CN107537575A - A kind of imidazole salts organic polymer catalyst and its preparation method and application - Google Patents

A kind of imidazole salts organic polymer catalyst and its preparation method and application Download PDF

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CN107537575A
CN107537575A CN201610464558.4A CN201610464558A CN107537575A CN 107537575 A CN107537575 A CN 107537575A CN 201610464558 A CN201610464558 A CN 201610464558A CN 107537575 A CN107537575 A CN 107537575A
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organic polymer
catalyst
imidazole
imidazole salts
salts organic
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CN107537575B (en
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丁云杰
李存耀
汪文龙
严丽
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a kind of imidazole salts organic polymer catalyst and its preparation method and application, the imidazole salts organic polymer mixes poly- form by the imidazole salt compound autohemagglutination of alkylene function dough or with crosslinking agent, lewis acid is added or is added without in obtained organic polymer, when adding lewis acid, N in metal ion and organic polymer and/or P in acid are coordinated, and products therefrom is imidazole salts organic polymer catalyst.The imidazole salts organic polymer catalyst of gained is applied to fixed bed, slurry bed system, the reactor such as tank reactor and trickle bed.Catalyst provided by the invention has performance well in epoxide and the reaction of carbon dioxide production cyclic carbonate ester, and activity is higher, generates that the selectivity of cyclic carbonate ester is good, and substrate applicability is strong.And the catalyst stability is good, the separation of catalyst and reactant, product is simple and efficient.

Description

A kind of imidazole salts organic polymer catalyst and its preparation method and application
Technical field
The invention belongs to heterogeneous catalysis and field of fine chemical, and in particular to a kind of imidazole salts organic polymer catalyst and Its preparation method and application.
Background technology
In recent years, with the continuous development of world industry process, CO2Discharge capacity be continuously increased, global warming is gentle Wait abnormal increasingly serious；And on the other hand, CO2It is a large amount of existing cheap and valuable C1 resources of nature again.Therefore, by two Carbon oxide conversion increasingly causes the attention of scientists for the chemicals of high added value.
Carbon dioxide can generate important industrial chemicals cyclic carbonate ester through addition reaction with epoxides.This is one The reaction of 100% Atom economy, generated without accessory substance, be CO2The important channel of trans-utilization.Cyclic carbonate ester has strong pole The advantages that property, higher boiling, high-flash, low evaporation rate, hypotoxicity and biodegradable, it can be used as the original of makrolon Material, or important fine chemical product intermediate.
Report for CO2It is very extensive with the catalyst system and catalyzing of epoxide cycloaddition reaction, such as alkali metal salt (Chem.Rev.,2007,107:2365), ionic liquid (J.Mol.Catal.A, 2008,279:230), metal halide (Tetrahedron Lett.,2004,45:8307), quaternary ammonium salt (J.Mol.Catal.A, 2006,249:And transition metal 143) (J.Am.Chem.Soc.,2001,123:11498) etc..But exploitation it is a kind of with high activity, high selectivity, easily reclaim it is non- Phase catalyst is still the important goal of people's research.
2013, and Deng Weiqiao et al. (Nat.Commun., 2013,4:1960) a kind of conjugation micropore Salen parts have been invented Polymer.The self-supported Co-CMP and Al-CMP catalyst of the polymer can be catalyzed CO2With the reaction of expoxy propane.It is but anti- Answer technique more complicated, it is necessary to which adding TBAB makees auxiliary agent.Epoxide substrate only tests expoxy propane, and reaction process is autoclave Reaction.And the problem of polymer stabilisation of Schiff bases is bigger.
2015, Yugen Zhang et al. (Chem.Commun., 2015,51,15708) pair method handles for gram crosslinking Quaternary phosphonium salt has been cross-linked into HCPs polymer, and has probed into this kind of catalyst in CO2With the application in epoxide addition, hair Now add ZnBr2Auxiliary agent rear catalyst activity is obviously improved, and catalyst has good substrate applicability.But catalyst Activity needs further to be lifted.
The content of the invention
In order to solve the above problems, it is an object of the invention to provide a kind of imidazole salts organic polymer catalyst and its system Preparation Method and application.
