CN107297222A - A kind of preparation of poly ion liquid solid acid catalyst and its application process - Google Patents
A kind of preparation of poly ion liquid solid acid catalyst and its application process Download PDFInfo
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- CN107297222A CN107297222A CN201710447667.XA CN201710447667A CN107297222A CN 107297222 A CN107297222 A CN 107297222A CN 201710447667 A CN201710447667 A CN 201710447667A CN 107297222 A CN107297222 A CN 107297222A
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
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- C07C2/70—Catalytic processes with acids
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A kind of preparation of poly ion liquid solid acid catalyst and its application process, it is related to a kind of ortho-xylene that is used for and prepares poly ion liquid solid acid catalyst of diarylethane and preparation method thereof with alkylated styrene reaction, the catalyst has higher alkylation conversion ratio, diarylethane yield and reusability under high temperature, normal pressure.The catalyst is will first to contain vinyl imidazole class monomer, N, N methylene-bisacrylamides crosslinking agent, initiator and dispersant obtain presoma porous polymer by hydro-thermal reaction, and gained presoma porous polymer adds halogenated alkane and strong acid react obtaining poly ion liquid catalyst.
Description
Technical field
The present invention relates to a kind of polyion liquid that diarylethane is prepared for ortho-xylene and alkylated styrene reaction
Body solid acid catalyst technology of preparing, belongs to industrial catalysis technical field.
Background technology
Diarylethane (1- phenyl -1- xylyl ethanes) is referred to as PXE, is to be developed by Japan and the United States the seventies in last century
What is gone out a kind of can substitute the product of askarel type power capacitor impregnating agent.The 1- phenyl that styrene is synthesized with dimethylbenzene-
1- xylyl ethanes (1-pHenyl-1-xylyelthane, abbreviation PXE), it has higher boiling, low viscosity, freezing point relatively low
The features such as, the solvent of NCR pressure sensitive dye is widely applied to, is added in addition, it also acts as organic heat-carrying agent, plastics
Plasticizer and lubricating oil of work etc..
Traditionally synthesis PXE reaction is directly to be used as acid catalyst by the use of the concentrated sulfuric acid.It is with the advantage of the concentrated sulfuric acid
Its is cheap and easy to get, acid strong.And the shortcoming of sulphuric acid catalysis is its strong corrosivity and oxidisability, its reaction condition is difficult to control
System, low yield, spent acid handle difficulty, to production equipment seriously corroded etc..
Solid acid catalyst is increasingly valued by people as a kind of new green environment protection type catalyst.Patent USA
3069478 (1962), use acid clay；JP 63238028 (1988), uses Y shape zeolite；EP-A-421340, is boiled using L
Stone；And the A of CN 101898931 (2010), use Al-MCM-41 molecular sieves.PXE yields are all less in above-mentioned all synthetic methods
Ideal, and solid acid catalyst preparation technology is complicated, expensive and needs frequent regeneration in process of production, and this is just hampered
Its further industrialization is hindered.
Increasing research shows to be urged with traditional liquid Bronsted acid is substituted with ionic liquid acid Lewis
Agent carries out catalysis Friedel-Crafts reaction.The A of patent CN 102603451 (2012) report using the concentrated sulfuric acid and ionic liquid mixed liquor as
Acidic catalyst reacts to be catalyzed the Friedel-Crafts of dimethylbenzene (or ethane) and styrene.However, research is more to have height
Although the chloro-aluminate type ionic liquid of catalytic activity is applied to catalytic reaction in the lab, this ionic liquid is to sky
Steam in gas is very sensitive, it is necessary to used under conditions of absolute, thus is also unfavorable for industrialized production.Therefore prepare
Efficiently, noresidue, environment-friendly solid acid catalyst substitution concentrated sulfuric acid catalyst have important theory significance and larger
Application value.
The content of the invention
Technical problem：It is an object of the invention to provide a kind of poly ion liquid solid acid of catalytic synthesis of diaryl ethane
Catalyst and preparation method thereof.The catalyst in the alkylated reaction of ortho-xylene and styrene there is higher alkylation to turn
Rate and diarylethane yield, catalyst are easily separated, are difficult to remain in the product, corrosivity is small, environment-friendly.
Technical scheme：The present invention is a kind of preparation method of poly ion liquid solid acid catalyst, the preparation of the catalyst
Method is will first to pass through containing vinyl imidazole class monomer, N,N methylene bis acrylamide crosslinking agent, initiator and dispersant
Hydro-thermal reaction obtains presoma porous polymer, and gained presoma porous polymer adds halogenated alkane and strong under the conditions of lucifuge
Acid react obtaining poly ion liquid catalyst.
