CN106631704A - Preparation method for styrenated phenol - Google Patents
Preparation method for styrenated phenol Download PDFInfo
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- CN106631704A CN106631704A CN201610700589.5A CN201610700589A CN106631704A CN 106631704 A CN106631704 A CN 106631704A CN 201610700589 A CN201610700589 A CN 201610700589A CN 106631704 A CN106631704 A CN 106631704A
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- phenol
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- styrenated phenol
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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
- C07C37/11—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
- C07C37/14—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 addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
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Abstract
The invention discloses a preparation method for styrenated phenol. The preparation method comprises the following steps: adding phenol and p-toluenesulfonic acid into a container, introducing nitrogen, carrying out sufficient stirring with a stirring device at a rotating speed of 300 to 350 r/min, carrying out heating to 85 DEG C and then starting addition of styrene drop by drop, wherein the addition lasts for less than 2.5 h; after completion of the addition of styrene, carrying out heating to 120 to 130 DEG C at a constant rate and maintaining the temperature for 2 to 2.5 h; and stopping heating, adding triethylamine into a mixture obtained in the previous step, carrying out full stirring, then successively carrying out filtering, pumping filtration and vacuum distillation until no liquid is distilled off, carrying out cooling to 80 DEG C or below, and then carrying out discharging. According to the invention, the catalyst p-toluenesulfonic acid used in the invention is an organic acid and exerts good promotion effect on the alkylation reaction of phenol with styrene; the acidity of p-toluenesulfonic acid is weaker compared with inorganic strong acids like sulfuric acid and hydrochloric acid, so corrosion to reaction equipment is small; and reaction process is smooth and steady, reaction temperature is easy to control, and prepared styrenated phenol has a shallow color.
Description
Technical field
The disclosure relates generally to antioxidant field, and in particular to antioxidant production field, more particularly to a kind of styrol
The preparation method of phenol.
Background technology
At present domestic traditional styrenated phenol production technology have that product yield is low, di-substituted content is not high, into
The problems such as this height, serious equipment corrosion.Catalyst used by earliest production technology is mainly sulphuric acid, and its advantage is reaction temperature
Low, response speed is fast.Have the disadvantage that sulphuric acid has oxidation to product, it is strong to equipment corrosion, to be neutralized in production technology, mistake
The post processings such as filter, washing, technique is loaded down with trivial details, and yield is low, have three-waste pollution.Later Some Enterprises adopted liquid acid catalyst：Hydrochloric acid,
Oxalic acid, phosphoric acid, polyphosphoric acid etc., but they are strong acid, and relatively acutely, product color is deeper for reaction.In recent years, it is thus proposed that adopt
Mineral, active hargil, ion exchange resin, zeolite replace inorganic acid catalyst synthesizing styrene phenol, amberlite
The catalytic action research of fat and zeolite catalyst also rests on the laboratory development stage, also there is resistance to heat differential, short life and hole
The low problem of skewness, conversion ratio.There is the deficiency such as noxious waste pollution, relatively costly in mineral and active hargil.
The content of the invention
In view of drawbacks described above of the prior art or deficiency, expect to provide that a kind of course of reaction is steady, reaction temperature is easy
The preparation method of the shallower styrenated phenol of control, product color.
The present invention provides a kind of excellent corrosion resisting property, good impact toughness, easy to process, intensity high styrol
The preparation method of phenol.
The preparation method of the styrenated phenol of the present invention, comprises the steps of：
Step one：Phenol and p-methyl benzenesulfonic acid input container are taken, leads to nitrogen, agitating device is sufficiently stirred for, stirring dress
The rotating speed put is 300～350r/min, is heated to 85 DEG C, starts Deca styrene, and time for adding is less than 2.5 hours；
Step 2：After the completion of Deca styrene, 120～130 DEG C are at the uniform velocity warming up to, and are incubated, temperature retention time is 2
～2.5 hours；
Step 3：Stop heating, in mixture triethylamine is added, filter after being sufficiently stirred for, then sucking filtration, vacuum are steamed
Evaporate, until no liquid is steamed, be cooled to less than 80 DEG C, discharging.
