CN108772102A - Miscellaneous more metal effective catalysts of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester - Google Patents
Miscellaneous more metal effective catalysts of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester Download PDFInfo
- Publication number
- CN108772102A CN108772102A CN201810335694.2A CN201810335694A CN108772102A CN 108772102 A CN108772102 A CN 108772102A CN 201810335694 A CN201810335694 A CN 201810335694A CN 108772102 A CN108772102 A CN 108772102A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carbon dioxide
- reaction
- miscellaneous
- cyclic carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
Abstract
The present invention provides a kind of method of miscellaneous more metal coordinating polymer material efficient catalytic carbon dioxide synthesizing cyclic carbonate esters, it is related to a kind of chemical synthesis catalyst and preparation method thereof.The catalyst is a kind of miscellaneous metal coordinating polymer material, and it is the planar structure of 1D double-strands to have good thermal stability, structure, and all active sites are all exposed to outside, have higher catalytic conversion efficiency and selectivity.The catalyst have stable structure, be not easily decomposed, reaction process is not necessarily to organic solvent, the applied widely, plurality of advantages such as product yield is high, synthesis cost is low.The present invention, which can solve to be catalyzed carbon dioxide in the past and be reacted with epoxide, is converted into the problems such as synthesis temperature and pressure high, catalyst amount is big, the reaction time is long, product yield is low, poor selectivity in cyclic carbonate ester reaction, can be used for the recycling of carbon dioxide greenhouse gas.
Description
Technical field
The present invention relates to chemical fields, more particularly to a kind of the miscellaneous mostly golden of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester
Belong to effective catalyst and preparation method thereof.
Technical background
In recent years, with the development of the attention and carbon geochemistry polluted to carbon, CO2As the final state of carbon resource, and it is main
Greenhouse gases and be important C1 resources.The features such as due to rich reserves, nontoxic and inertia, is by more and more chemical works
The attention of person.Rationally utilize CO2Environmental problem can not only be weakened, and have great meaning to alleviating energy crisis.But two
The chemical inertness of carbonoxide hinders its application in chemical reaction.In recent years, more and more people begin to focus on and visit
Rope can make the catalyst of carbon dioxide activation, and react synthesis with chemistry with other simple organics as raw material
The various organic compounds of utility value.It is molten that cyclic carbonate ester is widely used as fine-chemical intermediate, inertia aprotic polar
Agent, biological medicine precursor and makrolon raw material；Makrolon is then widely used in the fields such as engineering plastics.Carbonic ester
(including cyclic carbonate ester and makrolon) is the fixed CO of chemistry2One of successful example.Therefore, it is a kind of efficiently to rationally design exploitation
Environmental protection, mild condition, preparation process are simple, catalyst of low cost and high selectivity is necessary.Currently, having very
Catalyst of more document reports about carbon dioxide fixation mainly has inorganic metal catalyst, organic quaternary ammonium salt, phosphonium salt catalysis
Agent, organic catalyst, metal organic frame (MOF), organic framework materials (COF) and ionic-liquid catalyst etc., but these
Catalyst has disadvantage mostly, as catalyst is unstable, catalytic condition is harsh, catalytic efficiency is low, manufacturing cost is high and selective
The shortcomings of poor, cannot be satisfied large-scale industrialization demand.
In conclusion present invention design, which has synthesized a kind of miscellaneous more metal effective catalysts, is suitable for carbon dioxide and epoxidation
The reaction that object generates cyclic carbonate ester is closed, to solve the problems, such as above-mentioned major part, there is potential industrial applications value.
Invention content
The purpose of the present invention is be converted into asking for cyclic carbonate ester technical deficiency for current carbon dioxide and epoxide
Topic, provides a kind of method of miscellaneous more metal coordinating polymer material efficient catalytic carbon dioxide synthesizing cyclic carbonate esters, the catalysis
Agent can solve the problems such as other catalyst efficiency are low, stability is poor, condition is harsh.In order to which effective solution is catalyzed at present
Agent there are the problem of, present invention employs completely new mentalities of designing, and transition metal and rare earth metal are effectively combined, profit
Achieve the purpose that efficient catalytic with more metal concerted catalysis, design has synthesized a series of new catalyst, for being catalyzed titanium dioxide
The reaction of carbon and cyclic carbonate ester.
