CN1257873C - Method for synthesizing linear alkyl diphenyl ether - Google Patents
Method for synthesizing linear alkyl diphenyl ether Download PDFInfo
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- CN1257873C CN1257873C CN 03105027 CN03105027A CN1257873C CN 1257873 C CN1257873 C CN 1257873C CN 03105027 CN03105027 CN 03105027 CN 03105027 A CN03105027 A CN 03105027A CN 1257873 C CN1257873 C CN 1257873C
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Abstract
The present invention discloses a method for synthesizing linear alkyl diphenyl ether, which has the advantages of high mono alkylation yield, simple product separation and purification and no catalyst loss. An ionic liquid in place of traditional AlCl3 or hydrofluoric acid is used as a catalyst by the method to catalyze the reaction of an alkylating agent and phenyl ether so as to synthesize linear chain alkyl ether. Because the ionic liquid is used as the catalyst of the alkylation reaction of the alkylating agent and phenyl ether, the method has the advantages of no obvious vapor pressure, environmental friendliness, high catalytic activity, adjustable nature and direct cycling use without treatment. The process has mild conditions, easy separation of the product from the catalyst, simple operation and good reproducibility.
Description
Technical field
The present invention relates to the method for a kind of synthetic straight chained alkyl phenyl ether in the fine chemical technology field.
Background technology
Tensio-active agent industry as an important branch of fine chemistry industry is in developing period.The straight chained alkyl phenyl ether is a kind of important fine chemical material, United States Patent (USP) 5552071 (1996) (Mobil Oil Corp.) has been described the straight chained alkyl phenyl ether and has been had excellent low temperature viscosity characteristic and intermiscibility, can be used as the fabulous lubricating oil of thermostability and use, but its maximum purposes is to be to prepare long-chain alkyl benzene ether sulfonate (a kind of anion surfactant of excellent property).
The straight chained alkyl phenyl ether is that alkylating agent and phenyl ether carry out the alkylated reaction generation under the effect of catalyzer.Originally the most frequently used catalyzer of alkylated reaction is aluminum chloride (AlCl
3), ZnCl
2, BF
3Deng Lewis acid.After discover, other many catalyzer also have same katalysis, as hydrofluoric acid, are the main flow catalyzer in the present alkylbenzene suitability for industrialized production.Industrial general employing alpha-olefin is used the proton acid as catalyst as alkylating agent, has bibliographical information also can adopt ion exchange resin or super acids as catalyzer.But all there are some defectives in above catalyzer: as adopting AlCl
3Make catalyzer, though cheap and easy to get, catalytic activity good, can produce aluminium bisulfate waste liquor contaminate environment, and the Separation ﹠ Purification difficulty of product; The hydrofluoric acid price is more expensive, and corrodibility is extremely strong; The solid acid as catalyst often is subjected to the restriction of temperature of reaction, and is difficult to regeneration after losing efficacy.
Ionic liquid is a kind of room temperature melting salt, near (＜100 ℃) under the room temperature condition, is a kind of low-viscosity (mobile) liquid that is made of ion fully.Ion liquid research can be traced back to 1914, and the first research object is an ethylamine nitrate.Ionic liquid is as a kind of good ionogen, and its early stage research is concentrated on electrochemical field.To 20th century the mid-80, it is found that ionic liquid is a kind of good solvent and brand-new catalytic material, have organic solvent and traditional catalyst incomparable character.In the catalyticing research field; ionic liquid replaces traditional catalyzer and organic solvent; improved the chemical reaction process that many people know, as Diels-Alder reaction, Friedel-Crafts reaction, Heck reaction, hydrogenation and olefin hydroformylation etc.Studies show that ionic liquid replaces traditional catalyzer and organic solvent, can greatly improve reactive behavior.
Summary of the invention
The purpose of this invention is to provide a kind of monoalkylation productive rate that improves, simplify the Separation ﹠ Purification of product, avoid the method for the synthetic straight chained alkyl phenyl ether of catalyst loss.
A kind of method of synthetic straight chained alkyl phenyl ether is that alkylating agent and phenyl ether carry out the alkylated reaction generation under the effect of catalyzer, and described catalyzer is an ionic liquid.
Described ionic liquid is alkyl imidazole, alkylammonium salt compounds and metal halide synthetic.Described alkyl imidazole is preferably 1,3 alkyl imidazole, and the alkyl chain length of alkyl imidazole and alkylammonium salt is 1 to 10 carbon atom; Described metal halide is preferably aluminum chloride.