The catalyst p-methyl benzenesulfonic acid that adopts of preparation method of the styrenated phenol of the present invention for organic acid, Pyrogentisinic Acid and
Cinnamic alkylated reaction has good facilitation effect, and its acidity is weaker than inorganic acids such as sulphuric acid, hydrochloric acid, to consersion unit
Extent of corrosion less, course of reaction is steady, and reaction temperature is easily controlled, and using low temperature Deca styrene, can effectively suppress
Styrene gathers and coking phenomenon suddenly, and product color obtained in the preparation method of the present invention is shallower.Without industry " three in course of reaction
It is useless " discharge, greatly reduce the pollution to environment.Under the conditions of equivalent responses, the yield of feed stock conversion and product is higher.
Specific embodiment
The application is described in further detail with reference to embodiment.It is understood that tool described herein
Body embodiment is used only for explaining related invention, rather than the restriction to the invention.
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase
Mutually combination.The application is described in detail with reference to embodiment.
A kind of preparation method of styrenated phenol, comprises the steps of：
Step one：Phenol and p-methyl benzenesulfonic acid input container are taken, leads to nitrogen, agitating device is sufficiently stirred for, stirring dress
The rotating speed put is 300～350r/min, is heated to 85 DEG C, starts Deca styrene, and time for adding is less than 2.5 hours；
Step 2：After the completion of Deca styrene, 120～130 DEG C are at the uniform velocity warming up to, and are incubated, temperature retention time is 2
～2.5 hours；
Step 3：Stop heating, in mixture triethylamine is added, filter after being sufficiently stirred for, then sucking filtration, vacuum are steamed
Evaporate, until no liquid is steamed, be cooled to less than 80 DEG C, discharging.
Further, phenol purity is more than 99%, and styrene purity is more than 99%.
Further, styrene and the mass ratio of phenol are 1.9:1～2.3:1.
Further, Deca styrene in step one, dropping temperature is 88～92 DEG C, and rate of addition is 2.6～5g/min.
Further, p-methyl benzenesulfonic acid and the mass ratio of phenol are 1:100～1:50.
Further, in step 3, the vacuum of vacuum distilling is 0.095Mpa, and temperature is less than or equal to 140 DEG C.
Embodiment one
Accurately weigh 200g phenol and 2.0g p-methyl benzenesulfonic acid is put in the four-hole boiling flask of dried and clean, fix and install
Good stirring paddle, on its excess-three mouth of four-hole boiling flask thermocouple, bulb condensation return duct and nitrogen conduit are inserted respectively.By nitrogen
Heating melts phenol, opens stirring paddle, and rotating speed is in 300r/min.When temperature is raised to 85 DEG C, Deca 380g styrene, control
Rate of addition is 2.6g/min, and time for adding is less than 2.5h, and temperature maintains 88～92 DEG C.Drip off and be at the uniform velocity warming up to 120 DEG C,
Start insulation.Stop heating after 2h, add the neutralization of 1.2g triethylamines, filter after being sufficiently stirred for.Start vacuum pump, adjust vacuum
For 0.095Mpa, kettle temperature is less than 140 DEG C, until no liquid is steamed.Less than 80 DEG C are cooled to, discharging.Finally obtain product receipts
Rate is 97.3%, and two substitution product contents are 61.1%, and styrene-content is 0.2%.
Embodiment two
Accurately weigh 200g phenol and 4.0g p-methyl benzenesulfonic acid is put in the four-hole boiling flask of dried and clean, fix and install
Good stirring paddle, on its excess-three mouth of four-hole boiling flask thermocouple, bulb condensation return duct and nitrogen conduit are inserted respectively.By nitrogen
Heating melts phenol, opens stirring paddle, and rotating speed is in 350r/min.When temperature is raised to 85 DEG C, Deca 460g styrene, control
Rate of addition is 5g/min, and time for adding is less than 2.5h, and temperature maintains 92 DEG C.Drip off and be at the uniform velocity warming up to 120 DEG C, start to protect
Temperature.2.5h rear stop heating, the neutralization of 2.4g triethylamines is added, filtered after being sufficiently stirred for.Start vacuum pump, adjustment vacuum is
0.095Mpa, kettle temperature is less than 140 DEG C, until no liquid is steamed.Less than 80 DEG C are cooled to, discharging.Finally obtain product yield
For 97.0%, two substitution product contents are 84.5%, and styrene-content is 0.6%.
