CN102558230A - Quaternary phosphor salt acidic ionic liquid and application thereof in synthesizing benzyltoluene - Google Patents

Quaternary phosphor salt acidic ionic liquid and application thereof in synthesizing benzyltoluene Download PDF

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Publication number
CN102558230A
CN102558230A CN2010105989267A CN201010598926A CN102558230A CN 102558230 A CN102558230 A CN 102558230A CN 2010105989267 A CN2010105989267 A CN 2010105989267A CN 201010598926 A CN201010598926 A CN 201010598926A CN 102558230 A CN102558230 A CN 102558230A
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ionic liquid
liquid
acidic ion
lewis acidic
quaternary
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常卫星
李靖
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Nankai University
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Nankai University
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Abstract

The invention relates to a quaternary phosphor salt acidic ionic liquid and application thereof in synthesizing benzyltoluene, belonging to the field of preparation and application of ionic liquids. The general formula of the vapor-insensitive quaternary phosphor salt Lewis acidic ionic liquid is Bu3P<+>RB<->/ZnX2, wherein R is C12-16 aliphatic alkyl group, B- is one of Cl<->, Br<-> or PF6<->, and X is Cl<-> or Br<->. The preparation method comprises the following steps: adding a certain proportion of zinc halide into the Bu3P<+>RB-, and reacting under certain temperature to generate a transparent liquid. The ionic liquid can be used for catalytically preparing power capacitor insulating oil benzyltoluene. Compared with the prior art, the invention has the advantages of accessible raw materials, simple after-treatment and environment friendliness, can be recycled, and is insensitive to vapor.

