
Enter 2.0g magnesium silicate, in 60-70 DEG C of adsorption bleaching 2h, then slowly opens vacuum and risen to pressure≤0.099Mpa, while gradually
High-temperature carries out decompression dehydration to 105 DEG C, after cool to 50 DEG C colorless and transparent product be obtained by filtration.
Pass through detection, color 24, conversion ratio 99.1%, selectivity 98.4%.
Comparative example 1
244g 2 phenylethyl alcohol, 108g sodium methoxide are added in autoclave pressure, sets nitrogen 3 times, then slowly opens vacuum, keep pressure
Power≤- 0.098Mpa is closed vacuum, with nitrogen by force-displacement to normal pressure, and is delayed under nitrogen protection in 105 DEG C of 3 h of degassing
Slow that 163g 2 is added, 6- chlorophenesic acid, control reaction temperature is 110 DEG C of reaction 4h.
60 DEG C are cooled to, 291g crude product is obtained by filtration, 11.6g deionized water is added, phosphoric acid is added and is neutralized to pH=5-6, adds
Enter 0.87g magnesium silicate, in 60-70 DEG C of adsorption bleaching 2h, then slowly opens vacuum and risen to pressure≤0.099Mpa, while gradually
High-temperature carries out decompression dehydration to 105 DEG C, after cool to 50 DEG C colorless and transparent product be obtained by filtration.
Pass through detection, color 15, conversion ratio 74.3%, selectivity 87.2%.
Comparative example 2
244g 2 phenylethyl alcohol, 108g sodium methoxide are added in autoclave pressure, nitrogen is blasted by reactor bottom, flows back at 100 DEG C
3 h are reacted, vacuum is then slowly opened, turns down nitrogen, pressure≤- 0.098Mpa is kept to be then shut off in 105 DEG C of 3 h of degassing
Vacuum with nitrogen by force-displacement to normal pressure, and is slowly added to 163g 2 under nitrogen protection, 6- chlorophenesic acid, control reaction
Temperature is 110 DEG C of reaction 4h.
60 DEG C are cooled to, 291g crude product is obtained by filtration, 11.6g deionized water is added, phosphoric acid is added and is neutralized to pH=5-6, adds
Enter 0.87g magnesium silicate, in 60-70 DEG C of adsorption bleaching 2h, then slowly opens vacuum and risen to pressure≤0.099Mpa, while gradually
High-temperature carries out decompression dehydration to 105 DEG C, after cool to 50 DEG C colorless and transparent product be obtained by filtration.
Pass through detection, color 11, conversion ratio 91.1%, selectivity 94.2%.
Pass through embodiment 2 and comparative example 1, comparative example 2, it can be seen that only combining drum nitrogen flows back and first adds
Enter partially halogenated phenol, be possible to obtain high conversion with it is highly selective.
The above content is the preferred embodiments of combination the invention to further detailed made by provided technical solution
Describe in detail bright, and it cannot be said that the invention specific implementation is confined to these above-mentioned explanations, technology affiliated for the invention
For the those of ordinary skill in field, without departing from the concept of the premise of the invention, several simple deductions can also be made
Or replacement, it all shall be regarded as belonging to the protection scope of the invention.
Claims (10)
1. a kind of preparation method of styrylphenol, which comprises the steps of:
(1) catalyst, 2 phenylethyl alcohol and partially halogenated phenol are added in a kettle, is bubbled and is flowed back with nitrogen under certain temperature
Reaction a period of time；
(2) it is then bubbled with a small amount of nitrogen, while vacuumizing the small molecule that certain time removing generates；
(3) under nitrogen protection control reaction temperature be slowly added to remaining halogenation phenol, and the reaction was continued a period of time；
(4) then cooling to 60-70 DEG C is obtained by filtration crude product, and crude product is obtained finished product after purification.
2. a kind of preparation method of styrylphenol according to claim 1, it is characterised in that: in the step (1)
Catalyst be one or more of alkali metal, alkali metal alcoholates or alkali metal hydroxide mixture.
3. a kind of preparation method of styrylphenol according to claim 2, it is characterised in that: the alkali metal is
Na, K, the alkali metal alcoholates refer to the C of Na or K1-C4Alkoxide, the alkali metal hydroxide are sodium hydroxide or hydrogen-oxygen
Change potassium.