The purpose of the present invention is what is be achieved through the following technical solutions：
The raw material for preparing of organic ligand (L) needed for the synthetic catalyst includes：5- allyl -3- methoxysalicylics
Sour methyl esters, hydrazine hydrate and aromatic aldehyde, wherein the organic ligand L has following structure：
The structural formula of such ligand is as it appears from the above, R in formula1、R2、R3、R4、R5For substituent group identical or different on phenyl ring
In (H, hydroxyl, methyl, ethyl, alkoxy, tertiary butyl, carboxyl, aldehyde radical, dimethylamino, lignocaine, halogen, quaternary ammonium salt etc.)
Arbitrary group.
Further, organic ligand (L) preparation needed for the synthetic catalyst carries out in two steps, the first step,
5- allyls -3- methoxysalicylic acids methyl esters and hydrazine hydrate are reacted in a solvent and generate 5- allyl -3- methoxysalicylics
Hydrazides；Second step, 5- allyl -3- methoxysalicylics hydrazides are reacted with aromatic aldehyde, are waited for after reaction in a solvent, product warp
It is filtered, washed, is dried, obtain white solid.Wherein, the above process is expressed as with chemical equation：
Further, the catalyst synthesis step is：A certain amount of organic ligand L is added in the reactor, is added
Appropriate solvent adds after a certain proportion of triethylamine stirs 30 minutes, is added after quantitative metal salt and stirs to being completely dissolved,
Again plus it is a certain amount of enter rare-earth salts stir to solution clarify after filter, take suitable filtrate to be fitted into 10ml containers, in a constant temperature
After degree lower reaction a period of time, you can obtain crystalline catalysis agent material, crystalline material is filtered, washed, dry after it is spare.Its
In, the catalyst has the following structure：
Wherein Ln=Sc, Y, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb；
M=Zn, Cd, Fe, Ti, Co, Ni, Cr, Zr, Cu, Mn, Al, Mg.
Further, the catalysis reaction step is：Catalyst, co-catalyst and epoxide are weighed as high pressure
In reaction kettle, it is filled with the carbon dioxide of certain pressure, after reacting a period of time at a certain temperature, reaction was completed, waits for reaction kettle
After being cooled to room temperature, sample is taken to pass through1H NMR carry out quantitative analysis.
Further, in the first step synthesizes 5- allyl -3- methoxysalicylic hydrazides, 5- allyl -3- methoxyl group water
Poplar acid methyl esters and hydrazine hydrate molar ratio are 1：1 to 1：10；Solvent for use is in methanol, ethyl alcohol, acetonitrile and dioxane
Any one or its arbitrary proportion mixture, at 25~80 DEG C, the reaction time is 2~12h for reaction temperature control.
Further, in second step synthesis organic ligand L, 5- allyls -3- methoxysalicylics hydrazides and aromatic aldehyde are thrown
Expect that molar ratio is 1：1 to 1：3；Solvent for use is any one or its arbitrary proportion in methanol, ethyl alcohol, acetonitrile and dioxane
Mixture, at 25~80 DEG C, the reaction time is 2~12h for reaction temperature control.
Further, the molar ratio of ligand L, metal salt and rare-earth salts is 1 in catalyst synthesis：1：1 to 3：2：2；
Solvent for use is the mixture of any one or its arbitrary proportion in methanol, ethyl alcohol, acetonitrile and dioxane, triethylamine with match
The molar ratio of body L is 1：1 to 1：6, at 25~40 DEG C, the reaction time is 12~72h for reaction temperature control.