The preparation method of the catalyst is specially：
N,N-dimethylformamide is added to vinyl imidazole class monomer and N,N methylene bis acrylamide by step a)
In crosslinking agent and the mixture of initiator azodiisobutyronitrile, it is stirred continuously until that solid is completely dissolved, then 80~120
Continue at DEG C after hydro-thermal reaction, suction filtration, drying precipitate obtains white or faint yellow presoma porous polymer solid；
Absolute ethyl alcohol is added the presoma porous polymer solid that step a) is obtained by step b), until solid is completely molten
Solution, then adds halogenated alkane and continues to react, be evaporated at 60~100 DEG C, dry, obtain the polyion liquid of different cation chain lengths
Body；
Step c) are by the poly ion liquid of the obtained different cation chain lengths of step b) with 1mmol/L~30mmol/L's
After strong acid toluene solution dipping, suction filtration, sediment is washed after multiple times of filtration with a large amount of ether, product vacuum drying, you can obtain two
The poly ion liquid solid acid catalyst of aryl-ethane.
Wherein：
Step a) initial reaction temperature is 5~30 DEG C；Step b) initial reaction temperature is 5~30 DEG C；Step c's)
Initial reaction temperature is 20~30 DEG C.
Step a) drying precipitate temperature is 80~120 DEG C；Step b) drying temperature is 80~120 DEG C；Step c)
Product vacuum drying temperature be 40~50 DEG C.
The mass percent of the monomer of class containing vinyl imidazole and N,N methylene bis acrylamide crosslinking agent is 1:4~1:2.
The described monomer of class containing vinyl imidazole is 1- vinyl imidazoles, 2- methyl isophthalic acids-vinyl imidazole or 2- ethyls -1-
One kind in vinyl imidazole.
Described halogenated alkane is one kind in N- Hexyl Bromide, propane sultone, iodomethane or n-bromide butane.
Described strong acid is one kind in trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid or acrylic acid.
The catalyst of the present invention is that solid acid catalyst is used for the alkylated reaction of ortho-xylene and styrene, is urged
Diarylethane is combined to, after reaction terminates, suction filtration can obtain product through vacuum distillation, and catalyst is reusable.
Beneficial effect：The present invention provides a kind of system of the poly ion liquid solid acid catalyst of catalytic synthesis of diaryl ethane
Preparation Method, the catalyst has higher alkylation conversion ratio and diarylethane yield, reaction stability under high temperature, normal pressure
It is good, the catalyst reaction better performances after iterative regenerable, and regeneration.
The present invention compared with concentrated sulfuric acid catalyst, solid acid catalyst compared with chlorine aluminic acid type ionic-liquid catalyst,
Its superior effect is that catalyst activity height, the alkylation conversion ratio of styrene can reach 100%, diarylethane high income
Up to 94%, and post catalyst reaction is easily separated, is difficult to remain in the product, corrosivity is small, environment-friendly, with preferable economy
And social benefit.
Embodiment
The following examples can make those skilled in the art that the present invention is more fully understood, but not limit in any way
The present invention.
Embodiment 1:
1.68g crosslinking agents N,N methylene bis acrylamide, 0.50g 2- methyl isophthalic acids-vinyl imidazole and 0.025g trigger
After agent azodiisobutyronitrile (AIBN) mixing, said mixture is dissolved into 25ml DMFs, 20 DEG C of stirrings
3h, at 120 DEG C after hydro-thermal reaction 48h, suction filtration, sediment obtains faint yellow presoma porous polymer and consolidated in 120 DEG C of dry 12h
Body.By above-mentioned faint yellow presoma porous polymer solid dissolving in 30ml absolute ethyl alcohol, 20 DEG C of stirring 3h continue to add
Enter 3ml propane sultones to continue to react after 48h, be evaporated at 60 DEG C, 80 DEG C of dry 12h obtain the polyion of different cation chain lengths
Liquid.The poly ion liquid of different cation chain lengths obtained above is soaked at 30 DEG C with 10mmol/L sulfuric acid toluene solution
After stain 24h, suction filtration, sediment is washed after multiple times of filtration with a large amount of ether, and product is at 40 DEG C after vacuum drying 8h, you can obtained sour
Property polymeric ionic liquid solid acid catalyst.