Embodiment three
Accurately weigh 200g phenol and 3.0g p-methyl benzenesulfonic acid is put in the four-hole boiling flask of dried and clean, fix and install
Good stirring paddle, on its excess-three mouth of four-hole boiling flask thermocouple, bulb condensation return duct and nitrogen conduit are inserted respectively.By nitrogen
Heating melts phenol, opens stirring paddle, and rotating speed is in 330r/min.When temperature is raised to 85 DEG C, Deca 420g styrene, control
Rate of addition is 3.5g/min, and time for adding is less than 2.5h, and temperature maintains 90 DEG C.Drip off and be at the uniform velocity warming up to 120 DEG C, start
Insulation.Stop heating after 2.2h, add the neutralization of 1.8g triethylamines, filter after being sufficiently stirred for.Start vacuum pump, adjustment vacuum is
0.095Mpa, kettle temperature is less than 140 DEG C, until no liquid is steamed.Less than 80 DEG C are cooled to, discharging.Finally obtain product yield
For 97.1%, two substitution product contents are 75.1%, and styrene-content is 0.5%.Product yield is finally obtained for 97.1%, two
Substitution product content is 75.1%, and styrene-content is 0.5%.
The present invention takes the cinnamic processing step of low temperature Deca, can effectively suppress styrene poly- and coking phenomenon suddenly,
In hydrocarbons, cinnamic monomer reactivity is larger, can be by ionic mechanism and free radical during its storage and use
There are two kinds of polyreactions in mechanism, usual ionic mechanism polymerization is caused by catalyst, and free radical mechanism polymerization is to pass through
The reaction of thermal excitation.So the appropriate triethylamine catalyst neutralisation of low temperature Deca styrene and addition can effectively suppress
Styrene autohemagglutination gathers suddenly.In addition all of Organic substance is chronically in hot environment and all can have coking phenomenon, and low temperature Deca benzene
Ethylene can reduce coking risk.And be passed through nitrogen and protected, farthest improve the quality and color and luster of product.Pass through
Regulate and control cinnamic rate of addition, effectively reduce the generation of by-product, the distribution of each component is optimum in product, active component
Di-substituted content is higher.In the subsequent treatment of product, part is had neither part nor lot in the benzene second of reaction by the way of vacuum distilling
Alkene is steamed, and improves the utilization rate of raw material, reduces the pungent abnormal smells from the patient of product, substantially improves construction environment.
The present invention adopts p-methyl benzenesulfonic acid for catalyst, and reaction is gentle, and course of reaction is easily controlled, the corruption to consersion unit
Degree of corrosion is preferably minimized.Meanwhile, the conversion ratio of reaction raw materials is higher, and product yield reaches more than 97%.On feed way, benzene
Ethylene is slightly excessive to make phenol react completely, by controlling cinnamic rate of addition, the distribution ratio of each component in optimized product
Example, reduces the generation of by-product, the quality of improving product.Styrol obtained in the preparation method of styrenated phenol of the present invention
Preferably, modest viscosity, di-substituted content can reach more than 50% to phenol product color and luster.Course of reaction is without waste gas, waste water, useless
Slag is produced, and to environment severe contamination is not resulted in.The purpose for adding triethylamine is catalyst neutralisation p-methyl benzenesulfonic acid so that reaction
Terminate, be easy to long term storage, improve using effect.Superfluous styrene is separated by way of vacuum distilling, can be used as reaction
Raw material is continuing with, and improves the utilization rate of raw material；The reaction condition that the present invention is adopted is not harsh, and process is easily-controllable, and energy consumption is relatively low,
With considerable economic results in society.
Above description is only the preferred embodiment of the application and the explanation to institute's application technology principle.People in the art
Member should be appreciated that invention scope involved in the application, however it is not limited to the technology of the particular combination of above-mentioned technical characteristic
Scheme, while also should cover in the case of without departing from the inventive concept, is carried out by above-mentioned technical characteristic or its equivalent feature
Combination in any and other technical schemes for being formed.Such as features described above has similar work(with (but not limited to) disclosed herein
The technical scheme that the technical characteristic of energy is replaced mutually and formed.
Claims (6)
1. a kind of preparation method of styrenated phenol, it is characterised in that comprise the steps of：
Step one：Phenol and p-methyl benzenesulfonic acid input container are taken, leads to nitrogen, agitating device is sufficiently stirred for, the stirring dress
The rotating speed put is 300～350r/min, is heated to 85 DEG C, starts Deca styrene, and time for adding is less than 2.5 hours；
Step 2：After the completion of Deca styrene, be at the uniform velocity warming up to 120～130 DEG C, and be incubated, temperature retention time be 2～
2.5 hour；
Step 3：Stop heating, in mixture triethylamine is added, filter after being sufficiently stirred for, then sucking filtration, vacuum distilling, directly
Steam to no liquid, be cooled to less than 80 DEG C, discharging.
