CN104530290A - Polystyrene-supported nitrogen heterocyclic ring material as well as preparation method and application thereof - Google Patents
Polystyrene-supported nitrogen heterocyclic ring material as well as preparation method and application thereof Download PDFInfo
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- CN104530290A CN104530290A CN201510024809.2A CN201510024809A CN104530290A CN 104530290 A CN104530290 A CN 104530290A CN 201510024809 A CN201510024809 A CN 201510024809A CN 104530290 A CN104530290 A CN 104530290A
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- polystyrene
- heterocyclic ring
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Abstract
The invention discloses a polystyrene-supported nitrogen heterocyclic ring material and a preparation method thereof. A series of nitrogen heterocyclic ring materials are supported on chloromethylated polystyrene by use of a group grafting method and applied to the addition reaction of CO2 and epoxides. High selectivity and high conversion rate of the synthesis of cyclic carbonates are realized by virtue of the structure matching relationship between active group nitrogen heterocyclic rings and reactants, and the process is similar to the DNA assembling process. The synthesis method has the characteristics of simple and convenient catalyst synthesis, no introduction of metal salts, low pollution on the environment due to pure organic materials, high activity, high selectivity, multiple repeated utilization, high heat stability, long service life, easy product separation and catalyst recovery, and the like.
Description
Technical field
The present invention relates to organic catalysis synthesis field, particularly relate to a kind of loaded by polystyrene nitrogen heterocyclic ring catalytic material and preparation method thereof, and at CO
2with the application in the cycloaddition reaction of epoxide.
Background technology
Under low-carbon economy guides, as large, nontoxic, reproducible carbon resource, CO
2chemical as eco-friendly C1 construction unit synthesis high added value has huge magnetism.CO
2catalyzed conversion become and construct the important ring of global carbon.In recent years, CO
2study the most successfully CO with the cycloaddition reaction of propylene oxide
2transform one of example.Reaction is relatively easily carried out, and no matter product is propylene carbonate or poly-propylene carbonate, all has good application prospect.This reaction itself does not generate other by product, and Atom economy is good, meets green chemical concept, is specially adapted to large CO
2conversion.
Because ionic liquid is to CO
2there are good absorptive character, at CO
2also appear in the newspapers repeatly in catalyzed conversion, its active ingredient is nitrogen-containing heterocycle compound.For fear of the liquidus behavior of ionic liquid, it is immobilized is applied to heterogeneous catalysis and plays an important role to operations such as simplification later separation recovery.At present, ionic liquid is mainly concentrated both ways the research of this reaction: be carried out by the nucleophilic attack of Lewis acid metal compound coordination activation and Lewis basic ion liquid on the one hand simultaneously, realize the open loop to epoxide of soda acid synergistic effect, particularly halogen to play an important role; On the other hand, when not introducing metallic compound, can promote that reaction is carried out equally by grafted functional group on imidazole ring, as carboxyl and alcohol radical etc., hydrogen bond is conducive to intensifier ring addition reaction.Chinese patent CN200810102533 discloses a kind of method of preparing cyclic carbonates from carrying hydroxyl ionic liquid, just based on the effect of halogen and hydroxyl; Chinese patent CN201110275209 then introduces carboxyl in imidazole salts.Aforesaid method process is comparatively complicated, and makes catalyst stability poor due to the grafting load of unnecessary group, and easily come off, catalytic efficiency is low.
Summary of the invention
The object of the present invention is to provide a kind of loaded by polystyrene nitrogen heterocyclic ring catalytic material and preparation method thereof, and be applied to CO
2with the addition reaction of epoxide, the catalysis assembling concept being similar to DNA assembling is proposed.
The technical solution adopted for the present invention to solve the technical problems is: a kind of loaded by polystyrene nitrogen heterocyclic ring material structure formula is as follows:
Wherein R is nitrogen heterocyclic ring, include five-membered ring imidazoles (Im), Methylimidazole (Mim), the one in hexa-member heterocycle piperazine (Pi), pyrazine (Pz), pyrimidine (Pim), fused heterocycle benzoglyoxaline, VITAMIN B4 and guanine.
A kind of preparation method of above-mentioned loaded by polystyrene nitrogen heterocyclic ring material comprises the following steps:
1) to carry out constant temperature in a solvent swelling for Chloromethyl polystyrene;
2) in the Chloromethyl polystyrene solution in swelling, add nitrogen heterocyclic ring material and alkaline additive, under condensing reflux, constant temperature stirs for some time;
3) room temperature is cooled to reacted sample, carries out successively filtering, wash, vacuum-drying, obtained loaded by polystyrene nitrogen heterocyclic ring material.