Description

A kind of quaternary phosphine salt acidic ion liquid and the application in synthesize benzyl toluene thereof
Technical field
The present invention relates to ionic liquid preparation and Application Areas, further say so about a kind of the insensitive quaternary phosphine salt of steam Lewis acidic ion liquid and method for making and the application in the synthetic power capacitor transformer oil benzyl toluene of catalysis.
Background technology
Under acid catalysis, carrying out Friedel-Crafts reaction through toluene and benzyl chlorine as the benzyl toluene of power capacitor transformer oil prepares.Shortcoming with sulphuric acid catalysis is large usage quantity and can not recycles and produce a large amount of spent acid, difficult treatment, etching apparatus.In addition; Though the environment amenable solid acid catalysis method of exploitation has been used to the production of benzyl toluene type transformer oil in recent years; But the solid acid catalyst complicated process of preparation, cost an arm and a leg and need frequent regeneration in process of production; Make the production cost of benzyl toluene can not be in any more, limited promoting the use of of benzyl toluene.Research shows and can carry out acid catalyzed reaction (petrochemical complex, 33 (4), 297-302,2004 with having alternative traditional liquid bronsted acid catalyst and the solid acid catalyst of Lewis tart ionic liquid; Sanming College's journal, 26 (2), 19-193,2009).Yet; In the laboratory, be applied to catalyzed reaction though study more chloro-aluminate type ionic liquid with high catalytic activity; But this ionic liquid is very responsive to airborne steam; Need under absolute anhydrous condition, use, otherwise catalytic activity and selectivity have obvious decline, therefore seek the insensitive high stability acidic ion liquid of steam very necessary.
We know that ionic liquid is made up of zwitterion; In positively charged ion to researchs such as quaternary ammonium salt, pyroles, imidazoles with report that more Er quaternary phosphine positively charged ion also is one type of important ionic liquid positively charged ion; For the building-up reactions of quaternary alkylphosphonium salt study also comparatively ripe (CN200310100174); Particularly (14,16) Phosphonium are as sterilant commercialization, but utilize it less as the research of functionalized acidic ionic liquid, and the catalyzer that the conduct of especially preparing high stability by it prepares power capacitor transformer oil benzyl toluene does not appear in the newspapers for halogenation tributyl 12.
Summary of the invention
The object of the invention is exactly to traditional liquid acid, solid acid and the ion liquid deficiency of chlorine aluminic acid type, provides a kind of and has a quaternary phosphine salt Lewis acidic ion liquid that high stability and raw material are easy to get to steam is insensitive.And this quaternary phosphine salt Lewis acidic ion liquid is applied to catalytic preparation power capacitor transformer oil benzyl toluene.
Technical scheme of the present invention is following:
It is a kind of to the insensitive quaternary phosphine salt of steam Lewis acidic ion liquid that the present invention provides, and its general formula is: Bu 3P +RB -/ ZnX 2, wherein R is the aliphatic alkyl of C12～16, B -Be Cl -, Br -, PF 6 -In a kind of, X is Cl -Or Br -
The invention provides the method for making of above-mentioned Lewis acidic ion liquid, step is: quaternary alkylphosphonium salt Bu 3P +RB -The a certain proportion of zinc halide of middle adding is reacted into transparent liquid at a certain temperature and just gets the Lewis acidic ion liquid.
R in the said quaternary alkylphosphonium salt is the aliphatic alkyl of C12～16, and the ratio of said adding zinc halide is X=0.6～0.8 (an X=zinc halide mole number/zinc halide mole number+quaternary alkylphosphonium salt mole numbers), and said temperature of reaction is 100～150 ℃.Reaction times is 1～5 hour.
Above-mentioned Lewis acidic ion liquid is applied to the catalytic preparation benzyl toluene, and method is: toluene is mixed with benzyl chlorine according to a certain percentage, add a certain amount of above-mentioned quaternary phosphine salt Lewis acidic ion liquid, back flow reaction.
Said toluene and benzyl chlorine blending ratio are 2: 1～10: 1.Reaction times is 2～8 hours.
With existing liquid bronsted acid catalyst, solid acid catalyst and chloro-aluminate type ionic-liquid catalyst compared with techniques, aftertreatment of the present invention is simple, only needs to divide liquid catalyst just can to separate with product and recycle, and has reduced cost.The present invention is environmentally friendly, and is to steam and air-stable, easy and simple to handle simultaneously, is fit to suitability for industrialized production.In addition, utilize commercial quaternary alkylphosphonium salt to prepare acidic ion liquid and have more the advantage that raw material is easy to get.
Embodiment
Following embodiment can make those skilled in the art more fully understand the present invention, but does not limit the present invention in any way.
Embodiment 1