45g neighbour two is added into the 250mL four-hole boiling flasks equipped with agitator, condenser pipe, thermometer and constant pressure funnel
Toluene and the acid poly ion liquid catalyst of 0.2g, are heated to reflux, reaction temperature is 80 DEG C, is then slowly added dropwise under agitation
The mixed liquor of 90g ortho-xylenes and 18g styrene, is dripped off for 2 hours, continues to react 4 hours.After reaction terminates, room temperature is cooled to,
Stand, filtering, filtrate decompression distillation first boils off ortho-xylene, obtains crude product.Weigh, sample mark.Crude product gas-chromatography
Instrument is analyzed, and the yield that the alkylation conversion ratio for obtaining styrene is respectively 100%, diarylethane is 93.2%.
The catalyst of above-mentioned recovery is dried after 48h at 80 DEG C, it is reusable.Continue to equipped with agitator, condensation
Added in pipe, the 250mL four-hole boiling flasks of thermometer and constant pressure funnel above restored acid poly ion liquid catalyst and
45g ortho-xylenes, are heated to reflux, and reaction temperature is 80 DEG C, and 90g ortho-xylenes and 15g benzene second are then slowly added dropwise under agitation
The mixed liquor of alkene, is dripped off for 2 hours, continues to react 4 hours.After reaction terminates, room temperature is cooled to, is stood, filtering, filtrate decompression is steamed
Evaporate, first boil off ortho-xylene, obtain crude product.Weigh, sample mark.Crude product chromatographic, obtains the alkane of styrene
The yield that base conversion ratio is respectively 100%, diarylethane is 91.8%.
Embodiment 2:
1.68g crosslinking agents N,N methylene bis acrylamide, 0.68g 1- vinyl imidazoles and 0.007g initiator azos
After bis-isobutyronitrile (AIBN) mixing, said mixture is dissolved into 25ml DMFs, 20 DEG C are stirred 3h, 120
At DEG C after hydro-thermal reaction 12h, suction filtration, sediment obtains faint yellow presoma porous polymer solid in 120 DEG C of dry 12h.Will be upper
The faint yellow presoma porous polymer solid dissolving stated is in 30ml absolute ethyl alcohol, and 20 DEG C of stirring 3h are continuously adding 3ml just
Bromohexane continues to react after 24h, is evaporated at 60 DEG C, 80 DEG C of dry 12h obtain the poly ion liquid of different cation chain lengths.Will be upper
The poly ion liquid for stating obtained different cation chain lengths is impregnated with 3mmol/L trifluoromethanesulfonic acid toluene solution at 30 DEG C
After 48h, suction filtration, sediment is washed after multiple times of filtration with a large amount of ether, and product is at 40 DEG C after vacuum drying 8h, you can obtained acid
Polymeric ionic liquid solid acid catalyst.
45g neighbour two is added into the 250mL four-hole boiling flasks equipped with agitator, condenser pipe, thermometer and constant pressure funnel
Toluene and the acid poly ion liquid catalyst of 1.5g, are heated to reflux, reaction temperature is 80 DEG C, is then slowly added dropwise under agitation
The mixed liquor of 90g ortho-xylenes and 18g styrene, is dripped off for 2 hours, continues to react 4 hours.After reaction terminates, room temperature is cooled to,
Stand, filtering, filtrate decompression distillation first boils off ortho-xylene, obtains crude product.Weigh, sample mark.Crude product gas-chromatography
Instrument is analyzed, and the yield that the alkylation conversion ratio for obtaining styrene is respectively 100%, diarylethane is 94.0%.
The catalyst of above-mentioned recovery is dried after 48h at 120 DEG C, it is reusable.Continue to equipped with agitator, condensation
The acid polyion after 3 recovery is reused more than being added in the 250mL four-hole boiling flasks of pipe, thermometer and constant pressure funnel
Liquid catalyst and 45g ortho-xylenes, are heated to reflux, and reaction temperature is 80 DEG C, and the adjacent diformazans of 90g are then slowly added dropwise under agitation
The mixed liquor of benzene and 12g styrene, is dripped off for 2 hours, continues to react 4 hours.After reaction terminates, room temperature is cooled to, is stood, mistake
Filter, filtrate decompression distillation, first boils off ortho-xylene, obtains crude product.Weigh, sample mark.Crude product chromatographic,
The yield that the alkylation conversion ratio for obtaining styrene is respectively 98%, diarylethane is 89.8%.
