CN104324749B - A kind of alkaline ionic liquid catalyst of based on POSS of carbonate synthesis glyceride and preparation method thereof - Google Patents
A kind of alkaline ionic liquid catalyst of based on POSS of carbonate synthesis glyceride and preparation method thereof Download PDFInfo
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Abstract
Alkaline ionic liquid catalyst based on POSS (Polyhedral Oligomeric Silsesquioxanes, polyhedral oligomeric silsesquioxane) that the invention discloses a kind of carbonate synthesis glyceride and preparation method thereof.Catalyst carrier is eight chloropropyl silsesquioxane POSS Cl, and modifying component is alkali ionic liquid.The preparation method of catalyst is: first synthesis POSS Cl, then carries out the immobilized of alkali ionic liquid, modifies POSS, prepares alkaline ionic liquid catalyst based on POSS.It is an advantage of the current invention that obtained catalyst for catalyzing and synthesizing carbonic acid glyceride system, catalytic efficiency is high, and solvent-free, catalyst can be recycled, and production process is environmentally friendly.
Description
Technical field
The present invention relates to the alkaline ionic liquid catalyst based on POSS of carbonate synthesis glyceride preparation and
Application, belongs to the technical field of glycerol application.
Background technology
The whole world and environmental conservation pay attention to day by day in short supply to petroleum resources, it is new that development biodiesel becomes the whole world
The focus of energy development.The meeting a large amount of glycerol of by-product during production of biodiesel, it effectively utilizes and governs
The economy of production of biodiesel.Therefore, research and the application of the chemicals with glycerol as raw material causes the world
The extensive concern of various countries.
Carbonic acid glyceride, as a kind of green reproducible chemicals, can be widely used in polyurethane foam
Plastics, coating, detergent, cosmetic industry.Simultaneously carbonic acid glyceride as organic chemical industry important in
Mesosome, has the advantages such as combustibility is low, toxicity is little, boiling point is high, biodegradable, has good industry
Application prospect.
Alkali ionic liquid, as a kind of novel environmentally friendly solvent and liquid catalyst, was urged in recent years
The extensive application in change field, has the fixedness of high density reaction active site and solid catalyst, its structure
With active sites, there is adjustability, be the most programmable green catalyst.But most of ionic liquid
It is difficult to after precursor reactant separate with product, restricts its catalysis and prepare the process of industrialization of carbonic acid glyceride.
Using novel POSS to make carrier, alkali ionic liquid is made to modify component, and prepared is based on POSS
Alkaline ionic liquid catalyst had both had the high activity of homogeneous catalyst, during turn avoid heterogeneous catalysis
Diffusion-restricted, impart the easily separated characteristic of catalyst simultaneously, simplify operating process, reduce and operate into
This, cause people's extensive concern at present.
In order to solve the problems referred to above, the present invention provide the alkalescence based on POSS of a kind of carbonate synthesis glyceride from
Sub-liquid catalyst and preparation method thereof, meets the requirement of Green Chemistry, has tempting industrial prospect.
Summary of the invention
Object of the present invention is to provide the alkali ion liquid based on POSS of a kind of carbonate synthesis glyceride
Body catalyst and preparation method thereof.The active high and easily separated characteristic of catalyst obtained in this way.
The present invention is realized by the following technical scheme, a kind of carbonate synthesis glyceride based on POSS
Alkaline ionic liquid catalyst, described is glycerol and dimethyl carbonate synthesis carbonic acid glyceride, synthesize carbon
The preparation method of the alkaline ionic liquid catalyst based on POSS of acid glyceride, it is characterised in that include following
Process,
(1) preparation of POSS-Cl: take methanol 100～200ml, concentrated hydrochloric acid 5～15ml adds there-necked flask
In, and 3-chloropropyl triethoxysilane 10～20g is dropwise added drop-wise in above-mentioned solution, mechanical agitation 30～50h
After, add condensation catalyst 0.1～0.2g dibutyl stannane to said mixture, in the oil bath of 40～60 DEG C
Room temperature is down in middle reaction 30～50h, obtains white crystalline precipitation eight chloropropyl silsesquioxane POSS-Cl；
(2) alkali ionic liquid is immobilized: be dissolved in by 0.1～0.3g POSS-Cl in three neck round bottom flask
20～30ml dimethylformamides, and it is slowly added dropwise the N-alkyl imidazole of 0.08～0.1mol, under magnetic agitation
Being warming up to 60～75 DEG C, drip and complete continue to be stirred at reflux 18～32h, reduce pressure sucking filtration, ethyl acetate washing 2～5
The secondary white solid that obtains, is finally vacuum dried 18～32h at 60～90 DEG C, obtains presoma, take 0.8～2g KOH
Adding in 50ml single necked round bottom flask, and add 10～20ml dimethylformamides, stirring at normal temperatures makes it
Dissolve, be dividedly in some parts above-mentioned presoma 0.1～0.3g, room temperature reaction 2～5h under magnetic stirring, then in bottle
Adding 4～8ml ether, continue at room temperature reaction 18～32h, stopped reaction, rotation is evaporated off solvent, obtains
Solid catalyst imidazoles based on POSS alkali ionic liquid.