The technical scheme is that：
A kind of imidazole salts organic polymer catalyst, the imidazole salts organic polymer by alkylene function dough imidazoles Salt compounds autohemagglutination or with crosslinking agent is mixed poly- forms, add or be added without lewis acid in obtained organic polymer, add During lewis acid, acid in metal ion and organic polymer in N and/or P be coordinated, products therefrom be imidazole salts it is organic Polyalcohol catalyst.
The lewis acid is selected from more than one or both of Zn, Ca or Mg halide, halide MX2Represent, its In, M is metallic element, X=F, Cl, Br, I, and metal loading is 0.01~10wt% in catalyst.
The imidazole salt compound of the alkylene function dough is
The crosslinking agent is selected from
The imidazole salts organic polymer is prepared by solvent thermal polymerization method；
The imidazole salts organic polymer has hierarchical porous structure, and specific surface area is 100~3000m2/ g, simultaneously containing big Hole, mesopore and micropore, pore volume are 0.1~5.0cm3/ g, pore-size distribution is in 0.2~50.0nm.
The present invention also provides a kind of preparation method of above-mentioned imidazole salts organic polymer catalyst, including, by alkylene official Crosslinking agent can be added or be added without in the imidazole salt compound of dough, using solvent thermal polymerization method, draw through radical initiator Send out alkylene and polymerisation occurs, generation has the imidazole salts organic polymer of hierarchical porous structure, added in obtained polymer Or lewis acid is added without, obtain catalyst；The situation for adding Louis is that lewis acid is dissolved in solvent, adds imidazoles Salt organic polymer, stirring, makes the metal ion in lewis acid be matched somebody with somebody with the N in imidazole salts organic polymer and/or P Position, boils off volatile solvent, obtains catalyst afterwards.
Specific preparation process includes：
A) under 273~473K, inert gas atmosphere, in a solvent, the imidazole salt of alkylene function dough is added Whether compound, addition crosslinking agent or not, add radical initiator, after mixing, stir the mixture for 0.1~100 hour；
B) mixed solution made from step a) is transferred in synthesis autoclave, 273~473K, under inert gas atmosphere, Using solvent thermal polymerization method, stand 1~100 hour and carry out polymerisation, obtain a kind of immobilized ion liquid polymer；
C) the mixed polymers for obtaining step b), at ambient temperature vacuum extract solvent, that is, obtain with hierarchical porous structure Imidazole salts organic polymer；
D) under 273~473K, inert gas atmosphere, in containing lewis acidic solvent, add what step c) was obtained Imidazole salts organic polymer, stir 0.1~100 hour, vacuum extracts organic solvent, obtains catalyst；
According to step a)-c) or step a)-d) operation obtain imidazole salts organic polymer catalyst.
Solvent described in step a) is in water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform It is one or more kinds of；The crosslinking agent is styrene, ethene, propylene, divinylbenzene, trivinylbenzene, triphenylethylene base It is more than one or both of phosphine, dimethoxymethane, diiodomethane, paraformaldehyde or the acetylenylbenzenes of 1,3,5- tri-；It is described from It is that cyclohexanone peroxide, dibenzoyl peroxide, TBHP, azodiisobutyronitrile or azo two are different by base initiator The one or more of heptonitrile；
The imidazole salt compound of alkylene function dough described in step a) and the mol ratio of crosslinking agent are 0.01:1~ 100:1；The imidazole salt compound of alkylene function dough and the mol ratio of radical initiator are 300:1~10:1；Polymerization Into before organic mixed polymers, the concentration of the imidazole salt compound of alkylene function dough in organic solvent is 0.01-1000g/ L；
Solvent described in step d) is in water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform One or more, the lewis acid are ZnX2, CaX2Or MgX2One or both of more than, X=F, Cl, Br, I, urge Metal loading is 0.01~10wt% in agent.
According to the present invention, a kind of above-mentioned imidazole salts organic polymer catalyst is also provided in preparing cyclic carbonate ester and reacting Using.