4. a kind of preparation method of styrylphenol according to claim 1, it is characterised in that: in the step (1)
The molar ratio of catalyst charge and 2 phenylethyl alcohol is 1 ~ 1.1:1, and the amount for the partially halogenated phenol being added in the step (1) is
The 1/3-1/2 of halogenation phenol total amount.
5. a kind of preparation method of styrylphenol according to claim 1, it is characterised in that: the step (1) or
(3) the halogenation phenol in has structure below:
,,OrWherein R is halogen, such as Cl, Br, I.
6. a kind of preparation method of styrylphenol according to claim 1, it is characterised in that: in the step (1)
Certain temperature be 70-120 DEG C, the back flow reaction in the step (1) refers to back flow reaction 1-5 h for a period of time, described
The small molecule that the abjection of vacuum certain time generates in step (2) refers to the small molecule that vacuum 2-5h abjection generates, the step
(2) the case where vacuum is finger pressure≤- 0.098Mpa in.
7. a kind of preparation method of styrylphenol according to claim 1, it is characterised in that: the step (3)
In reaction temperature be 80-140 DEG C, reaction a period of time refers to reaction 1-6 h in the step (3).
8. a kind of preparation method of styrylphenol according to claim 1, it is characterised in that: the step (1) and
Molar ratio 1:1 ~ 3 of halogenation phenol total amount and 2 phenylethyl alcohol that step (3) is added.
9. a kind of preparation method of styrylphenol according to claim 1, which is characterized in that in the step (4)
Purification include the following steps: be added neutralizer neutralize, be added water, adsorbent in 60-70 DEG C of 2 h of adsorption bleaching, then depressurize
Distillation removing moisture, is obtained by filtration finished product.
10. a kind of preparation method of styrylphenol according to claim 9, it is characterised in that: the neutralizer
It is acetic acid, phosphoric acid, sulfuric acid, oxalic acid, citric acid, formic acid, nitric acid, hydrochloric acid, sulfamic acid, the additional amount of the neutralizer is by body
It is that pH is adjusted to 5-6, the additional amount of the water is the 3-5% of crude product quality, and the adsorbent is magnesium silicate, the absorption
The additional amount of agent is the 0.2-0.5% of crude product quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811491446.3A CN109627146A (en) | 2018-12-07 | 2018-12-07 | A kind of preparation method of styrylphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811491446.3A CN109627146A (en) | 2018-12-07 | 2018-12-07 | A kind of preparation method of styrylphenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109627146A true CN109627146A (en) | 2019-04-16 |
Family
ID=66071698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811491446.3A Pending CN109627146A (en) | 2018-12-07 | 2018-12-07 | A kind of preparation method of styrylphenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109627146A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280994A (en) * | 2000-08-09 | 2001-01-24 | 南京师范大学 | Process for preparing polyoxyvinethene as condensate of styrene, phenol and formaldehyde |
| CN101688143A (en) * | 2007-07-06 | 2010-03-31 | 科聚亚公司 | Liquid styrene phenols composition and forming method thereof |
| CN103880603A (en) * | 2014-03-25 | 2014-06-25 | 徐州工业职业技术学院 | Method for preparing styrenated phenol by catalysis |
| CN106631704A (en) * | 2016-08-22 | 2017-05-10 | 江苏飞亚化学工业有限责任公司 | Preparation method for styrenated phenol |
| CN107253902A (en) * | 2016-09-07 | 2017-10-17 | 西华大学 | A kind of method of the synthesizing styrene phenol in microreactor |
-
2018
- 2018-12-07 CN CN201811491446.3A patent/CN109627146A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280994A (en) * | 2000-08-09 | 2001-01-24 | 南京师范大学 | Process for preparing polyoxyvinethene as condensate of styrene, phenol and formaldehyde |