Loaded by polystyrene nitrogen heterocyclic ring materials synthesis route is as follows:
Wherein, circle represents polystyrene-divinylbenzene resin backbone structure.
Preferably, in step 1) in, the selection of described solvent is from deionized water (H
2o), ethanol (EtOH), acetonitrile (MeCN), DMF (DMF), N,N-dimethylacetamide (DMA), tetrahydrofuran (THF) (THF) and acetone (Me
2cO) one, in ethylene dichloride (DCE), normal hexane, toluene (PhMe), ethyl acetate or its combination.
Preferably, in step 1) in, swelling temperature is 25-100 DEG C, and swelling time is 1-5h.
Preferably, in step 2) in, temperature of reaction is 60-120 DEG C, and the reaction times is 1-3d.
Preferably, in step 2) in, described alkaline additive is selected from sodium hydroxide (NaOH), sodium hydride (NaH), sodium bicarbonate (NaHCO
3), sodium ethylate (CH
3cH
2oNa), tert-butyl lithium ((CH
3)
3cLi), lithium diisopropylamine (LDA) and two trimethyl silicon based ammonification sodium (NaN (SiMe
3)
2) in one or its combination.
Preferably, step 3) be after filtration after ethyl acetate and methyl alcohol are washed, vacuum-drying 3-6h at 90-120 DEG C.
Above-mentioned loaded by polystyrene nitrogen heterocyclic ring material is as CO
2application with the catalyzer of epoxide addition reaction, relates to CO
2as follows with the addition reaction route of epoxide:
Concrete grammar comprises the following steps: in reactor, drop into propylene oxide and described catalyzer, dress still; CO is added under room temperature
2gas; Heated and stirred makes it react; With cold hydrazine, reactor is cooled to less than 20 DEG C, residue CO in emptying still
2gas makes temperature in the kettle be plummeted to 0 DEG C; Filtering catalyst.
Preferably, described temperature of reaction is 60-140 DEG C, and reaction pressure is 1-5MPa, and the reaction times is 3-15h, and the catalyst levels of every milliliter of propylene oxide is 15-100mg.
The invention has the beneficial effects as follows:
1, describe a kind of method of synthesizing the strong basic resin of thermostability, wherein, loaded by polystyrene imidazoles material thermostability is up to nearly 400 DEG C, and common quaternary ammonium salt ion exchange resin thermostability is less than 150 DEG C.
2, based on the structure matching relation between this catalyst body of different nitrogen heterocyclic ring and this catalysis object of reactant:
Screening is for CO
2with the effective catalyst of epoxide addition reaction, five yuan of imidazole salts of loaded by polystyrene are proposed to CO
2the catalysis assembling concept of cycloaddition reaction, has original and important research and practical value.
3, synthesize easy, do not introduce metal-salt, environmental pollution is less, active high, selectivity is high, can repeatedly reuse, thermostability is high, long service life, product separation and catalyst recovery easy.
Below in conjunction with drawings and Examples, the present invention is described in further detail; But a kind of loaded by polystyrene nitrogen heterocyclic ring catalytic material of the present invention and its preparation method and application is not limited to embodiment.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of loaded by polystyrene imidazole salts, and X-coordinate is wave number wave number/cm
-1, curve a is imidazoles (Im), curve b is Chloromethyl polystyrene (PS-CH
2-Cl), curve c is loaded by polystyrene imidazoles (PS-Im), curve d is loaded by polystyrene Methylimidazole (PS-Mim).
Fig. 2 is a series of nitrogenous heterocyclic thermal multigraph of loaded by polystyrene, X-coordinate is temperature T/ DEG C, ordinate zou is rate of weight loss TG/%, curve a is loaded by polystyrene imidazoles (PS-Im), b is loaded by polystyrene pyrazine (PS-Pz), c is loaded by polystyrene piperazine (PS-Pi), d is loaded by polystyrene pyrimidine (PS-Pim), e is loaded by polystyrene Methylimidazole (PS-Min), f is loaded by polystyrene VITAMIN B4 (PS-Ad).
Embodiment
Embodiment 1
The impact of the selection p-poly-phenyl ethene load Methylimidazole synthesis of solvent:
1) Chloromethyl polystyrene (1%DVB, 1g, 4.1mmol cl content) swell in solvent selected by 50mL, comprise acetonitrile (MeCN), DMF (DMF), tetrahydrofuran (THF) (THF) and acetone (Me
2cO), constant temperature 50 DEG C stirs 2h.
2) add N-Methylimidazole (0.4g) and NaH (0.2g), be heated to 80 DEG C, condensing reflux, constant temperature stirs two days.