Add 40.7 gram (0.1mol) chlorination tributyls, 14 alkane base Phosphonium in the 250mL round-bottomed flask, add 40.8 gram (0.3mol) zinc chloride under 40 ℃ of stirrings in batches, be warming up to 120 ℃ of reactions 2 hours, become transparent liquid to be quaternary phosphine salt Lewis acidic ion liquid.Other gets the 250mL round-bottomed bottle, adds 64.4 gram (0.7mol) toluene and 8.9 gram (0.07mol) benzyl chlorine, adds the above-mentioned Bu of 8.2 grams again 3P +(CH 2) 13CH 3Cl -/ ZnCl 2Ionic liquid, back flow reaction 2 hours leaves standstill, separatory, the transformation efficiency that upper strata GC analyzes benzyl chlorine is 100%, productive rate is 95%.The ionic liquid of lower floor can be recycled.
Embodiment 2
Get the 250mL round-bottomed bottle, add 64.4 gram (0.7mol) toluene and 8.9 gram (0.07mol) benzyl chlorine, add the Bu that separatory reclaims among the embodiment 1 again 3P +(CH 2) 13CH 3Cl -/ ZnCl 2Ionic liquid, back flow reaction 2 hours leaves standstill, separatory, the transformation efficiency that upper strata GC analyzes benzyl chlorine is 100%, productive rate is 96%.The ionic liquid of lower floor can be recycled.
Embodiment 3
Add 42.3 gram (0.1mol) bromination tributyls, 12 alkane base Phosphonium in the 250mL round-bottomed flask, add 27.2 gram (0.2mol) zinc chloride under 40 ℃ of stirrings in batches, be warming up to 100 ℃ of reactions 3 hours, become transparent liquid to be quaternary phosphine salt Lewis acidic ion liquid.Other gets the 250mL round-bottomed bottle, adds 64.4 gram (0.7mol) toluene and 8.9 gram (0.07mol) benzyl chlorine, adds the above-mentioned Bu of 8.6 grams again 3P +(CH 2) 11CH 3Br -/ ZnCl 2Ionic liquid, back flow reaction 4 hours leaves standstill, separatory, the transformation efficiency that upper strata GC analyzes benzyl chlorine is 100%, productive rate is 95%.The ionic liquid of lower floor can be recycled.
Embodiment 4
Add 37.9 gram (0.1mol) chlorination tributyls, 12 alkane base Phosphonium in the 250mL round-bottomed flask, add 13.6 gram (0.3mol) zinc chloride under 40 ℃ of stirrings in batches, be warming up to 120 ℃ of reactions 4 hours, become transparent liquid to be quaternary phosphine salt Lewis acidic ion liquid.Other gets the 250mL round-bottomed bottle, adds 19.3 gram (0.21mol) toluene and 8.9 gram (0.07mol) benzyl chlorine, adds the above-mentioned Bu of 6.8 grams again 3P +(CH 2) 11CH 3Cl -/ ZnCl 2Ionic liquid, back flow reaction 4 hours leaves standstill, separatory, the transformation efficiency that upper strata GC analyzes benzyl chlorine is 100%, productive rate is 94%.The ionic liquid of lower floor can be recycled.
Embodiment 5
Add 51.7 gram (0.1mol) phosphofluoric acid tributyls, 14 alkane base Phosphonium in the 250mL round-bottomed flask, add 54.4 gram (0.4mol) zinc chloride under 40 ℃ of stirrings in batches, be warming up to 150 ℃ of reactions 2 hours, become transparent liquid to be quaternary phosphine salt Lewis acidic ion liquid.Other gets the 250mL round-bottomed bottle, adds 41.1 gram (0.45mol) toluene and 8.9 gram (0.07mol) benzyl chlorine, adds the above-mentioned Bu of 10.6 grams again 3P +(CH 2) 13CH 3PF 6 -/ ZnCl 2Ionic liquid, back flow reaction 4 hours leaves standstill, separatory, the transformation efficiency that upper strata GC analyzes benzyl chlorine is 100%, productive rate is 97%.The ionic liquid of lower floor can be recycled.
Embodiment 6
Add 40.7 gram (0.1mol) chlorination tributyls, 14 alkane base Phosphonium in the 250mL round-bottomed flask, add 67.5 gram (0.3mol) zinc bromides under 40 ℃ of stirrings in batches, be warming up to 120 ℃ of reactions 5 hours, become transparent liquid to be quaternary phosphine salt Lewis acidic ion liquid.Other gets the 250mL round-bottomed bottle, adds 64.4 gram (0.7mol) toluene and 44.5 gram (0.35mol) benzyl chlorine, adds the above-mentioned Bu of 10.9 grams again 3P +(CH 2) 13CH 3Cl -/ ZnBr 2Ionic liquid, back flow reaction 8 hours leaves standstill, separatory, the transformation efficiency that upper strata GC analyzes benzyl chlorine is 100%, productive rate is 94%.The ionic liquid of lower floor can be recycled.
Embodiment 7
Add 43.5 gram (0.1mol) chlorination tributyls, 16 alkane base Phosphonium in the 250mL round-bottomed flask, add 67.5 gram (0.3mol) zinc bromides under 40 ℃ of stirrings in batches, be warming up to 120 ℃ of reactions 3 hours, become transparent liquid to be quaternary phosphine salt Lewis acidic ion liquid.Other gets the 250mL round-bottomed bottle, adds 64.4 gram (0.7mol) toluene and 8.9 gram (0.07mol) benzyl chlorine, adds the above-mentioned Bu of 12.5 grams again 3P +(CH 2) 15CH 3Cl -/ ZnBr 2Ionic liquid, back flow reaction 6 hours leaves standstill, separatory, the transformation efficiency that upper strata GC analyzes benzyl chlorine is 100%, productive rate is 95%.The ionic liquid of lower floor can be recycled.
Embodiment 8
Add 47.9 gram (0.1mol) bromination tributyls, 16 alkane base Phosphonium in the 250mL round-bottomed flask, add 67.5 gram (0.3mol) zinc bromides under 40 ℃ of stirrings in batches, be warming up to 100 ℃ of reactions 3 hours, become transparent liquid to be quaternary phosphine salt Lewis acidic ion liquid.Other gets the 250mL round-bottomed bottle, adds 64.4 gram (0.7mol) toluene and 8.9 gram (0.07mol) benzyl chlorine, adds the above-mentioned Bu of 11.3 grams again 3P +(CH 2) 15CH 3Br -/ ZnBr 2Ionic liquid, back flow reaction 5 hours leaves standstill, separatory, the transformation efficiency that upper strata GC analyzes benzyl chlorine is 100%, productive rate is 96%.The ionic liquid of lower floor can be recycled.