The ratio of described 1,3 alkyl imidazole and alkylammonium salt and metal halide is 1: 1 to 1: 10.
The used ionic liquid of the present invention can adopt the ordinary method preparation: get a certain proportion of metal halide and alkyl imidazole or alkylammonium salt and directly mix in stink cupboard, with the ice bath cooling, the limpid liquid of formation is ionic liquid.
In the process of synthetic straight chained alkyl phenyl ether, described alkylating agent is the long-chain alpha-olefin of 10-20 carbon or the long-chain halogenated alkane of 10-20 carbon.Described alkylating agent and ionic liquid mol ratio are 0.2: 1 to 80: 1.
The feeding mode of straight chained alkyl phenyl ether building-up reactions has two kinds:
A kind of feeding mode is for dripping alkylating agent, and its reaction process is: a certain proportion of ionic liquid is mixed turn on agitator in there-necked flask with phenyl ether, be warming up to selected temperature of reaction, drip alkylating agent, react and stop stirring after 0.5 minute to 10 hours, make system reduce to room temperature.The system standing demix takes out product, and reaction back ionic liquid can not treatedly directly recycle.
Another kind of feeding mode is for dripping ionic liquid, and its reaction process is: a certain proportion of alkylating agent is mixed turn on agitator in there-necked flask with phenyl ether, be warming up to selected temperature of reaction, drip ionic liquid, react and stop stirring after 0.5 minute to 10 hours, make system reduce to room temperature.The system standing demix takes out product, and reaction back ionic liquid can not treatedly directly recycle.
With the synthetic straight chained alkyl phenyl ether of method of the present invention, ether alkene ratio should be 1: 1 to 50: 1 in the described synthesis material, and the temperature of described alkylated reaction is from room temperature to 200 ℃, is preferably 50 ℃; Reaction times is 0.5 minute to 10 hours.
The ionic liquid-catalyzed alkylating agent and the alkylated reaction of phenyl ether are typical Green Chemistry reactions.This reaction process transformation efficiency and selectivity are considerably beyond using AlCl
3Result when making catalyzer, target product productive rate height, and do not have environmental pollution problems.
Ionic liquid does not have remarkable vapour pressure as the catalyzer of alkylating agent and phenyl ether alkylated reaction, and is environmentally friendly, the catalytic activity height, and character is adjustable and can directly recycle without handling.This process reaction mild condition, product is easy to separate with catalyzer, and is simple to operate, favorable reproducibility.
Description of drawings
Fig. 1 is the influence of temperature of reaction to ionic liquid-catalyzed alkylated reaction productive rate
Fig. 2 is the influence of the ionic liquid-catalyzed alkylated reaction productive rate of ether alkene comparison
Embodiment
The synthetic single dodecyl phenyl ether of embodiment 1, ionic liquid-catalyzed laurylene and phenyl ether is reflected in the there-necked flask and carries out, and uses 81-2 type constant temperature blender with magnetic force to carry out temperature control and induction stirring, the oil bath heating systems.In the initial reaction system, phenyl ether and laurylene mol ratio are 8: 1, and the mol ratio of ionic liquid and laurylene is 1: 3.With a selected amount of ionic liquid with mix in phenyl ether places there-necked flask, turn on agitator is warming up to 50 ℃, drip laurylene from dropping funnel, react and stop after 5 minutes stirring, make the reaction system in the there-necked flask reduce to room temperature, reaction solution is transferred in the separating funnel.The system standing demix takes out product, and reaction back ionic liquid can not treatedly directly recycle.Detect the quality of single dodecyl phenyl ether in the product through high pressure liquid chromatography, calculate the single dodecyl phenyl ether of this reaction system productive rate and reach 87.35%.
Except that temperature of reaction, other reaction conditionss are with embodiment 1.Select 30 ℃, 50 ℃, 80 ℃, 100 ℃ respectively as temperature of reaction, investigate temperature of reaction reaction conversion ratio and optionally influence.The result as shown in Figure 1, the result shows the rising along with temperature of reaction, there is an optimum value in the productive rate of single dodecyl phenyl ether, product yield reaches the highest in the time of 50 ℃.
The influence of embodiment 3, the synthetic single dodecyl phenyl ether of ether alkene comparison
Except that ether alkene ratio, other reaction conditionss are with embodiment 1.Select 2: 1,3: 1,5: 1,8: 1,12: 1 ether alkene ratios respectively, investigate ether alkene comparison reaction conversion ratio and optionally influence as raw material.The result shows the rising along with ether alkene ratio as shown in Figure 2, and the productive rate of single dodecyl phenyl ether is in rising trend.