2. the preparation method of styrenated phenol according to claim 1, it is characterised in that the phenol purity is more than
99%, the styrene purity is more than 99%.
3. the preparation method of styrenated phenol according to claim 1, it is characterised in that the styrene and the benzene
The mass ratio of phenol is 1.9:1～2.3:1.
4. the preparation method of styrenated phenol according to claim 1, it is characterised in that Deca benzene in the step one
Ethylene, dropping temperature is 88～92 DEG C, and rate of addition is 2.6～5g/min.
5. the preparation method of the styrenated phenol according to any one of Claims 1 to 4, it is characterised in that described to first
Benzenesulfonic acid is 1 with the mass ratio of the phenol:100～1:50.
6. the preparation method of the styrenated phenol according to any one of Claims 1 to 4, it is characterised in that the step
In three, the vacuum of vacuum distilling is 0.095Mpa, and temperature is less than or equal to 140 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610700589.5A CN106631704A (en) | 2016-08-22 | 2016-08-22 | Preparation method for styrenated phenol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610700589.5A CN106631704A (en) | 2016-08-22 | 2016-08-22 | Preparation method for styrenated phenol |
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| CN106631704A true CN106631704A (en) | 2017-05-10 |
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| CN201610700589.5A Pending CN106631704A (en) | 2016-08-22 | 2016-08-22 | Preparation method for styrenated phenol |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141465A (en) * | 2017-06-05 | 2017-09-08 | 浙江皇马科技股份有限公司 | A kind of styrylphenol polyoxyethylene ether and preparation method thereof |
| CN109627146A (en) * | 2018-12-07 | 2019-04-16 | 浙江皇马科技股份有限公司 | A kind of preparation method of styrylphenol |
| CN110981701A (en) * | 2019-12-24 | 2020-04-10 | 江苏精禾界面科技有限公司 | Method for synthesizing polystyrolated phenol |
| CN116283504A (en) * | 2023-03-13 | 2023-06-23 | 江苏极易新材料有限公司 | Synthesis method of 2, 4-dicumyl phenol |
| CN117623871A (en) * | 2023-10-27 | 2024-03-01 | 山东峰泉新材料有限公司 | Synthesis method of monosubstituted styrenated phenol |
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| CN102267876A (en) * | 2011-06-20 | 2011-12-07 | 常州大学 | Preparation method of styrenated hindered phenol or styrenated phenol antioxidant product |
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Patent Citations (1)
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| CN102267876A (en) * | 2011-06-20 | 2011-12-07 | 常州大学 | Preparation method of styrenated hindered phenol or styrenated phenol antioxidant product |
Non-Patent Citations (1)
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| 张金龙等: "苯乙烯化苯酚的合成研究", 《精细石油化工进展》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107141465A (en) * | 2017-06-05 | 2017-09-08 | 浙江皇马科技股份有限公司 | A kind of styrylphenol polyoxyethylene ether and preparation method thereof |
| CN107141465B (en) * | 2017-06-05 | 2019-09-20 | 浙江皇马科技股份有限公司 | A kind of styrylphenol polyoxyethylene ether and preparation method thereof |
| CN109627146A (en) * | 2018-12-07 | 2019-04-16 | 浙江皇马科技股份有限公司 | A kind of preparation method of styrylphenol |
| CN110981701A (en) * | 2019-12-24 | 2020-04-10 | 江苏精禾界面科技有限公司 | Method for synthesizing polystyrolated phenol |
| CN110981701B (en) * | 2019-12-24 | 2022-10-18 | 江苏精禾界面科技有限公司 | Method for synthesizing polystyrolated phenol |
| CN116283504A (en) * | 2023-03-13 | 2023-06-23 | 江苏极易新材料有限公司 | Synthesis method of 2, 4-dicumyl phenol |
| CN116283504B (en) * | 2023-03-13 | 2023-10-10 | 江苏极易新材料有限公司 | Synthesis method of 2, 4-dicumyl phenol |
| CN117623871A (en) * | 2023-10-27 | 2024-03-01 | 山东峰泉新材料有限公司 | Synthesis method of monosubstituted styrenated phenol |
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