Cyclic carbonate ester course of reaction is that the catalyst being prepared is fitted into reactor, is passed through unstripped gas and reactant Expect epoxide, the key component of unstripped gas is CO2, CO2Volume content be 20~70%, reaction mass epoxide Purity is 20~100%, 323~573K of reaction temperature, 0.1~10.0MPa of reaction pressure, 100~20000h of gas space velocity-1, 0.01~10.0h of liquid hourly space velocity (LHSV)-1, described reactor is fixed bed, slurry bed system, trickle bed or tank reactor.
Epoxide of the present invention selected from but be not limited in following several epoxides:
The Polymer Blends catalyst of gained has very in epoxide and the reaction of carbon dioxide production cyclic carbonate ester Good performance.
The functionalization functional group of the imidazole salt compound of alkylene function dough is preferably vinyl-functional, described The imidazole salt compound of imidazole salt compound containing the alkylene most preferably iodine containing vinyl, described crosslinking agent is most Good is triphenylethylene base phosphine.
The reaction principle of the present invention：
Imidazole salt compound ionic liquid efficiently can be catalyzed CO under homogeneous phase condition2With the addition of epoxide Reaction, and imidazole salt compound ionic liquid and ZnX2, CaX2Or MgX2(X=F, Cl, Br, I) is used cooperatively effect more It is good.Novelty of the invention will introduce vinyl (Vinyl) group on typical imidazole salt compound ionic liquid, in high pressure Utilize solvent thermal polymerization method in kettle, autohemagglutination or mix combinate form into organic poly- with high surface area and multi-stage artery structure with crosslinking agent Compound.Using the polymer as catalyst carrier, catalyst activity metal component ZnX on dipping2, CaX2Or MgX2(X=F, Cl, Br, I) in one or more, you can form efficient CO2With the addition reaction effective catalyst of epoxide.
Imidazole salt compound and active metal component in catalyst organic polymer carrier framework provided by the present invention High dispersion state is in, therefore catalyst activity is higher.It is living and the component of activity is firmly embedded in polymer backbone Property component not easily runs off, and catalyst stability is preferable, and is easy to recycle.
Beneficial effects of the present invention are：
The imidazole salt compound and active metal component contained in catalyst backbone of the present invention is in high score Bulk state, catalyst activity are high, and to have such catalyst very high steady for the macromolecular chain of the high intensity formed when polymerizeing It is qualitative.This kind of catalyst has multi-stage artery structure, and substrate molecule easily spreads in the catalyst, assigns such catalyst substrate The feature of strong applicability.
Polyalcohol catalyst provided by the present invention is applied to fixed bed, slurry bed system, the reaction such as tank reactor and trickle bed Technique, pass through solvent heat on the premise of it can ensure imidazole salt compound high catalytic activity and selectivity during catalyst preparation The method of polymerization is got off active component is immobilized.Active component is in high dispersion state in the polyalcohol catalyst of formation, and And the polymeric chain formed has very strong flexibility, homogeneous imidazole salt compound high catalytic activity obtains with selectivity Retain.A kind of production method of new cyclic carbonate ester provided by the present invention and application can solve CO2With epoxide Long-standing stability and poor selectivity during catalysts heterogeneouss, and the problems such as loss of active component is serious. Production method substrate applicability is strong simultaneously, and separating for reactant and product and catalyst is simple and efficiently, is CO2With epoxidation The reaction of compound provides new industrialization technology.
Brief description of the drawings
Fig. 1 is the imidazole salt compound ionic liquid structural representation of typical alkylene functionalization.
Fig. 2 is a kind of imidazole salt compound ion liquid polymerization technology path schematic diagram of alkylene functionalization.
Fig. 3 is the schematic diagram for the typical crosslinking agent used in polymerization.
Fig. 4 is the Vinyl ILBr's of vinyl functional dough1H is composed.
Fig. 5 is the Vinyl ILBr's of vinyl functional dough13C is composed.
Fig. 6 is N2The catalyst thermogravimetric curve that embodiment 1 synthesizes under atmosphere.
Fig. 7 is the schematic arrangement of reaction raw materials substrate.