Embodiment 4, employing drip the ionic liquid mode and carry out phenyl ether and laurylene alkylated reaction
Reaction conditions is with embodiment 1, just with a selected amount of laurylene with mix in phenyl ether places there-necked flask, from dropping funnel dropping ionic liquid.Investigate the dropping mode to reaction conversion ratio and optionally influence.Detect the quality of single dodecyl phenyl ether in the product through high pressure liquid chromatography, calculating the single dodecyl phenyl ether of this reaction system productive rate is 73.32%.
In the present embodiment, alkylating agent is selected chlorinated dodecane for use.Phenyl ether and chlorinated dodecane mol ratio are 8: 1, the mol ratio of ionic liquid and chlorinated dodecane is 1: 3, with ionic liquid with mix in phenyl ether places there-necked flask, turn on agitator, be warming up to 50 ℃, drip chlorinated dodecane, react and stopped stirring in 5 minutes from dropping funnel, make the reaction system in the there-necked flask reduce to room temperature, reaction solution is transferred in the separating funnel.The system standing demix takes out product.Detect the quality of single dodecyl phenyl ether in the product through high pressure liquid chromatography, calculate the single dodecyl phenyl ether of this reaction system productive rate and reach 78.1%.
Claims (11)
1, a kind of method of synthetic straight chained alkyl phenyl ether is that alkylating agent and phenyl ether carry out the alkylated reaction generation under the effect of catalyzer, and it is characterized in that: described catalyzer is an ionic liquid.
2, method according to claim 1 is characterized in that: described ionic liquid is alkyl imidazole or alkylammonium salt compounds and metal halide synthetic.
3, method according to claim 2 is characterized in that: described alkyl imidazole is 1, and 3-alkyl imidazole, the alkyl chain length of alkyl imidazole and alkylammonium salt are 1 to 10 carbon atom; Described metal halide is an aluminum chloride.
4, method according to claim 3 is characterized in that: described 1, the ratio of 3-alkyl imidazole or alkylammonium salt and metal halide is 1: 1 to 1: 10.
5, method according to claim 1 is characterized in that: described alkylating agent is the long-chain alpha-olefin of 10-20 carbon or the long-chain halogenated alkane of 10-20 carbon.
6, according to any described method among the claim 1-5, it is characterized in that: described alkylating agent and ionic liquid mol ratio are 0.2: 1 to 80: 1.
7, method according to claim 1 is characterized in that: the feeding mode of described straight chained alkyl phenyl ether building-up reactions is for to drip alkylating agent in phenyl ether and ionic-liquid catalyst.
8, method according to claim 1 is characterized in that: the feeding mode of described straight chained alkyl phenyl ether building-up reactions is for to drip ionic liquid in phenyl ether and alkylating agent.
9, method according to claim 1 is characterized in that: the mol ratio of ether alkene is 1: 1 to 50: 1 in the described synthesis material.
10, method according to claim 1 is characterized in that: the temperature of described alkylated reaction is from room temperature to 200 ℃; Reaction times is 0.5 minute to 10 hours.
11, method according to claim 10 is characterized in that: the temperature of described alkylated reaction is 50 ℃.
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| CN 03105027 CN1257873C (en) | 2003-02-27 | 2003-02-27 | Method for synthesizing linear alkyl diphenyl ether |
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|---|---|---|---|
| CN 03105027 CN1257873C (en) | 2003-02-27 | 2003-02-27 | Method for synthesizing linear alkyl diphenyl ether |
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| CN1257873C true CN1257873C (en) | 2006-05-31 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787840A (en) * | 2014-02-11 | 2014-05-14 | 常州大学 | Method for catalyzing alkylation of olefin and diphenyl ether by use of solid superacid |
| CN107759637A (en) * | 2017-11-16 | 2018-03-06 | 山东大学 | The fluoridation catalyst of a kind of phosphonitrile and phosphazene derivative and its synthetic method of fluoride |
| CN108479849A (en) * | 2018-02-09 | 2018-09-04 | 中国日用化学工业研究院有限公司 | The solid-loaded ionic-liquid catalyst and preparation method and application of synthesis of alkyl diphenyl ether |
| CN109970521A (en) * | 2019-05-09 | 2019-07-05 | 福建师范大学 | A kind of preparation method of dodecyl diphenyl oxide |
| CN111454130A (en) * | 2020-04-20 | 2020-07-28 | 中国日用化学研究院有限公司 | Process for preparing alkyl diphenyl ether by catalyzing reaction of olefin and diphenyl ether with solid acid |
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