CN107537563A - A kind of quaternary phosphonium salt organic polymer catalyst and its preparation method and application - Google Patents
A kind of quaternary phosphonium salt organic polymer catalyst and its preparation method and application Download PDFInfo
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Abstract
Application the present invention relates to a kind of quaternary phosphonium salt organic polymer catalyst and preparation method thereof and in cyclic carbonate ester production.The quaternary phosphonium salt organic polymer catalyst mixes poly- form by the quaternary phosphonium salt 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, metal ion in acid is coordinated with the N in quaternary phosphonium salt organic polymer and/or P, and products therefrom is quaternary phosphonium salt organic polymer catalyst.The polyalcohol catalyst of gained is specially a kind of heterogeneous catalyst, suitable for fixed bed, slurry bed system, the reactor such as tank reactor and trickle bed.Quaternary phosphonium salt organic polymer catalyst provided by the invention is in epoxide and CO2Show excellent in addition production cyclic carbonate ester reaction, the activity of catalyst is higher, generates that the selectivity of cyclic carbonate ester is good, and substrate applicability is strong.And the catalyst stability is good, can be easily separated with reactant and product.
Description
Technical field
The invention belongs to heterogeneous catalysis and field of fine chemical, and in particular to a kind of quaternary phosphonium salt organic polymer catalyst and
Its application in cyclic carbonate ester production.
Background technology
With the continuous quickening of world industry process, CO2Discharge capacity be continuously increased, global warming and unusual weather conditions day
It is beneficial severe；And on the other hand, CO2It is a large amount of existing cheap and valuable C1 resources of nature again.Therefore, carbon dioxide is turned
The chemicals for turning to high added value increasingly causes the attention of scientists.
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.
2012, and Han Jinyu et al. (chemical industry and engineering, 2012,1:1) quaternary phosphonium ionic liquid/zinc halide is reported
It is catalyzed CO2 cycloaddition reactions.It is prepared for a kind of Lewis being made up of zinc chloride and hexyl myristyl quaternary phosphonium ionic liquid
Acid/base composite catalyst system, the cycloaddition reaction of epoxyalkane is used it for, show high catalytic activity, but be catalyzed
System is homogeneous, and catalyst is difficult to recovery and used.
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 quaternary phosphonium salt organic polymer catalyst and its system
Preparation Method and the application in cyclic carbonate ester production.
The technical scheme is that：
A kind of quaternary phosphonium salt organic polymer catalyst, the quaternary phosphonium salt organic polymer by alkylene function dough season phosphine
Salt autohemagglutination or with crosslinking agent is mixed poly- forms, add or be added without lewis acid in obtained organic polymer, add lewis acid
When, acid in metal ion be coordinated with the N in quaternary phosphonium salt organic polymer and/or P, products therefrom be quaternary phosphonium salt it is organic gather
Mixture catalyst.
The lewis acid is selected from more than one or both of Rh, Co, Zn, Mg or Ca halide, halide MX2Table
Show, wherein, M is metallic element, X=F, Cl, Br, I；Metallic element loading is 0.01~10wt% in catalyst.
The quaternary phosphonium salt of the alkylene function dough is
N=0-18 X=F Cl Br I.
The crosslinking agent is selected from
The quaternary phosphonium salt organic polymer is prepared by solvent thermal polymerization method；
The quaternary phosphonium salt organic polymer catalyst has hierarchical porous structure, and specific surface area is 100~3000m2/ g, simultaneously
Containing macropore, mesopore and micropore, pore volume is 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 quaternary phosphonium salt organic polymer catalyst, including:By alkylene official
Crosslinking agent can be added or be added without in the quaternary phosphonium salt of dough, using solvent thermal polymerization method, trigger alkylene through radical initiator
Generation polymerisation, generation have a supported quaternary phosphonium salt organic polymer of hierarchical porous structure, in obtained polymer addition or
Lewis acid is added without, obtains catalyst；It is that lewis acid is dissolved in solvent to add lewis acidic situation, adds season phosphine
Salt organic polymer, stirring, makes the metal ion in lewis acid be matched somebody with somebody with the N in quaternary phosphonium salt 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, quaternary phosphonium salt, the addition of alkylene function dough are added
Or do not add crosslinking agent, 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 quaternary phosphonium ionic liquid polymerization
Thing；
C) vacuum extracts solvent to the polymer for obtaining step b) at ambient temperature, that is, obtains having hierarchical porous structure
Quaternary phosphonium salt organic polymer；
D) under 273~473K, inert gas atmosphere, in containing lewis acidic solvent, add what step c) was obtained
Quaternary phosphonium salt organic polymer, stir 0.1~100 hour, vacuum extracts solvent, obtains catalyst；
According to step a)-c) or step a)-d) operation obtain quaternary phosphonium salt 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 quaternary phosphonium salt of alkylene function dough described in step a) and the mol ratio of crosslinking agent are 0.01:1~100:1；Alkene
The quaternary phosphonium salt of hydrocarbyl functional dough and the mol ratio of radical initiator are 300:1~10:1；Before aggregating into organic mixed polymers, alkene
The concentration of the quaternary phosphonium salt of hydrocarbyl functional 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 RhX2, CoX2, ZnX2, MgX2Or CaX2One or both of more than, wherein X
=F, Cl, Br, I, metal loading scope is 0.01~10wt% in catalyst.