Above-mentioned N-alkyl imidazole is N-Methylimidazole., N-ethyl imidazol(e), N-isopropylimdazole, N-pi-allyl miaow
Azoles or any one of N-vinyl imidazole.
Above-mentioned prepared alkaline ionic liquid catalyst based on POSS is used for the technique of carbonate synthesis glyceride, its
It is characterised by including procedure below:
(1) glycerol and dimethyl carbonate are added in reactor according to mol ratio 1: 5～1: 15, add
Quality is 1～the alkaline ionic liquid catalyst based on POSS of 10% of reactant gross mass, in reaction temperature
Degree is 50～200 DEG C, and pressure is 1～3Mpa, under the conditions of stir speed (S.S.) is 500～1200rpm, and the response time
It is 1～10h, obtains the mixture containing carbonic acid glyceride；
(2) filtering step (1) mixture, the solid catalyst leached continues cycling through use.
It is an advantage of the current invention that the active high and easily separated characteristic of catalyst, it is expected to become great competition
The cleaning procedure route of power.
Below by specific embodiment, the present invention is further illustrated with, but is not intended to the present invention.
Detailed description of the invention
[embodiment 1]
The preparation of POSS-Cl: take methanol 150ml, concentrated hydrochloric acid 10ml and add in there-necked flask, and by 3-chlorine
Propyl-triethoxysilicane 15g is dropwise added drop-wise in above-mentioned solution, after mechanical agitation 32h, by condensation catalyst
0.12g dibutyl stannane adds said mixture to, reacts 36h and be down to room temperature and obtain white in the oil bath of 50 DEG C
Color crystalline precipitation eight chloropropyl silsesquioxane POSS-Cl；
Alkali ionic liquid immobilized: in three neck round bottom flask, the POSS-Cl of 0.15g is dissolved in 25ml
Dimethylformamide, and it is slowly added dropwise N-Methylimidazole. 0.08mol, it is warming up to 60 DEG C under magnetic agitation, drips
After adding, continuing to be stirred at reflux 24h, reduce pressure sucking filtration, and ethyl acetate washs 3 times to obtain white solid, finally
At 65 DEG C, it is vacuum dried 24h, obtains presoma.The KOH taking 1g adds 50ml single necked round bottom flask
In, and adding 15ml dimethylformamide, stirring at normal temperatures makes it dissolve, and is dividedly in some parts 0.2g forerunner
Body, under magnetic stirring room temperature reaction 3h, then in bottle, add 6ml ether, continue at room temperature to react
24h, stopped reaction, rotation is evaporated off solvent, obtains solid catalyst imidazoles based on POSS alkali ion liquid
Body.
[embodiment 2]
In the case of the preparation condition of catalyst is identical with embodiment 1, only by the N-in preparation method
Methylimidazole. changes N-ethyl imidazol(e) into, obtains imidazoles alkaline ionic liquid catalyst based on POSS.
[embodiment 3]
In the case of the preparation condition of catalyst is identical with embodiment 1, only by the N-in preparation method
Methylimidazole. changes N-isopropylimdazole into, obtains imidazoles alkaline ionic liquid catalyst based on POSS.
[embodiment 4]
In the case of the preparation condition of catalyst is identical with embodiment 1, only by the N-in preparation method
Methylimidazole. changes N-allyl imidazole into, obtains imidazoles alkaline ionic liquid catalyst based on POSS.
[reaction embodiment 5-8]
In 1L reactor, add reactant 9.2g glycerol and 60.8g dimethyl carbonate, add 3.5g base
In the imidazoles alkaline ionic liquid catalyst of POSS, being 100 DEG C in reaction temperature, pressure is 2Mpa, stirs
Mixing under the conditions of speed is 800rpm, the response time is 6h.With carbonic acid glyceride selectivity and yield as index,
Gained reactivity worth is as shown in table 1.
The reaction result of table 1 imidazoles based on POSS alkaline ionic liquid catalyst carbonate synthesis glyceride
[reaction embodiment 9]
The recycling performance of imidazoles alkaline ionic liquid catalyst based on POSS.
In 1L reactor, add reactant 9.2g glycerol and 60.8g dimethyl carbonate, add 3.5g base
In the imidazoles alkaline ionic liquid catalyst of POSS, being 100 DEG C in reaction temperature, pressure is 2Mpa, stirs
Mixing under the conditions of speed is 800rpm, the response time is 6h.By catalyst filtration after reaction, 90 DEG C of dry 4h,
By recycled for this catalyst, with carbonic acid glyceride selectivity and yield as index, gained reactivity worth is such as
Shown in table 2.