3) reaction terminates, cool to room temperature, and successively through filtration, ethyl acetate washing and methanol wash, product is vacuum-drying 4h at 110 DEG C, is designated as PS-Mim.
Under different solvents, the grafting amount of Methylimidazole on Chloromethyl polystyrene is if table 1 is as shown:
The selection of table 1. solvent is on the impact of Methylimidazole grafting amount on Chloromethyl polystyrene
Embodiment 2
The impact of different additive p-poly-phenyl ethene load Methylimidazole synthesis:
1) Chloromethyl polystyrene (1%DVB, 1g, 4.1mmol cl content) swells in 50mL acetonitrile, and constant temperature 50 DEG C stirs 2h.
2) add N-Methylimidazole (0.4g) and selected additive, selected additive comprises sodium hydroxide (NaOH), sodium hydride (NaH), sodium bicarbonate (NaHCO
3), two trimethyl silicon based ammonification sodium (NaN (SiMe
3)
2), be heated to 80 DEG C, condensing reflux, constant temperature stirs two days.
3) reaction terminates, cool to room temperature, and successively through filtration, ethyl acetate washing and methanol wash, product is vacuum-drying 4h at 110 DEG C.
Different additive on the impact of Methylimidazole grafting amount on Chloromethyl polystyrene if table 2 is as shown:
Table 2. different additive is on the impact of the grafting amount of Methylimidazole on Chloromethyl polystyrene
Embodiment 3
A series of nitrogen heterocyclic ring materials of loaded by polystyrene:
1) Chloromethyl polystyrene (1%DVB, 1g, 4.1mmol cl content) swells in 50mL acetonitrile, and constant temperature 50 DEG C stirs 2h.
2) NaH (0.2g) and selected nitrogen-containing heterocycle compound (0.4g) is added, comprise piperazine (Pi), pyrazine (Pz), pyrimidine (Pim), imidazoles (Im), N-Methylimidazole and VITAMIN B4 (Ad), be heated to 80 DEG C, condensing reflux, constant temperature stirs 2 days.
3) reaction terminates, cool to room temperature, and successively through filtration, ethyl acetate washing and methanol wash, product is vacuum-drying 4h at 110 DEG C.Be designated as PS-Pi, PS-Pz, PS-Pim, PS-Im, PS-Mim, PS-Ad successively.
The grafting amount of different nitrogen-containing heterocycle compound on Chloromethyl polystyrene is if table 3 is as shown:
Table 3. ultimate analysis calculates the grafting amount of nitrogen heterocycle perssad on Chloromethyl polystyrene
Catalytically active assessment is carried out, all with CO to above-mentioned loaded by polystyrene nitrogen heterocyclic ring material
2adding with the ring of propylene oxide reacts for technical indicator, specific as follows:
Adopt 300ml Parr reactor, drop into propylene oxide and the 1.5g catalyzer of 30ml, dress still.Under room temperature, first use a small amount of CO
2air in slow emptying still, and then add the CO of 3MPa
2gas.Then, reactor is heated to 100 DEG C, stirring reaction, does not become the mark of reaction terminating with pressure.In reaction process, and no longer additionally add CO
2to maintain constant pressure.After reaction terminates, with the cold hydrazine of-15 DEG C, reactor is cooled to less than 20 DEG C, residue CO in slow emptying still
2gas, now temperature in the kettle can be plummeted to about 0 DEG C, ensures that propylene oxide is pulled away less as far as possible.Filter out catalyzer, adopt GC and GCMS analytic sample composition; Described catalyzer is selected from loaded by polystyrene nitrogen heterocyclic ring material, and using N-Methylimidazole monomer as reference.Result is as table 4.
Table 4. loaded by polystyrene nitrogen heterocyclic serial application is in CO
2the catalytically active assessment of cycloaddition reaction
Above result shows, PS-Im and PS-Mim of five-membered ring structure has higher activity, productive rate be respectively 97.4% and 62.5%, TON be respectively 66.6 and 62.5 (adopt the catalyzer of same quality in reaction process, but charge capacity being different).Six-ring material activity is lower than five-ring.This let us is recognized, not only the molecular structure (five-ring or six-ring) of nitrogen heterocyclic has impact to activity, and in heterocycle, the position of two nitrogen-atoms also affects obviously activity, that is to say there is obvious structure activity relationship between catalyst body nitrogen heterocycle perssad and object reactant.
In addition, catalyst life research is carried out to PS-Im, after every secondary response, resin is only simply washed, dry, then repeat above-mentioned reaction process.Result is as table 5.