Fig. 8 is the nitrogen physisorption (A) and pore-size distribution (B) spectrogram of the heterogeneous catalyst synthesized in embodiment 1.
Fig. 9 is the SEM (A) and TEM (B) spectrogram of the heterogeneous catalyst synthesized in embodiment 1.
Embodiment
Following embodiments better illustrate to the present invention, but do not limit invention which is intended to be protected.
Embodiment 1
It is under 298K and inert gas shielding atmosphere, 10.0 grams of Vinyl ILBr monomers (accompanying drawing 1, n=1, X=Br) are molten In 100.0ml tetrahydrofuran solvents, while 2.5g crosslinking agents three (4- vinyl benzenes) base phosphine (L1) is added, into above-mentioned solution 1.0 grams of radical initiator azodiisobutyronitriles are added, are stirred 2 hours.The solution being stirred is moved in autoclave, in 373K With under inert gas shielding atmosphere polymerization 24h is carried out using solvent thermal polymerization method.Solution after above-mentioned polymerization is cooled to room temperature, Room temperature condition vacuum takes solvent away, that is, obtain by Vinyl ILBr and three (4- vinyl benzenes) base phosphine organic monomers copolymerization it is organic Polymer support.Fig. 2 is the schematic diagram of the organic mixed copolymer carrier polymerization technique routes of Vinyl ILBr.Weigh 70 milligrams of ZnBr2 It is dissolved in 10.0ml tetrahydrofuran solvents, adds 1.0 grams and be copolymerized what is obtained by Vinyl ILBr and three (4- vinyl benzenes) base phosphines Organic mixed copolymer carrier, this mixture is stirred 24 hours under 298K and inert gas shielding atmosphere, then in room temperature condition Lower vacuum takes solvent away, that is, obtains and be applied to CO2With the heterogeneous catalyst of epoxide addition reaction.
Embodiment 2
In example 2, except weighing 10.0 grams of crosslinking agents three (4- vinyl benzenes) base phosphine (L1), 2.5 grams of crosslinkings are substituted Agent three (4- vinyl benzenes) base phosphine (L1), remaining catalyst synthesis processes are same as Example 1.
Embodiment 3
In embodiment 3,1.0 grams of free radicals initiations are substituted except weighing 0.1 gram of radical initiator azodiisobutyronitrile Outside agent azodiisobutyronitrile, remaining catalyst synthesis processes is same as Example 1.
Embodiment 4
In example 4, in addition to substituting 100.0ml tetrahydrofuran solvents with 50.0ml tetrahydrofuran solvents, remaining Catalyst synthesis processes are same as Example 1.
Embodiment 5
In embodiment 5, except substituting 100.0ml tetrahydrofuran solvents with 100.0ml DMFs solvent Outside, remaining catalyst synthesis processes is same as Example 1.
Embodiment 6
In embodiment 6, in addition to substituting 373K polymerization temperatures with 393K polymerization temperatures, remaining catalyst synthesis processes It is same as Example 1.
Embodiment 7
In embodiment 7, except with 12h polymerization times substitute 24h polymerization times in addition to, remaining catalyst synthesis processes with Embodiment 1 is identical.
Embodiment 8
In embodiment 8,2.5 grams of triphenylethylene base phosphines are substituted except adding 10.0 grams of triphenylethylene base benzene (Fig. 3, L22) Substituted as outside crosslinking agent, remaining catalyst synthesis processes is same as Example 1.
Embodiment 9
In embodiment 9, weigh 55.5 milligrams of calcium chloride replacement zinc bromides and be dissolved in outside 10.0ml tetrahydrofuran solvents, remaining Catalyst synthesis processes it is same as Example 1.
Embodiment 10
The catalyst 0.5g of above-mentioned preparation is encased in fixed bed reactors, both ends load quartz sand.Unstripped gas CO2It is empty Speed elects 2000h as-1, liquid charging stock expoxy propane (Fig. 7, S1, n=0) liquid speed per hour is 5h-1, carried out under 393K, 2.0MPa CO2With the addition reaction of expoxy propane.Constant temperature (273K) collecting tank of product through a 60ml is collected.Obtained product uses HP-7890N gas chromatographic analysis equipped with HP-5 capillary columns and fid detector, makees internal standard using n-butanol.Reaction result arranges In table 1.