The recycling performance of table 2 imidazoles based on POSS alkaline ionic liquid catalyst
Claims (3)
1. a preparation method for the alkaline ionic liquid catalyst based on POSS of carbonate synthesis glyceride,
It is characterized in that including procedure below,
(1) preparation of POSS-Cl: take methanol 100～200ml, concentrated hydrochloric acid 5～15ml adds there-necked flask
In, and 3-chloropropyl triethoxysilane 10～20g is dropwise added drop-wise in above-mentioned solution, mechanical agitation 30～50h
After, add condensation catalyst 0.1～0.2g dibutyl stannane to said mixture, in the oil bath of 40～60 DEG C
Room temperature is down in middle reaction 30～50h, obtains white crystalline precipitation eight chloropropyl silsesquioxane POSS-Cl；
(2) alkali ionic liquid is immobilized: be dissolved in by 0.1～0.3g POSS-Cl in three neck round bottom flask
20～30ml dimethylformamides, and it is slowly added dropwise the N-alkyl imidazole of 0.08～0.1mol, under magnetic agitation
Being warming up to 60～75 DEG C, drip and complete continue to be stirred at reflux 18～32h, reduce pressure sucking filtration, ethyl acetate washing 2～5
The secondary white solid that obtains, is finally vacuum dried 18～32h at 60～90 DEG C, obtains presoma, take 0.8～2g KOH
Adding in 50ml single necked round bottom flask, and add 10～20ml dimethylformamides, stirring at normal temperatures makes it
Dissolve, be dividedly in some parts above-mentioned presoma 0.1～0.3g, room temperature reaction 2～5h under magnetic stirring, then in bottle
Adding 4～8ml ether, continue at room temperature reaction 18～32h, stopped reaction, rotation is evaporated off solvent, obtains
Solid catalyst imidazoles based on POSS alkali ionic liquid.
2. alkali ionic liquid based on the POSS catalysis of the carbonate synthesis glyceride as described in claim 1
The preparation method of agent, it is characterised in that above-mentioned N-alkyl imidazole is N-Methylimidazole., N-ethyl imidazol(e) or N-
Any one of isopropylimdazole.
3. the catalyst that the preparation method of the catalyst as described in claim 1 obtains is for catalyzing and synthesizing carbonic acid
The technique of glyceride, it is characterised in that include procedure below:
(1) glycerol and dimethyl carbonate are added in reactor according to mol ratio 1: 5～1: 15, add
Quality is 1～the alkaline ionic liquid catalyst based on POSS of 10% of reactant gross mass, in reaction temperature
Degree is 50～200 DEG C, and pressure is 1～3MPa, under the conditions of stir speed (S.S.) is 500～1200rpm, and the response time
It is 1～10h, obtains the mixture containing carbonic acid glyceride；
(2) filtering step (1) mixture, the solid catalyst leached continues cycling through use.
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| CN109575292B (en) * | 2017-09-29 | 2021-05-11 | 中国石油化工股份有限公司 | Ion exchange resin and use thereof |
| CN109575295B (en) * | 2017-09-29 | 2021-05-11 | 中国石油化工股份有限公司 | Method for catalytic hydration of alkylene oxides |
| CN109574794B (en) * | 2017-09-29 | 2021-05-11 | 中国石油化工股份有限公司 | Method for producing ethylene glycol by catalytic hydration of alkylene oxide |
| CN109574793B (en) * | 2017-09-29 | 2021-05-28 | 中国石油化工股份有限公司 | Method for preparing glycol by hydrating alkylene oxide |
| CN109574807B (en) * | 2017-09-29 | 2021-05-11 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol by catalytic hydration of alkylene oxide |
| CN109517176A (en) * | 2018-12-11 | 2019-03-26 | 怀化学院 | Silsesquioxane ionic liquid and preparation method thereof |
| CN110467730B (en) * | 2019-09-10 | 2021-06-01 | 哈尔滨工业大学 | Synthetic method of octachloropropyl POSS |
| CN112619705B (en) * | 2019-09-24 | 2023-08-04 | 中国石油化工股份有限公司 | Alkylene oxide addition reaction catalyst and application thereof |
| CN115490864B (en) * | 2022-09-29 | 2023-08-15 | 长兴化学（天津）有限公司 | POSS hybridized waterborne polyurethane emulsion and preparation method and application thereof |
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| CN102250051A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Preparation method of glycerol carbonate |
| CN103212445A (en) * | 2013-04-10 | 2013-07-24 | 江南大学 | Basic ionic liquid modified magnetic nanoparticle catalyst for synthesizing biodiesel and preparation method thereof |
| CN103588808A (en) * | 2013-11-08 | 2014-02-19 | 复旦大学 | Polyhedral oligomeric silsesquioxane (POSS)-based solid ionic liquid, and preparation method and application thereof |
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|---|---|---|---|---|
| CN102250051A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Preparation method of glycerol carbonate |
| CN103212445A (en) * | 2013-04-10 | 2013-07-24 | 江南大学 | Basic ionic liquid modified magnetic nanoparticle catalyst for synthesizing biodiesel and preparation method thereof |
| CN103588808A (en) * | 2013-11-08 | 2014-02-19 | 复旦大学 | Polyhedral oligomeric silsesquioxane (POSS)-based solid ionic liquid, and preparation method and application thereof |
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