Further, co-catalyst is PPN-Cl, that is, bi triphenyl phosphine ammonium chloride, the TBAB, that is, tetrabutyl in catalyst reaction
One kind in ammonium bromide, TBACl, that is, tetrabutylammonium chloride, TBAI, that is, tetrabutylammonium iodide and TBAAc, that is, tetrabutylammonium acetate ammonium；On
The molar ratio for stating catalyst, co-catalyst and epoxide is 1：10：100 to 1：100：400；Pressure carbon dioxide is 0.1
~1.5MPa；Reaction temperature is 60~120 DEG C.
Advantages of the present invention is with effect：
1, the miscellaneous more metal coordinating polymer effective catalysts of one kind provided by the invention, as a kind of efficient catalytic titanium dioxide
The catalyst of carbon synthesizing cyclic carbonate ester, not only high catalytic efficiency, also has the characteristics that the good, stable structure of selectivity.
2, miscellaneous more metal coordinating polymer effective catalysts provided by the invention have without using solvent, catalytic condition temperature
With advantage applied widely, there is potential industrialized utilization to be worth.
3, preparation method provided by the invention is simple, and mild condition is easily controllable, energy conservation and environmental protection, and product purity is high, rear to locate
Manage the advantages that facilitating.The experimental results showed that：The catalyst can realize carbon dioxide and epoxidation under conditions of one mild
The catalyzed conversion of object is closed, TOF is up to 30000h-1More than, the high conversion rate of such reaction has potential up to 80~95% or more
Industrial application value.The present invention relates to field of catalytic chemistry.
Description of the drawings
Fig. 1 is catalysis reaction schematic diagram；
Fig. 2 coordination polymer catalyst synthesizes schematic diagram；
Fig. 3 is the infrared spectrogram of organic ligand coordination polymer different from two kinds；
Fig. 4 is the simulation XRD of two kinds of different coordination polymers and practical XRD test results figure；
Fig. 5 is the hot weight curve of two kinds of different coordination polymers；
Fig. 6 is propylene oxide and carbon dioxide reaction product1H NMR quantitative analysis figures；
Fig. 7 is epoxychloropropane and carbon dioxide reaction product1H NMR quantitative analysis figures
Fig. 8 is epoxy styrene and carbon dioxide reaction product1H NMR quantitative analysis figures
Specific implementation mode
Below in conjunction with the accompanying drawings to the present invention implementation be described in detail so that advantages and features of the invention be easier to by
It will be understood by those skilled in the art that make clearer define to protection scope of the present invention.Referring to Fig. 1,2,3,4,
5,6,7 and 8.
Embodiment 1：
2.22g 5- allyl -3- methoxies are added into the 25ml two-mouth bottles equipped with reflux condensing tube, thermometer and magneton
Base gaultherolin and 3.50g hydrazine hydrates add 10ml methanol as solvent, and control temperature is waited in 60~65 DEG C of anti-12h
It is down to room temperature after reaction, white solid is precipitated, after solid is filtered, is washed, drying, obtain white 5- allyls-
3- methoxysalicylic hydrazides solids.
Embodiment 2：
2.22g 5- allyl -3- methoxies are added into the 25ml two-mouth bottles equipped with reflux condensing tube, thermometer and magneton
Base salicylyl hydrazine and 2.34g 3,5- di-tert-butyl salicylaldehydes add 10ml methanol as solvent, and control temperature is 60~65
DEG C reaction 6h, waits for being down to room temperature after reaction, white solid is precipitated, after solid is filtered, is washed, drying, obtain white
Color organic ligand solid.
Embodiment 3：
By catalyst 0.01mol%, co-catalyst TBAB 0.75mol%, substrate is epoxy styrene 10mmol, is added
Into the autoclave of 30ml, it is filled with 1MPa CO2, reaction kettle is placed in constant-temperature heating sleeve after being warming up to 120 DEG C, is reacted
Reaction kettle is finally cooled to room temperature by 1h, releases residual gas, and sampling utilizes1H NMR carry out quantitative analysis, and conversion ratio is
95%, selectivity is more than 99%.