Embodiment 11
Catalyst 0.5g prepared by embodiment 1 is encased in the paste state bed reactor of 50ml capacity, and adds 30ml carbon Acid propylene ester is slurry liquid.Reaction condition is 393K, 2.0MPa, unstripped gas CO2Air speed elects 2000h as-1, liquid charging stock epoxy third Alkane (Fig. 7, S1, n=0) liquid speed per hour is 5h-1, slurry bed system stir speed (S.S.) is 750 revs/min.Constant temperature of the product through a 60ml (273K) collecting tank is collected, and is all collected with the reaction product and slurry liquid of tail gas entrainment in collecting tank.Other same embodiments 10, data are listed in table 1
Embodiment 12
Made except substituting expoxy propane of epoxy chloropropionate alkene (Fig. 7, S2, n=1) substrate outside reaction substrate, remaining is the same as implementation Example 10, reaction result are listed in table 1.
Embodiment 13
In embodiment 13, except replacing embodiment 1 with 10.0 grams of Vinyl ILBr monomers (accompanying drawing 1, n=8, X=Br) In 10.0 grams of Vinyl ILBr monomers it is outer (accompanying drawing 1, n=1, X=Br), remaining catalyst synthesis processes and the phase of embodiment 1 Together.
The specific surface area of catalyst and propylene response data synthesized in the embodiment 1-12 of table 1
* experiment condition：120 DEG C, 2MPa, unstripped gas CO2Air speed is 2000h-1, liquid charging stock expoxy propane (Fig. 7, S1) liquid Body speed per hour is 5h-1.TOF thinks that all imidazole salt compound ionic liquids are avtive spots when calculating.The work of embodiment 9 Property component is Ca.

Claims (10)

  1. A kind of 1. imidazole salts organic polymer catalyst, it is characterised in that:The imidazole salts organic polymer is by alkylene function The imidazole salt compound autohemagglutination of dough or with crosslinking agent is mixed poly- forms, add or be added without Louis in obtained organic polymer This acid, add lewis acid when, acid in metal ion and organic polymer in N and/or P be coordinated, products therefrom is Imidazole salts organic polymer catalyst.
  2. 2. imidazole salts organic polymer catalyst according to claim 1, it is characterised in that:The lewis acid is selected from It is more than one or both of Zn, Ca or Mg halide, halide MX2Represent, wherein, M is metallic element, X=F, Cl, Br, I, metal loading is 0.01~10wt% in catalyst.
  3. 3. imidazole salts organic polymer catalyst according to claim 1, it is characterised in that:The alkene
    The imidazole salt compound of hydrocarbyl functional dough is n=1-18X=F Cl Br I.
  4. 4. imidazole salts organic polymer catalyst according to claim 1, it is characterised in that:The crosslinking agent is selected from
  5. 5. imidazole salts organic polymer catalyst according to claim 1, it is characterised in that:The imidazole salts organic polymer Thing is prepared by solvent thermal polymerization method；
    The imidazole salts organic polymer has hierarchical porous structure, and specific surface area is 100~3000m2/ g, simultaneously containing macropore, in Hole and micropore, pore volume are 0.1~5.0cm3/ g, pore-size distribution is in 0.2~50.0nm.
  6. A kind of 6. preparation method of any imidazole salts organic polymer catalyst of claim 1-5, it is characterised in that:By alkene Crosslinking agent is added or be added without in the imidazole salt compound of hydrocarbyl functional dough, using solvent thermal polymerization method, is drawn through free radical Sending out agent triggers alkylene that polymerisation, imidazole salts organic polymer of the generation with hierarchical porous structure, obtained polymer occurs Middle addition is added without lewis acid, obtains catalyst；The situation for adding Louis is that lewis acid is dissolved in solvent, is added Enter imidazole salts organic polymer, stir, the metal ion in lewis acid is entered with the N in imidazole salts organic polymer and/or P Row coordination, boils off volatile solvent, obtains catalyst afterwards.