Claims (5)

1. one kind to the insensitive quaternary phosphine salt of steam Lewis acidic ion liquid, and its general formula is: Bu 3P +RB -/ ZnX 2
2. according to the Lewis acidic ion liquid of claim 1, it is characterized in that R is the aliphatic alkyl of C12～16, B -Be Cl -, Br -, PF 6 -In a kind of, X is Cl -Or Br -
3. the preparation method of the described Lewis acidic ion liquid of claim 1 is: quaternary alkylphosphonium salt Bu 3P +RX -The a certain proportion of zinc halide of middle adding is reacted into transparent liquid at a certain temperature and just gets the Lewis acidic ion liquid.
4. according to the method for making of claim 3; It is characterized in that said quaternary alkylphosphonium salt R is the aliphatic alkyl of C12～16; The ratio of said adding zinc halide is X=0.6～0.8 (an X=zinc halide mole number/zinc halide mole number+quaternary alkylphosphonium salt mole numbers); Said temperature of reaction is 60～150 ℃, and the reaction times is 1～5 hour.
5. according to the described Lewis acidic ion liquid of claim 1, it is characterized in that can be used as the catalyzer of preparation power capacitor transformer oil benzyl toluene.
CN2010105989267A 2010-12-21 2010-12-21 Quaternary phosphor salt acidic ionic liquid and application thereof in synthesizing benzyltoluene Pending CN102558230A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103319297A (en) * 2013-06-26 2013-09-25 四川东材科技集团股份有限公司 Method for preparing phenyl ethylbenzene ethane capacitor insulating oil through catalysis of acidic ionic liquid
CN103804111A (en) * 2012-11-09 2014-05-21 中化化工科学技术研究总院 Preparation method of heat conduction oil
CN103801402A (en) * 2012-11-09 2014-05-21 中化化工科学技术研究总院 Quaternary phosphonium salt ionic liquid composite catalyst, preparation method and application thereof
CN103805307A (en) * 2012-11-09 2014-05-21 中化化工科学技术研究总院 Preparation method for capacitor insulating oil
CN103804118A (en) * 2012-11-09 2014-05-21 中化化工科学技术研究总院 Friedel-Crafts alkylation reaction method
CN103833508A (en) * 2012-11-23 2014-06-04 中国石油天然气股份有限公司 Method for catalysis synthesis of dibenzyl toluene through solid acid catalyst
CN103833509A (en) * 2012-11-23 2014-06-04 中国石油天然气股份有限公司 Method for catalysis synthesis of benzyl toluene through solid acid catalyst
CN105017144A (en) * 2014-04-25 2015-11-04 江苏圣奥化学科技有限公司 Rubber aging inhibitor RD and preparation method for same

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103805307B (en) * 2012-11-09 2015-07-15 中化化工科学技术研究总院 Preparation method for capacitor insulating oil
CN103804111A (en) * 2012-11-09 2014-05-21 中化化工科学技术研究总院 Preparation method of heat conduction oil
CN103801402A (en) * 2012-11-09 2014-05-21 中化化工科学技术研究总院 Quaternary phosphonium salt ionic liquid composite catalyst, preparation method and application thereof
CN103805307A (en) * 2012-11-09 2014-05-21 中化化工科学技术研究总院 Preparation method for capacitor insulating oil
CN103804118A (en) * 2012-11-09 2014-05-21 中化化工科学技术研究总院 Friedel-Crafts alkylation reaction method
CN103804118B (en) * 2012-11-09 2016-03-09 中化化工科学技术研究总院 A kind of Friedel-Crafts reaction method
CN103801402B (en) * 2012-11-09 2016-03-09 中化化工科学技术研究总院 A kind of quaternary phosphonium salt ionic liquid composite catalyst and its preparation method and application
CN103804111B (en) * 2012-11-09 2015-07-15 中化化工科学技术研究总院 Preparation method of heat conduction oil
CN103833509A (en) * 2012-11-23 2014-06-04 中国石油天然气股份有限公司 Method for catalysis synthesis of benzyl toluene through solid acid catalyst
CN103833508A (en) * 2012-11-23 2014-06-04 中国石油天然气股份有限公司 Method for catalysis synthesis of dibenzyl toluene through solid acid catalyst
CN103319297A (en) * 2013-06-26 2013-09-25 四川东材科技集团股份有限公司 Method for preparing phenyl ethylbenzene ethane capacitor insulating oil through catalysis of acidic ionic liquid
CN105017144A (en) * 2014-04-25 2015-11-04 江苏圣奥化学科技有限公司 Rubber aging inhibitor RD and preparation method for same
CN105017144B (en) * 2014-04-25 2019-05-28 圣奥化学科技有限公司 A kind of rubber antiager RD and preparation method thereof

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Application publication date: 20120711