Embodiment 4：
By catalyst 0.01mol%, co-catalyst TBAB 0.75mol%, substrate is propylene oxide 10mmol, is added to
In the autoclave of 30ml, it is filled with 1MPa CO2, reaction kettle is placed in constant-temperature heating sleeve after being warming up to 120 DEG C, reacts 1h,
Finally reaction kettle is cooled to room temperature, releases residual gas, sampling utilizes1H NMR progress quantitative analyses, conversion ratio 99%,
Selectivity is more than 99%.
Embodiment 5：
By catalyst 0.01mol%, co-catalyst TBAB 0.75mol%, substrate is epoxy butane 10mmol, is added to
In the autoclave of 30ml, it is filled with 1MPa CO2, reaction kettle is placed in constant-temperature heating sleeve after being warming up to 120 DEG C, reacts 1h,
Finally reaction kettle is cooled to room temperature, releases residual gas, sampling utilizes1H NMR progress quantitative analyses, conversion ratio 98%,
Selectivity is more than 99%.
Embodiment 6：
By catalyst 0.01mol%, co-catalyst TBAB 0.75mol%, substrate is oxepane 10mmol, is added to
In the autoclave of 30ml, it is filled with 1MPa CO2, reaction kettle is placed in constant-temperature heating sleeve after being warming up to 120 DEG C, reacts 1h,
Finally reaction kettle is cooled to room temperature, releases residual gas, sampling utilizes1H NMR progress quantitative analyses, conversion ratio 94%,
Selectivity is more than 99%.
Embodiment 7：
By catalyst 0.01mol%, co-catalyst TBAB 0.75mol%, substrate is epoxychloropropane 10mmol, is added
Into the autoclave of 30ml, it is filled with 1MPa CO2, reaction kettle is placed in constant-temperature heating sleeve after being warming up to 120 DEG C, is reacted
Reaction kettle is finally cooled to room temperature by 1h, releases residual gas, and sampling utilizes1H NMR carry out quantitative analysis, and conversion ratio is
99%, selectivity is more than 99%.
Embodiment 8：
By catalyst 0.01mol%, co-catalyst TBAB 0.75mol%, substrate is epoxy bromopropane 10mmol, is added
Into the autoclave of 30ml, it is filled with 1MPa CO2, reaction kettle is placed in constant-temperature heating sleeve after being warming up to 120 DEG C, is reacted
Reaction kettle is finally cooled to room temperature by 1h, releases residual gas, and sampling utilizes1H NMR carry out quantitative analysis, and conversion ratio is
98%, selectivity is more than 99%.
Embodiment 9：
By catalyst 0.01mol%, co-catalyst TBAB 0.75mol%, substrate is glycidol 10mmol, is added to
In the autoclave of 30ml, it is filled with 1MPa CO2, reaction kettle is placed in constant-temperature heating sleeve after being warming up to 120 DEG C, reacts 1h,
Finally reaction kettle is cooled to room temperature, releases residual gas, sampling utilizes1H NMR progress quantitative analyses, conversion ratio 96%,
Selectivity is more than 99%.
Embodiment 10：
By catalyst 0.01mol%, co-catalyst TBAB 0.75mol%, substrate is tertiary butyl glycidyl ether
10mmol is added in the autoclave of 30ml, is filled with 1MPa CO2, reaction kettle is placed in constant-temperature heating sleeve and is warming up to
After 120 DEG C, 1h is reacted, is finally cooled to room temperature reaction kettle, release residual gas, sampling utilizes1H NMR are quantitatively divided
Analysis, conversion ratio 90%, selectivity are more than 99%.
Embodiment 11：
By catalyst 0.01mol%, co-catalyst TBAB 0.75mol%, substrate is vinyl glycidyl ether
10mmol is added in the autoclave of 30ml, is filled with 1MPa CO2, reaction kettle is placed in constant-temperature heating sleeve and is warming up to
After 120 DEG C, 1h is reacted, is finally cooled to room temperature reaction kettle, release residual gas, sampling utilizes1H NMR are quantitatively divided
Analysis, conversion ratio 98%, selectivity are more than 99%.