| CN101688143A (en) * | 2007-07-06 | 2010-03-31 | 科聚亚公司 | Liquid styrene phenols composition and forming method thereof |
| CN103880603A (en) * | 2014-03-25 | 2014-06-25 | 徐州工业职业技术学院 | Method for preparing styrenated phenol by catalysis |
| CN106631704A (en) * | 2016-08-22 | 2017-05-10 | 江苏飞亚化学工业有限责任公司 | Preparation method for styrenated phenol |
| CN107253902A (en) * | 2016-09-07 | 2017-10-17 | 西华大学 | A kind of method of the synthesizing styrene phenol in microreactor |
Non-Patent Citations (7)
| Title |
|---|
| ANTONIC ARCADI,ORAZIO.A.ATTANASI,STEFANO BERRETTA等: "Synthesis of New Cardanol Derivatives through Combined Iodination/Palladium-Catalysed Cross-Coupling Reactions", 《SYNTHESIS-STUTTGART》 * |
| HONG ZHANG, PAULA RUIZ-CASTILLO, AND STEPHEN L. BUCHWALD: "Palladium-Catalyzed C−O Cross-Coupling of Primary Alcohols", 《ORGANIC LETTERS》 * |
| RYAN S. SAWATZKY,BREANNA K. V. HARGREAVES,AND MARK STRAD: "A Comparative Ancillary igand Survey in Palladium-Catalyzed C–O Cross-Coupling of Primary and Secondary Aliphatic Alcohols", 《EUROPEAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| TATIANA RIOS CARVAJAL,STEPHEN M. KUEBLER,CESAR A. SIERRA: "Synthesis of novel phenylenevinylene linkers with electron-donating substituents by the Heck reaction", 《SYNTHETIC METALS》 * |
| 刘庆俭: "《有机化学 上》", 30 November 2018, 同济大学出版社 * |
| 宋东伟，张义友主编: "《有机化学》", 31 July 2017, 吉林大学出版社 * |
| 王积涛等主编: "《有机化学 第3版上》", 31 December 2009, 南开大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106588618A (en) | Method for catalyzing oxidation of phenol and hydrogen peroxide with selenium-containing catalyst for synthesis of p-benzoquinone | |
| Tsuji et al. | Development of new propylene oxide process | |
| CN109627146A (en) | A kind of preparation method of styrylphenol | |
| CN106632147B (en) | The method for preparing propylene oxide using micro passage reaction | |
| DE102020103799B4 (en) | PROCESS FOR THE PREPARATION OF 9,9-BIS(3-PHENYL-4-(2-HYDROXYETHOXY)PHENYL)FLUORENE | |
| EP3626340B1 (en) | Method for synthesizing propylene glycol phenyl ether | |
| CN116640047A (en) | Preparation method of 4-hydroxy biphenyl | |
| JP2006517229A (en) | Production method of high purity phenol | |
| US20190225567A1 (en) | System for producing phenol and bisphenol a including removal unit for removing methanol and acetone | |
| KR101535987B1 (en) | Preparation method of acetophenone | |
| CN111825530A (en) | Method for hydrofining ethylene glycol | |
| CN111348990A (en) | Preparation method of p-bromophenyl alkyl ether | |
| CN109134281B (en) | Method for synthesizing m-dialkylaminophenol | |
| CN117510307A (en) | Preparation process of benzenediol | |
| CN113773185B (en) | Preparation method of 3, 6-dimethoxy-2, 7-dimethyl-4-octenedialdehyde | |
| JP4078547B2 (en) | Phenol and its production method | |
| CN109250694A (en) | A method of hydroxylamine hydrochloride is prepared using hydrogen chloride dry gas | |
| US6875898B2 (en) | Process for preparing phenols | |
| CN101842351B (en) | Method for producing alkylbenzene hydroperoxide | |
| CN116332722A (en) | Auxiliary agent for preparing cyclohexanol by cyclohexene hydration and application thereof | |
| US7763755B2 (en) | Method for producing dialkylhydroperoxybenzenes | |
| WO2022117071A1 (en) | Method for synthesizing benzyl ether from polyhydric phenol | |
| CN115784908B (en) | Synthesis method of m-dialkylaminophenol | |
| CN116903455A (en) | Safe production method and application of 2-hydroxy-1, 4-naphthoquinone | |
| CN115716837B (en) | Preparation method and application of quaternary ammonium salt template agent and titanium silicalite molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190416 |