Embodiment 3:
1.68g crosslinking agents N,N methylene bis acrylamide, 0.76g 2- ethyl -1- vinyl imidazoles and 0.07g trigger
After agent azodiisobutyronitrile (AIBN) mixing, said mixture is dissolved into 30ml DMFs, 20 DEG C of stirrings
3h, at 120 DEG C after hydro-thermal reaction 24h, suction filtration, sediment obtains faint yellow presoma porous polymer and consolidated in 120 DEG C of dry 12h
Body.By above-mentioned faint yellow presoma porous polymer solid dissolving in 30ml absolute ethyl alcohol, 20 DEG C of stirring 3h continue to add
Enter 3ml iodomethane to continue to react after 24h, be evaporated at 60 DEG C, 80 DEG C of dry 12h obtain the poly ion liquid of different cation chain lengths.
The poly ion liquid of different cation chain lengths obtained above is impregnated at 30 DEG C with 15mmol/L acrylic acid toluene solution
After 48h, suction filtration, sediment is washed after multiple times of filtration with a large amount of ether, and product is at 40 DEG C after vacuum drying 8h, you can obtained acid
Polymeric ionic liquid solid acid catalyst.
45g neighbour two is added into the 250mL four-hole boiling flasks equipped with agitator, condenser pipe, thermometer and constant pressure funnel
Toluene and the acid poly ion liquid catalyst of 3.1g, are heated to reflux, reaction temperature is 80 DEG C, is then slowly added dropwise under agitation
The mixed liquor of 90g ortho-xylenes and 18g styrene, is dripped off for 2 hours, continues to react 4 hours.After reaction terminates, room temperature is cooled to,
Stand, filtering, filtrate decompression distillation first boils off ortho-xylene, obtains crude product.Weigh, sample mark.Crude product gas-chromatography
Instrument is analyzed, and the yield that the alkylation conversion ratio for obtaining styrene is respectively 100%, diarylethane is 93.5%.
The catalyst of above-mentioned recovery is dried after 48h at 120 DEG C, it is reusable.Continue to equipped with agitator, condensation
The acid polyion after 5 recovery is reused more than being added in the 250mL four-hole boiling flasks of pipe, thermometer and constant pressure funnel
Liquid catalyst and 45g ortho-xylenes, are heated to reflux, and reaction temperature is 80 DEG C, and the adjacent diformazans of 90g are then slowly added dropwise under agitation
The mixed liquor of benzene and 12g styrene, is dripped off for 2 hours, continues to react 4 hours.After reaction terminates, room temperature is cooled to, is stood, mistake
Filter, filtrate decompression distillation, first boils off ortho-xylene, obtains crude product.Weigh, sample mark.Crude product chromatographic,
The yield that the alkylation conversion ratio for obtaining styrene is respectively 98%, diarylethane is 86.8%.
Claims (9)
1. a kind of preparation method of poly ion liquid solid acid catalyst, it is characterised in that the preparation method of the catalyst is first will
Obtained containing vinyl imidazole class monomer, N,N methylene bis acrylamide crosslinking agent, initiator and dispersant by hydro-thermal reaction
To presoma porous polymer, gained presoma porous polymer adds halogenated alkane under the conditions of lucifuge and strong acid is reacted
Obtain poly ion liquid catalyst.
2. the preparation method of a kind of poly ion liquid solid acid catalyst according to claims 1, it is characterised in that should
The preparation method of catalyst is specially：
N,N-dimethylformamide is added to step a) into vinyl imidazole class monomer and N,N methylene bis acrylamide is crosslinked
In the mixture of agent and initiator azodiisobutyronitrile, it is stirred continuously until that solid is completely dissolved, then at 80~120 DEG C
Continue after hydro-thermal reaction, suction filtration, drying precipitate obtains white or faint yellow presoma porous polymer solid；
Absolute ethyl alcohol is added the presoma porous polymer solid that step a) is obtained by step b), until solid is completely dissolved, so
Halogenated alkane is added afterwards to continue to react, and is evaporated at 60~100 DEG C, is dried, obtain the poly ion liquid of different cation chain lengths；
Step c) are by poly ion liquid 1mmol/L~30mmol/L of the obtained different cation chain lengths of step b) strong acid
After toluene solution dipping, suction filtration, sediment is washed after multiple times of filtration with a large amount of ether, product vacuum drying, you can obtain diaryl
The poly ion liquid solid acid catalyst of ethane.
3. a kind of preparation method of poly ion liquid solid acid catalyst according to claims 2, it is characterised in that step
Suddenly initial reaction temperature a) is 5~30 DEG C；Step b) initial reaction temperature is 5~30 DEG C；Step c) initial reaction temperature
Spend for 20~30 DEG C.