Embodiment 12：
By catalyst 0.01mol%, co-catalyst TBAB 0.75mol%, substrate is phenyl glycidyl ether 10mmol,
It is added in the autoclave of 30ml, is filled with 1MPa CO2, reaction kettle is placed in constant-temperature heating sleeve after being warming up to 120 DEG C,
1h is reacted, is finally cooled to room temperature reaction kettle, releases residual gas, sampling utilizes1H NMR carry out quantitative analysis, conversion ratio
It is 95%, selectivity is more than 99%.
Embodiment 13：
By catalyst 0.01mol%, co-catalyst TBAB 0.75mol%, substrate is isopropyl glycidyl ether
10mmol is added in the autoclave of 30ml, is filled with 1MPa CO2, reaction kettle is placed in constant-temperature heating sleeve and is warming up to
After 120 DEG C, 1h is reacted, is finally cooled to room temperature reaction kettle, release residual gas, sampling utilizes1H NMR are quantitatively divided
Analysis, conversion ratio 93%, selectivity are more than 99%.
Embodiment 14：
By catalyst 0.01mol%, co-catalyst TBAB 0.75mol%, substrate is glycidyl methacrylate
10mmol is added in the autoclave of 30ml, is filled with 1MPa CO2, reaction kettle is placed in constant-temperature heating sleeve and is warming up to
After 120 DEG C, 1h is reacted, is finally cooled to room temperature reaction kettle, release residual gas, sampling utilizes1H NMR are quantitatively divided
Analysis, conversion ratio 99%, selectivity are more than 99%.
Only several embodiments of the present invention are expressed for example described above, and what is described is more specific and detailed, but simultaneously
It cannot be therefore understands that being all scope limitations of this patent.It should be pointed out that for those of ordinary skill in the art,
Under the premise of not departing from present inventive concept, various modifications and improvements can be made, these are all within the scope of protection of the present invention.
Therefore, the protection content of patent of the present invention should be determined by the appended claims.
Claims (8)
1. a kind of miscellaneous more metal effective catalysts of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester, which is characterized in that described
The raw material for preparing for the organic ligand L that synthetic catalyst uses includes：5- allyl -3- methoxysalicylic acids methyl esters, hydrazine hydrate
And aromatic aldehyde, wherein the organic ligand L structures are：
R in formula1、R2、R3、R4、R5For substituent group (H, hydroxyl, methyl, ethyl, alkoxy, tertiary fourth identical or different on phenyl ring
Base, carboxyl, aldehyde radical, dimethylamino, lignocaine, halogen, quaternary ammonium salt etc.) in arbitrary group.
2. miscellaneous more metal effective catalysts of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester according to claim 1,
It is characterized in that, organic ligand (L) preparation needed for the synthetic catalyst carries out in two steps, the first step, by 5- allyls
Base -3- methoxysalicylic acids methyl esters and hydrazine hydrate react in a solvent generates 5- allyl -3- methoxysalicylic hydrazides；
Second step, 5- allyl -3- methoxysalicylics hydrazides are reacted with aromatic aldehyde, are waited for after reaction in a solvent, product warp
It is filtered, washed, is dried, obtain white solid.
3. a kind of miscellaneous more metal efficient catalytics of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester according to claim 1
Agent, which is characterized in that the catalyst synthesis step is：A certain amount of organic ligand L is added in the reactor, is added appropriate
Solvent adds after a certain proportion of triethylamine stirs 30 minutes, adds after quantitative metal salt and stirs to being completely dissolved, then
It is added after a certain amount of rare-earth salts is stirred to solution clarification and filters, take suitable filtrate to be fitted into 10ml containers, in certain temperature
After lower reaction a period of time, you can obtain crystalline catalysis agent material, crystal is filtered, washed, dry after it is spare.Wherein, described
Catalyst has the following structure：
One of wherein Ln=Sc, Y, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb；
One of M=Zn, Cd, Fe, Ti, Co, Ni, Cr, Zr, Cu, Mn, Al, Mg.