  7. 7. the preparation method of heterogeneous catalyst according to claim 6, it is characterised in that:
    Specifically preparation process is：
    A) under 273~473K, inert gas atmosphere, in a solvent, the imidazole salt compound of addition alkylene function dough, Whether addition crosslinking agent or not, add radical initiator, after mixing, stirs the mixture for 0.1~100 hour；
    B) mixed solution made from step a) is transferred in synthesis autoclave, 273~473K, under inert gas atmosphere, used Solvent thermal polymerization method, stand 1~100 hour and carry out polymerisation, obtain a kind of immobilized ion liquid polymer；
    C) the mixed polymers for obtaining step b), at ambient temperature vacuum extract solvent, that is, obtain the miaow with hierarchical porous structure Azoles salt organic polymer；
    D) under 273~473K, inert gas atmosphere, in containing lewis acidic solvent, the imidazoles that step c) is obtained is added Salt organic polymer, stir 0.1~100 hour, vacuum extracts organic solvent, obtains catalyst；
    According to step a)-c) or step a)-d) operation obtain imidazole salts organic polymer catalyst.
  8. 8. according to the preparation method described in claim 7, it is characterised in that：Solvent described in step a) is water, benzene, toluene, four It is one or more kinds of in hydrogen furans, methanol, ethanol, dichloromethane or chloroform；The crosslinking agent be styrene, ethene, Propylene, divinylbenzene, trivinylbenzene, triphenylethylene base phosphine, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3, It is more than one or both of acetylenylbenzenes of 5- tri-；The radical initiator be cyclohexanone peroxide, dibenzoyl peroxide, The one or more of TBHP, azodiisobutyronitrile or ABVN；
    The imidazole salt compound of alkylene function dough described in step a) and the mol ratio of crosslinking agent are 0.01:1~100: 1；The imidazole salt compound of alkylene function dough and the mol ratio of radical initiator are 300:1~10:1；Aggregate into Before machine mixes polymers, the concentration of the imidazole salt compound of alkylene function dough in organic solvent is 0.01-1000g/L；
    Solvent described in step d) is a kind of in water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform Or it is two or more, the lewis acid is ZnX2, CaX2Or MgX2One or both of more than, X=F, Cl, Br, I, catalyst Middle metal loading is 0.01~10wt%.
  9. A kind of 9. any imidazole salts organic polymer catalyst of claim 1-5 answering in preparing cyclic carbonate ester and reacting With.
  10. 10. according to the application described in claim 9, it is characterised in that：Course of reaction is to load the catalyst being prepared instead Answer in device, be passed through unstripped gas and reaction mass epoxide, the key component of unstripped gas is CO2, CO2Volume content be 20 ~70%, reaction mass epoxide purity is 20~100%, 323~573K of reaction temperature, reaction pressure 0.1~ 10.0MPa, 100~20000h of gas space velocity-1, 0.01~10.0h of liquid hourly space velocity (LHSV)-1, described reactor is fixed bed, slurry Bed, trickle bed or tank reactor.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108097308A (en) * 2018-01-10 2018-06-01 南开大学 For the preparation method and its application method of the non-metallic catalyst of acetylene hydrochlorination reaction
CN108273551A (en) * 2018-01-17 2018-07-13 福州大学 A kind of solid-carrying type Performance of Isomerization Catalysts for Light n-Paraffin and its preparation and application
CN109364993A (en) * 2018-12-17 2019-02-22 太原理工大学 For normal pressure catalyzed conversion CO2Poly ion liquid catalyst and preparation method thereof
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
CN112812230A (en) * 2019-11-15 2021-05-18 浙江大学 Catalytic load polymer and preparation method and application thereof