Table 5.PS-Im is used for CO
2the reperformance test of cycloaddition reaction
Result shows that this catalytic material has higher chemical stability, uses continuously and has no obvious activity decrease four times.
Above-described embodiment is only used for further illustrating a kind of loaded by polystyrene nitrogen heterocyclic ring material of the present invention and its preparation method and application; but the present invention is not limited to embodiment; every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all fall in the protection domain of technical solution of the present invention.
Claims (10)
1. a loaded by polystyrene nitrogen heterocyclic ring material, is characterized in that its structural formula is as follows:
Wherein R is nitrogen heterocyclic ring, include five-membered ring imidazoles (Im), Methylimidazole (Mim), the one in hexa-member heterocycle piperazine (Pi), pyrazine (Pz), pyrimidine (Pim), fused heterocycle benzoglyoxaline, VITAMIN B4 and guanine.
2. a preparation method for loaded by polystyrene nitrogen heterocyclic ring material as claimed in claim 1, is characterized in that comprising the following steps:
1) to carry out constant temperature in a solvent swelling for Chloromethyl polystyrene;
2) in the Chloromethyl polystyrene solution in swelling, add nitrogen heterocyclic ring material and alkaline additive, under condensing reflux, constant temperature stirs and reacts;
3) room temperature is cooled to reacted sample, carries out successively filtering, wash, vacuum-drying, obtained loaded by polystyrene nitrogen heterocyclic ring material.
3. the preparation method of loaded by polystyrene nitrogen heterocyclic ring material as claimed in claim 2, is characterized in that in step 1) in, the selection of described solvent is from deionized water (H
2o), ethanol (EtOH), acetonitrile (MeCN), DMF (DMF), N,N-dimethylacetamide (DMA), tetrahydrofuran (THF) (THF) and acetone (Me
2cO) one, in ethylene dichloride (DCE), normal hexane, toluene (PhMe), ethyl acetate or its combination.
4. the preparation method of loaded by polystyrene nitrogen heterocyclic ring material as claimed in claim 2 or claim 3, is characterized in that in step 1) in, swelling temperature is 25-100 DEG C, and swelling time is 1-5h.
5. the preparation method of loaded by polystyrene nitrogen heterocyclic ring material as claimed in claim 2, is characterized in that in step 2) in, temperature of reaction is 60-120 DEG C, and the reaction times is 1-3 days.
6. the preparation method of loaded by polystyrene nitrogen heterocyclic ring material as claimed in claim 2, it is characterized in that in step 2) in, described alkaline additive is selected from sodium hydroxide (NaOH), sodium hydride (NaH), sodium bicarbonate (NaHCO
3), sodium ethylate (CH
3cH
2oNa), tert-butyl lithium ((CH
3)
3cLi), lithium diisopropylamine (LDA) and two trimethyl silicon based ammonification sodium (NaN (SiMe
3)
2) in one or its combination.
7. the preparation method of loaded by polystyrene nitrogen heterocyclic ring material as claimed in claim 2, is characterized in that in step 3) be after filtration after ethyl acetate and methyl alcohol are washed, vacuum-drying 3-6h at 90-120 DEG C.
8. loaded by polystyrene nitrogen heterocyclic ring material as claimed in claim 1 is as CO
2with the application of the catalyzer of epoxide addition reaction.
9. apply as claimed in claim 8, it is characterized in that the concrete grammar of described application comprises the following steps: in reactor, drop into propylene oxide and described catalyzer, dress still; CO is added under room temperature
2gas; Heated and stirred makes it react; With cold hydrazine, reactor is cooled to less than 20 DEG C, residue CO in emptying still
2gas makes temperature in the kettle be plummeted to 0 DEG C; Filtering catalyst.
10. apply as claimed in claim 9, it is characterized in that, described temperature of reaction is 60-140 DEG C, and reaction pressure is 1-5MPa, and the reaction times is 3-15h, and the catalyst levels of every milliliter of propylene oxide is 15-100mg.
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| CN109731610A (en) * | 2018-12-29 | 2019-05-10 | 上海予利生物科技股份有限公司 | A kind of carrier model trifluoroacetophenone catalyst and its preparation method and application |
| CN114369080A (en) * | 2022-01-19 | 2022-04-19 | 凯瑞环保科技股份有限公司 | Device and method for synthesizing ethylene carbonate or propylene carbonate |
| CN114425442A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing alkylene carbonate and its preparing process and application |
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| CN114369080B (en) * | 2022-01-19 | 2024-03-29 | 凯瑞环保科技股份有限公司 | Device and method for synthesizing ethylene carbonate or propylene carbonate |
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