4. a kind of miscellaneous more metal efficient catalytics of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester according to claim 1
Agent, which is characterized in that the catalysis reaction step is：Weighing catalyst, co-catalyst and epoxide, to be placed in high pressure anti-
It answers in kettle, is filled with the carbon dioxide of 1MPa-2MPa, after reacting a period of time at a certain temperature, reaction was completed, waits for that reaction kettle is cold
But to taking sample to pass through after room temperature1H NMR carry out quantitative analysis.
5. a kind of miscellaneous more metal efficient catalytics of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester according to claim 2
Agent, which is characterized in that in the first step synthesizes 5- allyl -3- methoxysalicylic hydrazides, 5- allyl -3- methoxysalicylic acids
Methyl esters and hydrazine hydrate molar ratio are 1：1 to 1：10；Solvent for use is appointing in methanol, ethyl alcohol, acetonitrile and dioxane
It anticipates a kind of or its arbitrary proportion mixture, at 25~80 DEG C, the reaction time is 2~12h for reaction temperature control.
6. a kind of miscellaneous more metal efficient catalytics of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester according to claim 2
Agent, which is characterized in that in second step synthesis organic ligand L, 5- allyls -3- methoxysalicylics hydrazides and aromatic aldehyde feed intake and rub
You are than being 1：1 to 1：3；Solvent for use is the mixed of any one or its arbitrary proportion in methanol, ethyl alcohol, acetonitrile and dioxane
Object is closed, at 25~80 DEG C, the reaction time is 2~12h for reaction temperature control.
7. a kind of miscellaneous more metal efficient catalytics of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester according to claim 3
Agent, which is characterized in that the molar ratio of ligand L, metal salt and rare-earth salts is 1 in catalyst synthesis：1：1 to 3：2：2；It is used
Solvent is the mixture of any one or its arbitrary proportion in methanol, ethyl alcohol, acetonitrile and DMF, mole of triethylamine and ligand L
Than being 1：1 to 1：6, at 25~40 DEG C, the reaction time is 12~72h for reaction temperature control.
8. a kind of miscellaneous more metal efficient catalytics of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester according to claim 4
Agent, which is characterized in that co-catalyst is PPN-Cl, that is, bi triphenyl phosphine ammonium chloride, TBAB, that is, tetrabutyl phosphonium bromide in catalyst reaction
One kind in ammonium, TBACl, that is, tetrabutylammonium chloride, TBAI, that is, tetrabutylammonium iodide and TBAAc, that is, tetrabutylammonium acetate ammonium；It is above-mentioned to urge
The molar ratio of agent, co-catalyst and epoxide is 1：10：100 to 1：100：400；Pressure carbon dioxide be 0.1~
1.5MPa；Reaction temperature is 60~120 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810335694.2A CN108772102B (en) | 2018-04-16 | 2018-04-16 | High-efficiency catalyst of heteropolymetal for synthesizing cyclic carbonate by high-efficiency catalysis of carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810335694.2A CN108772102B (en) | 2018-04-16 | 2018-04-16 | High-efficiency catalyst of heteropolymetal for synthesizing cyclic carbonate by high-efficiency catalysis of carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108772102A true CN108772102A (en) | 2018-11-09 |
| CN108772102B CN108772102B (en) | 2021-04-23 |
Family
ID=64033891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810335694.2A Active CN108772102B (en) | 2018-04-16 | 2018-04-16 | High-efficiency catalyst of heteropolymetal for synthesizing cyclic carbonate by high-efficiency catalysis of carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108772102B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111215148A (en) * | 2020-03-10 | 2020-06-02 | 辽宁大学 | ZIF @ TU-POP composite catalyst and preparation method and application thereof |