According to the present invention, a kind of any quaternary phosphonium salt organic polymer catalyst of the present invention is provided in preparing cyclic carbonate ester
Application in reaction.
The course of reaction of cyclic carbonate ester is that the catalyst being prepared is fitted into reactor, is passed through unstripped gas and reaction
Material epoxide, the key component of unstripped gas is CO2, CO2Volume content be 20~70%, reaction mass epoxy compound
Thing 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 is in epoxide and CO2Showed in addition production cyclic carbonate ester reaction excellent
It is different.
The functionalization functional group of the quaternary phosphonium salt of alkylene function dough is preferably vinyl-functional, and described contains alkene
The quaternary phosphonium salt of the quaternary phosphonium salt of the base most preferably iodine containing vinyl, described crosslinking agent most preferably triphenylethylene base phosphine.
The reaction principle of the present invention：
Quaternary phosphonium ionic liquid efficiently can be catalyzed CO under homogeneous phase condition2With the addition reaction of epoxide, and
And quaternary phosphonium ionic liquid and RhX2, CoX2, ZnX2, MgX2Or CaX2(X=F, Cl, Br, I) is with the use of better.This hair
It is bright originally vinyl (Vinyl) group to be introduced on typical quaternary phosphonium ionic liquid, solvent heat is utilized in autoclave
Polymerization, autohemagglutination or mixes combinate form into the quaternary phosphonium salt organic polymer with high surface area and multi-stage artery structure with crosslinking agent.With
The polymer is as catalyst carrier, impregnated catalyst active metal component RhX2, CoX2, ZnX2, MgX2Or CaX2(X=F, Cl,
Br, I) in one or more, you can form efficient CO2With the efficient quaternary phosphonium salt organic polymer of addition reaction of epoxide
Thing catalyst.
Quaternary phosphonium salt and active metal in quaternary phosphonium salt organic polymer polymerization catalyst thing carrier framework provided by the present invention
Component is in high dispersion state, therefore catalyst activity is higher.And the component of activity is firmly embedded in polymer backbone
In, active component not easily runs off, and catalyst stability is preferable, and is easy to recycle.
Beneficial effects of the present invention are：
The quaternary phosphonium salt and active metal component contained in quaternary phosphonium salt organic polymer catalyst backbone of the present invention is equal
In high dispersion state, catalyst activity is high, and the macromolecular chain of the high intensity formed when polymerizeing has such catalyst
Very high stability.This kind of catalyst has multi-stage artery structure simultaneously, and substrate molecule easily spreads in the catalyst, and assigning should
The feature of class catalyst substrate strong applicability.
A kind of quaternary phosphonium salt organic polymer catalyst provided by the present invention and its application in cyclic carbonate ester production, make
Quaternary phosphonium salt organic polymer heterogeneous catalyst is applied to fixed bed, slurry bed system, the reaction work such as tank reactor and trickle bed
Skill, it can ensure during catalyst preparation on the premise of quaternary phosphonium salt higher catalytic activity and selectivity by the method for solvent thermal polymerization
Its immobilized is got off.Active component is in high dispersion state in the polyalcohol catalyst of formation, and the polymer formed is high
Strand has very strong flexibility, and homogeneous quaternary phosphonium salt higher catalytic activity is retained with selectivity.Kind provided by the present invention
Quaternary phosphonium salt organic polymer catalyst and its application in cyclic carbonate ester production can solve epoxide and CO2Addition is anti-
Long-standing stability and poor selectivity during catalyst heterogeneouss, and active component is answered to be difficult to reclaim and be lost in serious
The problems such as.Production method substrate applicability is strong simultaneously, and reactant and product be can be easily separated with catalyst, and catalyst, which is easily recycled, to be made
With being CO2Addition reaction with epoxide provides new industrialization technology.