4. a kind of preparation method of poly ion liquid solid acid catalyst according to claims 2, it is characterised in that step
Suddenly drying precipitate temperature a) is 80~120 DEG C；Step b) drying temperature is 80~120 DEG C；Step c) product vacuum
The temperature of drying is 40~50 DEG C.
5. a kind of preparation method of poly ion liquid solid acid catalyst according to claims 1 or 2, its feature exists
In the mass percent of the monomer of class containing vinyl imidazole and N, N- methylene-bisacrylamide crosslinking agent is 1:4~1:2.
6. a kind of preparation method of poly ion liquid solid acid catalyst according to claims 1 or 2, its feature exists
In the described monomer of class containing vinyl imidazole is 1- vinyl imidazoles, 2- methyl isophthalic acids-vinyl imidazole or 2- ethyl -1- ethene
One kind in base imidazoles.
7. a kind of preparation method of poly ion liquid solid acid catalyst according to claims 1 or 2, its feature exists
In described halogenated alkane is one kind in N- Hexyl Bromide, propane sultone, iodomethane or n-bromide butane.
8. a kind of preparation method of poly ion liquid solid acid catalyst according to claims 1 or 2, its feature exists
In described strong acid is one kind in trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid or acrylic acid.
9. a kind of application of such as acid catalyst prepared by the method for claims 1 or 2, it is characterised in that the described catalyst
It is used for the alkylated reaction of ortho-xylene and styrene for solid acid catalyst, catalytic synthesis of diaryl ethane is reacted after terminating,
Suction filtration, product can be obtained through vacuum distillation, and catalyst is reusable.
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| CN108579807A (en) * | 2018-05-21 | 2018-09-28 | 江苏棋成化工有限公司 | A kind of cross-linked polymeric acidic ion liquid alkylation catalyst and preparation method thereof |
| CN108620124A (en) * | 2018-05-24 | 2018-10-09 | 绍兴文理学院 | A kind of porous polymer solid acid catalyst for alkynes hydration reaction |
| CN109569730A (en) * | 2018-11-27 | 2019-04-05 | 江苏师范大学 | A kind of catalyst and its application |
| CN109939731A (en) * | 2019-03-20 | 2019-06-28 | 合肥学院 | One kind being used for normal pressure CO2The mesoporous poly ion liquid catalyst of cycloaddition reaction, preparation method and application |
| CN110354899A (en) * | 2019-08-22 | 2019-10-22 | 华东师范大学 | A kind of solid acid catalyst and preparation method and the application in epoxide hydration |
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| CN109939731A (en) * | 2019-03-20 | 2019-06-28 | 合肥学院 | One kind being used for normal pressure CO2The mesoporous poly ion liquid catalyst of cycloaddition reaction, preparation method and application |
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| CN110354899A (en) * | 2019-08-22 | 2019-10-22 | 华东师范大学 | A kind of solid acid catalyst and preparation method and the application in epoxide hydration |
| CN110787841A (en) * | 2019-11-15 | 2020-02-14 | 中国科学院武汉物理与数学研究所 | Super-strong solid acid material containing nitrogen MOFs and application thereof |
| CN111013657A (en) * | 2019-12-27 | 2020-04-17 | 常州大学 | Polymeric ionic liquid solid acid catalyst for catalyzing esterification reaction of trimethylolpropane and oleic acid and preparation method thereof |
| CN111013657B (en) * | 2019-12-27 | 2023-03-21 | 常州大学 | Polymeric ionic liquid solid acid catalyst for catalyzing esterification reaction of trimethylolpropane and oleic acid and preparation method thereof |
| CN112374978A (en) * | 2020-10-16 | 2021-02-19 | 宁波保税区华萌生物科技有限公司 | Preparation method of phenylacetic acid |
| CN113042099A (en) * | 2021-03-19 | 2021-06-29 | 江南大学 | Solid acid catalyst for catalytic esterification synthesis of gallic acid ester |
| CN113042099B (en) * | 2021-03-19 | 2022-06-07 | 江南大学 | Solid acid catalyst for catalytic esterification synthesis of gallic acid ester |
| CN115888824A (en) * | 2022-10-27 | 2023-04-04 | 惠州市绿色能源与新材料研究院 | Method for catalytically synthesizing carbonic ester by amide functionalized polymerized ionic liquid |
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| CN107297222B (en) | 2020-03-31 |
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