| WO2020169035A1 (en) * | 2019-02-19 | 2020-08-27 | 山东石大胜华化工集团股份有限公司 | Method for preparing alkylene carbonate from alkylene oxide and carbon dioxide |
| CN112961193A (en) * | 2021-02-26 | 2021-06-15 | 西安石油大学 | Linear magnetic tetranuclear nickel complex and preparation method and application thereof |
| CN113289683A (en) * | 2021-06-29 | 2021-08-24 | 福州大学 | Method for synthesizing cyclic carbonate by catalyzing carbon dioxide with polymer as hydrogen bond donor |
| CN114716371A (en) * | 2022-03-10 | 2022-07-08 | 上海应用技术大学 | N-containing active center metal organic catalyst for synthesizing cyclic carbonate and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6737531B1 (en) * | 2002-12-17 | 2004-05-18 | Brookhaven Science Associates, Llc | Catalysts for hydrogenation and hydrosilylation, methods of making and using the same |
| CN1151145C (en) * | 2002-12-06 | 2004-05-26 | 大连理工大学 | Double-function catalyst for synthesizing cyclic carbonate and methyl carbonate |
| CN102229745A (en) * | 2011-06-09 | 2011-11-02 | 大连理工大学 | Crystallizable polycarbonate material based on carbon dioxide and preparation method thereof |
| WO2012121508A2 (en) * | 2011-03-08 | 2012-09-13 | Sk Innovation Co., Ltd. | Method for preparing carbon dioxide/epoxide copolymers containing ether linkages |
| CN106423282A (en) * | 2016-09-21 | 2017-02-22 | 大连理工大学 | Preparation method and application of triphenylamino metal organic framework compound capable of catalyzing carbon dioxide-epoxy compound cycloaddition |
| CN107778473A (en) * | 2017-10-30 | 2018-03-09 | 河南工程学院 | A kind of catalyst for preparing polycyclohexene with 7-oxa-bicyclo[4.1.0 copolyreaction for carbon dioxide |
-
2018
- 2018-04-16 CN CN201810335694.2A patent/CN108772102B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151145C (en) * | 2002-12-06 | 2004-05-26 | 大连理工大学 | Double-function catalyst for synthesizing cyclic carbonate and methyl carbonate |
| US6737531B1 (en) * | 2002-12-17 | 2004-05-18 | Brookhaven Science Associates, Llc | Catalysts for hydrogenation and hydrosilylation, methods of making and using the same |
| WO2012121508A2 (en) * | 2011-03-08 | 2012-09-13 | Sk Innovation Co., Ltd. | Method for preparing carbon dioxide/epoxide copolymers containing ether linkages |
| CN102229745A (en) * | 2011-06-09 | 2011-11-02 | 大连理工大学 | Crystallizable polycarbonate material based on carbon dioxide and preparation method thereof |
| CN106423282A (en) * | 2016-09-21 | 2017-02-22 | 大连理工大学 | Preparation method and application of triphenylamino metal organic framework compound capable of catalyzing carbon dioxide-epoxy compound cycloaddition |
| CN107778473A (en) * | 2017-10-30 | 2018-03-09 | 河南工程学院 | A kind of catalyst for preparing polycyclohexene with 7-oxa-bicyclo[4.1.0 copolyreaction for carbon dioxide |
Non-Patent Citations (2)
| Title |
|---|
| CONG XU ETAL.: "New Lanthanide (III) Coordination Polymers: Synthesis, Structural Features, and Catalytic Activity in CO2 Fixation", 《DALTON TRANSACTIONS》 * |
| 柏东升等: "双功能金属卟啉催化环氧化合物与CO2偶联反应合成环碳酸酯", 《催化学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020169035A1 (en) * | 2019-02-19 | 2020-08-27 | 山东石大胜华化工集团股份有限公司 | Method for preparing alkylene carbonate from alkylene oxide and carbon dioxide |
| CN111215148A (en) * | 2020-03-10 | 2020-06-02 | 辽宁大学 | ZIF @ TU-POP composite catalyst and preparation method and application thereof |
| CN111215148B (en) * | 2020-03-10 | 2022-06-14 | 辽宁大学 | ZIF @ TU-POP composite catalyst and preparation method and application thereof |
| CN112961193A (en) * | 2021-02-26 | 2021-06-15 | 西安石油大学 | Linear magnetic tetranuclear nickel complex and preparation method and application thereof |
| CN112961193B (en) * | 2021-02-26 | 2023-09-29 | 西安石油大学 | Linear magnetic tetranuclear nickel complex and preparation method and application thereof |
| CN113289683A (en) * | 2021-06-29 | 2021-08-24 | 福州大学 | Method for synthesizing cyclic carbonate by catalyzing carbon dioxide with polymer as hydrogen bond donor |