CN113234017A (en) * 2021-05-21 2021-08-10 天津包钢稀土研究院有限责任公司 Imidazole salt compound with antibacterial effect and preparation method and application thereof
CN114874487A (en) * 2022-05-27 2022-08-09 中国科学院兰州化学物理研究所 Rigid carrier loaded high polymer material and preparation method and application thereof
CN114933698A (en) * 2022-06-23 2022-08-23 武汉工程大学 For CO 2 Non-metal catalyst for synthesizing polycarbonate and preparation method thereof
CN116196896A (en) * 2023-04-25 2023-06-02 淮安兴淮消防设备有限公司 N-doped porous carbon-MoSe 2 Composite material of (C) and application thereof in wastewater adsorption

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101280042A (en) * 2007-04-03 2008-10-08 中国科学院化学研究所 Polymer loaded with ion liquid, preparation and application thereof
CN103657450A (en) * 2013-11-08 2014-03-26 江南大学 Polyvinyl acetate/polyion liquid semi-interpenetrating polymer network film and thermosetting preparation method thereof
US20150045570A1 (en) * 2012-06-08 2015-02-12 Massachusetts Institute Of Technology Phosphine-ligated palladium sulfonate palladacycles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101280042A (en) * 2007-04-03 2008-10-08 中国科学院化学研究所 Polymer loaded with ion liquid, preparation and application thereof
US20150045570A1 (en) * 2012-06-08 2015-02-12 Massachusetts Institute Of Technology Phosphine-ligated palladium sulfonate palladacycles
CN103657450A (en) * 2013-11-08 2014-03-26 江南大学 Polyvinyl acetate/polyion liquid semi-interpenetrating polymer network film and thermosetting preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MENGSHUAI LIU ET AL.: "Kinetics and Mechanistic Insight into Efficient Fixation of CO2 to Epoxides over N‑Heterocyclic Compound/ZnBr2 Catalysts", 《IND.ENG.CHEM.RES.》 *
QI SUN ET AL.: "Porous polymer catalysts with hierarchical structures", 《CHEM.SOC.REV.》 *

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CN108097308A (en) * 2018-01-10 2018-06-01 南开大学 For the preparation method and its application method of the non-metallic catalyst of acetylene hydrochlorination reaction
CN108273551A (en) * 2018-01-17 2018-07-13 福州大学 A kind of solid-carrying type Performance of Isomerization Catalysts for Light n-Paraffin and its preparation and application
CN109364993A (en) * 2018-12-17 2019-02-22 太原理工大学 For normal pressure catalyzed conversion CO2Poly ion liquid catalyst and preparation method thereof
CN109364993B (en) * 2018-12-17 2021-03-30 太原理工大学 For catalytic conversion of CO at normal pressure2Polyion liquid catalyst and preparation method thereof
CN109939731B (en) * 2019-03-20 2022-01-18 合肥学院 For atmospheric CO2Mesoporous polyion liquid catalyst for cycloaddition reaction, preparation method and 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
CN112812230A (en) * 2019-11-15 2021-05-18 浙江大学 Catalytic load polymer and preparation method and application thereof
CN113234017A (en) * 2021-05-21 2021-08-10 天津包钢稀土研究院有限责任公司 Imidazole salt compound with antibacterial effect and preparation method and application thereof
CN114874487A (en) * 2022-05-27 2022-08-09 中国科学院兰州化学物理研究所 Rigid carrier loaded high polymer material and preparation method and application thereof
CN114874487B (en) * 2022-05-27 2023-02-17 中国科学院兰州化学物理研究所 Rigid carrier loaded high polymer material and preparation method and application thereof
CN114933698A (en) * 2022-06-23 2022-08-23 武汉工程大学 For CO 2 Non-metal catalyst for synthesizing polycarbonate and preparation method thereof
CN114933698B (en) * 2022-06-23 2023-09-22 武汉工程大学 For CO 2 Nonmetallic catalyst for synthesizing polycarbonate and preparation method thereof
CN116196896A (en) * 2023-04-25 2023-06-02 淮安兴淮消防设备有限公司 N-doped porous carbon-MoSe 2 Composite material of (C) and application thereof in wastewater adsorption
CN116196896B (en) * 2023-04-25 2024-05-28 北京知投家知识产权运营有限公司 N-doped porous carbon-MoSe2Composite material of (C) and application thereof in wastewater adsorption

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