Brief description of the drawings
Fig. 1 is the quaternary phosphonium ionic liquid structural representation of typical alkylene functionalization.
Fig. 2 is a kind of quaternary phosphonium ionic liquid polymerization technique route schematic diagram of alkylene functionalization.
Fig. 3 is the schematic diagram for the typical crosslinking agent used in polymerization.
Fig. 4 is the Vinyl PILC of vinyl functional dough2Br's (accompanying drawing 1, n=1, X=Br)1H is composed.
Fig. 5 is the Vinyl PILC of vinyl functional dough2Br's (accompanying drawing 1, n=1, X=Br)13C is composed.
Fig. 6 is the Vinyl PILC of vinyl functional dough2Br's (accompanying drawing 1, n=1, X=Br)31P is composed.
Fig. 7 is N2The catalyst thermogravimetric curve that embodiment 1 synthesizes under atmosphere.
Fig. 8 is the schematic arrangement of reaction raw materials substrate.
Fig. 9 is the nitrogen physisorption (A) and pore-size distribution (B) spectrogram of the heterogeneous catalyst synthesized in embodiment 1.
Figure 10 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
Under 298K and inert gas shielding atmosphere, by 10.0 grams of Vinyl PILC2Br monomers (accompanying drawing 1, n=1, X=
Br) it is dissolved in 100.0ml tetrahydrofuran solvents, while adds 2.5g crosslinking agents three (4- vinyl benzenes) base phosphine (L1), to above-mentioned
1.0 grams of radical initiator azodiisobutyronitriles are added in solution, are stirred 2 hours.The solution being stirred is moved in autoclave,
Under 373K and inert gas shielding atmosphere polymerization 24h is carried out using solvent thermal polymerization method.Solution cooling after above-mentioned polymerization
To room temperature, room temperature condition vacuum takes solvent away, that is, obtains by Vinyl PILC2Br and three (4- vinyl benzenes) base phosphine organic monomers
The organic polymer carrier of copolymerization.Accompanying drawing 2 is Vinyl PILC2The schematic diagram of the organic mixed copolymer carrier polymerization technique routes of Br.
Weigh 70 milligrams of ZnBr2It is dissolved in 10.0ml tetrahydrofuran solvents, adds 1.0 grams by Vinyl PILC2Br and three (4- vinyl
Benzene) base phosphine is copolymerized obtained organic mixed copolymer carrier, it is small that this mixture is stirred under 298K and inert gas shielding atmosphere to 24
When, then vacuum takes solvent away at ambient temperature, that is, obtains and be applied to CO2With the heterogeneous catalysis of epoxide addition reaction
Agent.
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 weighing 10.0 grams of Vinyl PILC8Br monomers (accompanying drawing 1, n=8, X=I), substitute
10.0 grams of Vinyl PILC2Br monomers (accompanying drawing 1, n=1, X=Br) outside, 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 quaternary phosphonium ionic liquids are avtive spots when calculating.The active component of embodiment 9 is
Ca。
Claims (10)
- A kind of 1. quaternary phosphonium salt organic polymer catalyst, it is characterised in that:The quaternary phosphonium salt organic polymer is by alkylene function The quaternary phosphonium salt autohemagglutination of dough or with crosslinking agent is mixed poly- forms, add or be added without lewis acid in obtained organic polymer, add When entering lewis acid, the metal ion in acid is coordinated with the N in quaternary phosphonium salt organic polymer and/or P, and products therefrom is season Phosphonium salt organic polymer catalyst.
- 2. quaternary phosphonium salt organic polymer catalyst according to claim 1, it is characterised in that:The lewis acid is selected from more than one or both of Rh, Co, Zn, Mg or Ca halide, halide MX2Represent, its In, M is metallic element, X=F, Cl, Br, I；Metallic element loading is 0.01~10wt% in catalyst.
- 3. quaternary phosphonium salt organic polymer catalyst according to claim 1, it is characterised in that:It is describedThe quaternary phosphonium salt of alkylene function dough is n=0-18X=F Cl Br I.
- 4. quaternary phosphonium salt organic polymer catalyst according to claim 1, it is characterised in that:The crosslinking agent is selected from
- 5. quaternary phosphonium salt organic polymer catalyst according to claim 1, it is characterised in that:The quaternary phosphonium salt organic polymer Thing is prepared by solvent thermal polymerization method；The quaternary phosphonium salt organic polymer catalyst has hierarchical porous structure, and specific surface area is 100~3000m2/ g, contains simultaneously Macropore, mesopore and micropore, pore volume are 0.1~5.0cm3/ g, pore-size distribution is in 0.2~50.0nm.
- A kind of 6. preparation method of any quaternary phosphonium salt organic polymer catalyst of claim 1-5, it is characterised in that:By alkene Crosslinking agent is added or be added without in the quaternary phosphonium salt of hydrocarbyl functional dough, using solvent thermal polymerization method, is triggered through radical initiator Polymerisation occurs for alkylene, and generating has the supported quaternary phosphonium salt organic polymer of hierarchical porous structure, in obtained polymer Lewis acid is added or be added without, obtains catalyst；It is that lewis acid is dissolved in solvent to add lewis acidic situation, is added Enter quaternary phosphonium salt organic polymer, stir, the metal ion in lewis acid is entered with the N in quaternary phosphonium salt organic polymer and/or P Row coordination, boils off volatile solvent, obtains catalyst afterwards.
- 7. preparation method according to claim 6, it is characterised in that:Specifically preparation process is：A) under 273~473K, inert gas atmosphere, in a solvent, add alkylene function dough quaternary phosphonium salt, addition or not Addition crosslinking agent, radical initiator is added, after mixing, stirred 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 quaternary phosphonium ionic liquid polymer；C) vacuum extracts solvent to the polymer for obtaining step b) at ambient temperature, that is, obtains the season phosphine with hierarchical porous structure Salt organic polymer；D) under 273~473K, inert gas atmosphere, in containing lewis acidic solvent, the season phosphine that step c) is obtained is added Salt organic polymer, stir 0.1~100 hour, vacuum extracts solvent, obtains catalyst；According to step a)-c) or step a)-d) operation obtain quaternary phosphonium salt organic polymer catalyst.
- 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 quaternary phosphonium salt of alkylene function dough described in step a) and the mol ratio of crosslinking agent are 0.01:1~100:1；Alkylene The quaternary phosphonium salt of function dough and the mol ratio of radical initiator are 300:1~10:1；Before aggregating into organic mixed polymers, alkylene The concentration of the quaternary phosphonium salt of 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 RhX2, CoX2, ZnX2, MgX2Or CaX2One or both of more than, wherein X=F, Cl, Br, I, metal loading scope is 0.01~10wt% in catalyst.
- A kind of 9. any quaternary phosphonium salt organic polymer catalyst of claim 1-5 answering in preparing cyclic carbonate ester and reacting With.
- 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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| CN111111775A (en) * | 2018-11-01 | 2020-05-08 | 中国科学院大连化学物理研究所 | Organic phosphine-containing polymer carrier-loaded Rh-based catalyst, and preparation and application thereof |
| CN112898149A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for preparing acetic acid by low-temperature catalytic oxidation of ethane with monatomic catalyst |
| CN111533837A (en) * | 2020-04-20 | 2020-08-14 | 浙江师范大学 | Acidic polymeric ionic liquid and preparation method and application thereof |
| CN115463694A (en) * | 2021-06-10 | 2022-12-13 | 中国科学院大连化学物理研究所 | Application of quaternary phosphonium salt ionic polymer supported palladium catalyst in alkyne carbonylation reaction |
| CN114773171A (en) * | 2022-03-10 | 2022-07-22 | 中国科学院大连化学物理研究所 | Method for propylene hydroformylation reaction by using phosphine oxide polymer supported catalyst |
| CN114989408A (en) * | 2022-07-12 | 2022-09-02 | 郑州大学 | Solid-phase catalyst for carbon dioxide/epoxy compound copolymerization and preparation method thereof |
| CN114989408B (en) * | 2022-07-12 | 2023-04-25 | 郑州大学 | Solid phase catalyst for carbon dioxide/epoxy compound copolymerization and preparation method thereof |
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