| CN114716371A (en) * | 2022-03-10 | 2022-07-08 | 上海应用技术大学 | N-containing active center metal organic catalyst for synthesizing cyclic carbonate and preparation method and application thereof |
| CN114716371B (en) * | 2022-03-10 | 2023-09-26 | 上海应用技术大学 | N-containing active center metal organic catalyst for synthesizing cyclic carbonate, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108772102B (en) | 2021-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108772102A (en) | Miscellaneous more metal effective catalysts of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester | |
| CN104497018B (en) | Triazole-copper perchlorate complex with p-fluorophenylboronic acid catalyzing effect and preparation method of triazole-copper perchlorate complex | |
| CN105348071B (en) | One class is based on the preparation method and applications of the discrete type metal organic nanotube that tetraphenyl ethylene derivative is constructed | |
| CN106423282B (en) | The preparation method and application of triphenylamine base metal organic framework compound with catalysis carbon dioxide and epoxide cycloaddition | |
| CN109134881A (en) | A kind of preparation method and application based on copper complex heterogeneous catalysis material | |
| CN103396457A (en) | Schiff base cobalt compound and preparation method thereof as well as preparation method of polycarbonate | |
| CN107739444A (en) | Based on amino functional YbIIIMetal-organic framework material of six core molecule construction units and its preparation method and application | |
| CN107175133A (en) | A kind of silicon dioxide carried copper dipyridyl catalyst and preparation method thereof | |
| CN109734740A (en) | A kind of borate family metal organic framework compound and preparation method thereof | |
| CN101830918A (en) | Synthetic method of polynitrogen azole zinc/cadmium framework material | |
| CN105566623A (en) | Polycarbonate material and preparation method thereof | |
| CN104801337A (en) | Ethanol catalyst prepared from synthesis gas and dimethyl ether with one-step method as well as preparation method of ethanol catalyst | |
| CN106748994A (en) | Based on YbIIIThe metal-organic framework material of five core molecule construction units and its preparation method and application | |
| CN114716371A (en) | N-containing active center metal organic catalyst for synthesizing cyclic carbonate and preparation method and application thereof | |
| CN113817174A (en) | Preparation method and application of in-situ hydrazide three-dimensional MOFs material | |
| CN113694968A (en) | Palladium-loaded magnetic UiO-66 ternary composite catalytic material and preparation method and application thereof | |
| CN110885314B (en) | Metal ion liquid, preparation method thereof and application of metal ion liquid in preparation of cyclic carbonate by catalyzing carbon dioxide cycloaddition reaction | |
| CN117244594A (en) | Method for preparing MOF-76 catalyst with carbon dioxide cycloaddition catalysis performance in large scale | |
| CN114790281B (en) | Metal-based ionic liquid catalyst for preparing polyester by coupling reaction and preparation method and application thereof | |
| CN110302840A (en) | A kind of MnO2The preparation method and application of/Cu-Al-BTC ternary metal organic framework material | |
| CN105504305A (en) | Coordination polymer containing 3-(4-pyridine) pyrazole-propionic acid as well as preparation method and application thereof | |
| CN109261204A (en) | A kind of green scale is combined to the method and application of functionalization UiO-66 (Zr) | |
| CN109453757A (en) | A kind of CO2Efficient Conversion is the nano-composite catalyst and preparation method thereof of cyclic carbonate ester | |
| CN105732487B (en) | A kind of metal organic frame containing five core ytterbium cluster molecule construction units and its preparation method and application | |
| CN113351253A (en) | Preparation method of MOF @ COF core-shell composite material with acid-base concerted catalysis function |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |