CN116355227A - Double-metal cyanide complex catalyst modified by metal organic framework material, preparation method and application thereof - Google Patents
Double-metal cyanide complex catalyst modified by metal organic framework material, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 46
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 39
- 229920000570 polyether Polymers 0.000 claims abstract description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 33
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 33
- 239000013148 Cu-BTC MOF Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 21
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims description 45
- 239000013110 organic ligand Substances 0.000 claims description 40
- 238000001914 filtration Methods 0.000 claims description 38
- 239000011259 mixed solution Substances 0.000 claims description 33
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- -1 halide anion Chemical group 0.000 claims description 13
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- OSASVXMJTNOKOY-UHFFFAOYSA-N chlorobutanol Chemical compound CC(C)(O)C(Cl)(Cl)Cl OSASVXMJTNOKOY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 6
- 229960004926 chlorobutanol Drugs 0.000 claims description 5
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229920001748 polybutylene Polymers 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- BAVMXDNHWGQCSR-UHFFFAOYSA-N 1-[2-(2,3-dimethylphenyl)ethyl]-2,3-dimethylbenzene Chemical group CC1=CC=CC(CCC=2C(=C(C)C=CC=2)C)=C1C BAVMXDNHWGQCSR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 abstract description 6
- 229920000515 polycarbonate Polymers 0.000 abstract description 6
- 239000004417 polycarbonate Substances 0.000 abstract description 6
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 5
- 125000002947 alkylene group Chemical group 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 17
- 229910007564 Zn—Co Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910017061 Fe Co Inorganic materials 0.000 description 6
- 239000004593 Epoxy Chemical class 0.000 description 5
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910007567 Zn-Ni Inorganic materials 0.000 description 3
- 229910007614 Zn—Ni Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
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- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000013084 copper-based metal-organic framework Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- VZHHNBNSMNNUAD-UHFFFAOYSA-N cobalt 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound [Co].OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VZHHNBNSMNNUAD-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
- C08G64/183—Block or graft polymers containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a double-metal cyanide complex catalyst modified by a metal organic framework material, a preparation method and application thereof, wherein the double-metal cyanide complex catalyst is modified by introducing a Cu-based HKUST-1 metal organic framework material by an impregnation method, and the preparation method is simple in preparation steps and convenient to operate; the double metal cyanide complex catalyst modified by the metal organic framework material can realize the copolymerization of carbon dioxide and alkylene oxide under a milder condition without adding a cocatalyst and a solvent, and the catalyst conversion rate and selectivity of the polycarbonate polyether prepared by the copolymerization of carbon dioxide and propylene oxide can be effectively improved due to the synergistic effect of the metal organic framework material HKUST-1 and DMC metal center ions, so that the prepared polycarbonate-polyether has higher carbonate unit content and lower cyclic carbonate content.
Description
Technical Field
The invention relates to the technical field of catalyst modification, in particular to a double metal cyanide complex catalyst modified by a metal organic framework material, a preparation method and application thereof.
Background
Carbon dioxide is considered to be the main gas responsible for the "greenhouse effect", but is also the main carbon resource on earth, with a total reserve greater than the sum of the total reserves of coal, oil, and gas. Therefore, the carbon dioxide is fully utilized as the resource endowment of the maximum carbon resource to prepare the polymer material, so that the harm to the environment can be reduced, and the excessive consumption of non-renewable carbon resources such as petroleum can be reduced, so that the development environment of the polymer material is friendly and sustainable.
The polycarbonate-polyether prepared by copolymerizing carbon dioxide and epoxy compounds (ethylene oxide, propylene oxide and the like) is one of high polymer materials with great development prospect. The polycarbonate-polyether is a high molecular compound with a structure comprising polycarbonate chain links and polyether chain links, and the polyurethane material prepared by the polycarbonate-polyether has the excellent characteristics of polyester polyurethane and polyether polyurethane, can effectively improve the physical characteristics of tear resistance, compression deformation, elongation and the like of polyurethane products, and is widely applied to the fields of adhesives, toughening agents, composite materials and the like.
Common catalysts reported for the copolymerization of carbon dioxide and an epoxy compound include metal carboxylate catalyst systems, metalloporphyrin catalyst systems, diethyl zinc catalyst systems, salen-Co catalyst systems, double Metal Cyanide (DMC) catalyst systems, etc., which have been attracting attention due to their high catalytic activity and the feature of no need for post-treatment.
Patent US4500704 reports a process for preparing double metal cyanide catalysts with glyme as a ligand and using it to catalyze the copolymerization of carbon dioxide and epoxy compounds to prepare aliphatic polycarbonates, the polycarbonate content being 76%, but the by-product cyclic carbonate reaching 18%; patent CN102432857a reports a method of using Zn 3 [Co(CN) 6 ] 2 Method for preparing composite catalyst by doping rare earth with double metal cyanide, and composite catalyst used for catalyzing carbon dioxide and epoxyThe copolymerization of the compound has high reaction efficiency, but the fixed amount of carbon dioxide is low. Patent CN101020747a reports that a functional Salen MnX catalyst performs copolymerization of carbon dioxide and propylene oxide, and the content of carbonate units in the product reaches more than 99%, but the catalytic activity is lower than that of the DMC catalyst. Patent CN110964192a reports a method for improving amorphous and amorphous structure proportion of a catalyst by adopting a mixed modification bimetallic catalyst of inorganic acid and organic acid, and the catalyst is used for copolymerization of carbon dioxide and epoxy compound, the fixed amount of carbon dioxide is higher, but the content of byproduct cyclic carbonate is higher, and the molecular weight distribution of polycarbonate is wider. .
Disclosure of Invention
Therefore, based on the background, the invention improves the prior art, provides a method for modifying the double metal cyanide complex catalyst by adopting a metal organic framework material, prepares the double metal cyanide complex catalyst modified by the metal organic framework material, and applies the double metal cyanide complex catalyst to a reaction system for preparing polycarbonate-polyether by carbon dioxide and an epoxy compound, and has the advantages of low catalyst consumption, high catalytic activity, high carbonate content and the like.
The technical scheme provided by the invention is as follows:
a double metal cyanide complex catalyst modified with a metal organic framework material, characterized in that its composition can be represented by the chemical formula of formula (1):
M 1 a [M 2 b (CN) c ] d ·wM 1 X 2 ·xL 1 ·yL 2 ·zH 2 O@HKUST-1 (1)
wherein M is 1 Is a divalent metal ion; m is M 2 Is a divalent or trivalent metal ion; x is a halide anion;
L 1 is an organic ligand of alcohols, ketones and ethers;
L 2 is an organic ligand;
in the formula (1), a, b, c, d is a positive integer; w, x, y, z is zero or positive.
Further, the M 1 Selected from Zn 2+ 、Fe 2+ 、Cu 2+ 、Co 2+ 、Ni 2+ One of the following;
the M is 2 Selected from Ni 2+ 、Cu 2+ 、Fe 3+ 、Co 3+ One of the following;
x is selected from halogen anions, F — 、Cl — 、Br — 、I — One of the following;
the L is 1 One selected from propanol, n-butanol, isopropanol, tert-butanol, chlorobutanol, 2, 3-pentanedione, 2, 5-hexanedione, 2' -dichloro diethyl ether and dioxane;
the L is 2 One selected from polytetrahydrofuran polyether, polytetrahydrofuran propoxylene polyether, polytetrahydrofuran ethoxylene polyether, polytetrahydrofuran propoxylene block polyether and polybutylene oxide polyether.
Further, the metal organic framework material used for modification is selected from Cu-based HKUST-1 metal organic framework materials.
Preferably, the preparation method of the Cu-based HKUST-1 metal organic framework material can be disclosed by reference to Stephen S. -Y.Chui, et al, science,1999,283,1148-1150.
Specifically, the following are:
cu (NO) 3 ) 2 ·3H 2 O-dissolved deionized water;
dissolving trimesic acid (BTC) in ethanol;
mixing and stirring the two solutions;
the mixed solution is reacted for 8 hours at 120 ℃ in a reaction kettle, cooled and filtered;
and repeatedly washing the filtered solid with dichloromethane for 3 times, soaking the solid with dichloromethane for 24 hours, and vacuum drying the obtained solid at 80 ℃ to obtain the Cu-based HKUST-1 metal organic framework material.
The invention also provides:
the preparation method of the double metal cyanide complex catalyst modified by the metal organic framework material comprises the following steps:
s1, taking deionized waterL 1 Mixing organic ligand solution to prepare L 1 An organic ligand mixed solution;
dissolving water-soluble halogenated metal salt in L 1 Adding Cu-based HKUST-1 metal organic framework material into the organic ligand mixed solution after fully stirring and mixing, fully dispersing, and standing to enable halogenated metal salt to be fully attached to the inside of a pore canal of the HKUST-1 metal organic framework material;
s2, dissolving cyanide metal salt in deionized water, slowly adding the cyanide metal salt into the S1 mixed solution, fully stirring, filtering and separating, and taking a filter cake;
s3, use L 1 Washing the filter cake separated by the S2 by the organic ligand mixed solution, and then filtering and separating to obtain a filter cake;
continue to use L after 1 Further washing the filter cake by the organic ligand solution, filtering and separating to obtain the filter cake;
s4, use L 1 Slurrying the filter cake obtained in the step S3 by using an organic ligand solution, and adding L 2 And (3) stirring and mixing the organic ligand, filtering, and vacuum drying the obtained filter cake to obtain the metal-organic framework material modified double metal cyanide complex catalyst (DMC@HKUST-1 catalyst).
Further, the mass ratio of the water-soluble halogenated metal salt to the Cu-based HKUST-1 metal organic framework material used in the step S1 is 0.05-10:1,
preferably 0.1-8:1, more preferably 0.2-5:1.
Further, the mass ratio of the water-soluble metal halide salt to the metal cyanide salt used in steps S1 and S2 is 0.5-20:1, preferably 1-15:1, more preferably 1-10:1.
Further, deionized water and L in step S1 1 The volume ratio of the organic ligand solution is 0.1-5:1, preferably 0.2-3:1, more preferably 0.5-2:1.
Further, the L in step S4 2 The number average molecular weight of the organic ligand is 1000 to 16000, preferably 1500 to 10000, more preferably 2000 to 8000.
Further, L is adopted in the S3 1 The times of washing and filtering the filter cake by the organic ligand mixed solution is 1-5;
using L 1 The organic ligand solution is washed and filtered for 1-3 times.
Further, the operation temperature of each of the steps S1 to S4 is controlled to 10 to 100 ℃, preferably 10 to 90 ℃, more preferably 20 to 80 ℃.
The invention also provides:
the preparation method of polycarbonate-polyether adopts the double metal cyanide complex catalyst modified by the metal organic framework material as a catalyst to carry out copolymerization reaction.
Further, it comprises the following steps:
(1) Adding an initiator and a catalyst into a high-pressure reaction kettle to carry out high-temperature dehydration; then introducing carbon dioxide gas for replacement;
(2) Propylene oxide or ethylene oxide is added, carbon dioxide gas is pressed in, a certain pressure of a reaction kettle is maintained, and the reaction is carried out at a certain temperature;
(3) Releasing unreacted carbon dioxide gas;
vacuumizing the product to remove small molecular monomers, adding a solvent for dilution, and filtering to obtain filtrate;
and (3) sequentially carrying out reduced pressure distillation, washing and drying on the filtrate to obtain the polycarbonate-polyether.
Further, the initiator is selected from one or more of small molecule alcohols, polyether polyols, carboxylic acids and phenols.
Further, the reaction temperature in the step (2) is controlled to be 30 to 160 ℃, preferably 40 to 120 ℃, more preferably 50 to 100 ℃;
the pressure is controlled to be 0.5 to 5MPa, preferably 1 to 4MPa, more preferably 1.5 to 3MPa.
Further, the mass ratio of the propylene oxide or the ethylene oxide to the catalyst is 1000:1-100000:1, preferably 2000:1-80000:1, more preferably 5000:1-50000:1.
Further, the reaction time of the copolymerization in the step (2) is controlled to be 5 to 24 hours, preferably 6 to 18 hours, more preferably 8 to 16 hours.
Further, the solvent used for dilution in step (3) is selected from one or more of dichloromethane, dichloroethane, acetone, tetrahydrofuran and absolute ethanol.
By adopting the technical scheme, the beneficial effects are as follows:
the Cu-based HKUST-1 metal organic framework material is introduced by an impregnation method to modify the double-metal cyanide complex catalyst, and the preparation method has the advantages of simple preparation steps and convenient operation;
the double metal cyanide complex catalyst modified by the metal organic framework material can realize the copolymerization of carbon dioxide and alkylene oxide under a milder condition without adding a cocatalyst and a solvent, and the catalyst conversion rate and selectivity of the polycarbonate polyether prepared by the copolymerization of carbon dioxide and propylene oxide can be effectively improved due to the synergistic effect of the metal organic framework material HKUST-1 and DMC metal center ions, so that the prepared polycarbonate-polyether has higher carbonate unit content and lower cyclic carbonate content.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is further illustrated below with reference to examples.
Example 1: the preparation method of the bimetal (Zn-Co) cyanide complex catalyst modified by the metal organic framework material comprises the following steps:
1. preparation of Cu-based HKUST-1 metal organic framework material:
8.46g Cu (NO) 3 ) 2 ·3H 2 O-dissolved 15mL deionized water; 3.89g of trimesic acid (BTC) was dissolved in 150mL of ethanol; mixing the above two solutions, and stirring for 45min; mixing the solution toReacting for 8 hours at 120 ℃ in a reaction kettle, cooling and filtering; the solid obtained by filtering is repeatedly washed 3 times by using 100mL of dichloromethane, then is soaked for 24 hours by using 100mL of dichloromethane, and the obtained solid is dried in vacuum at 80 ℃ to obtain the Cu-based HKUST-1 metal organic framework material.
2. Preparation of Zn-Co DMC@HKUST-1 catalyst:
s1, mixing deionized water (30 mL) and tertiary butanol (30 mL) to prepare tertiary butanol organic ligand mixed solution;
3.75g ZnCl was weighed out 2 Dissolving in tertiary butanol organic ligand mixed solution, stirring thoroughly for 30min, adding 5g of Cu-based metal organic framework material HKUST-1, oscillating for 30min, placing in an ultrasonic dispersing instrument for ultrasonic dispersion for 2 hr with ultrasonic power of 100W, standing for 8 hr to obtain ZnCl 2 Fully attached to the inside of the pore canal of the HKUST-1 material;
s2, weighing 1.41 and 1.41g K 3 [Co(CN) 6 ]Dissolving in 10mL deionized water, slowly dripping into the S1 mixed solution, fully mixing and stirring for 2 hours, and filtering to separate a filter cake;
s3, washing and filtering the filter cake separated from the S2 by using a tertiary butanol organic ligand mixed solution for 3 times; further washing and filtering the filter cake by using 50mL of tertiary butanol solution for 2 times;
s4, slurrying the filter cake by using 20mL of tertiary butanol solution, adding polytetrahydrofuran polyether with the number average molecular weight of 3000, stirring and mixing for 30min, standing for 1 hour, filtering, and vacuum drying the obtained filter cake at 60 ℃ for 24 hours to prepare the Zn-Co DMC-1@HKUST-1 catalyst.
The purity of the t-butanol solution used in this example was 99.5% or more, and the purity of the small molecule alcohol used in the following example was similar.
Example 2: the preparation method of the bimetal (Zn-Co) cyanide complex catalyst modified by the metal organic framework material comprises the following steps:
1. preparation of Cu-based HKUST-1 metal organic framework material:
as in example 1.
2. Preparation of Zn-Co DMC-2@HKUST-1 catalyst:
in this example, 6g of Cu-based HKUST-1 metal organic framework material was added in step S1, and the other operations were the same as in example 1 to prepare a Zn-Co DMC-2@HKUST-1 catalyst.
Example 3: the preparation method of the bimetal (Zn-Fe) cyanide complex catalyst modified by the metal organic framework material comprises the following steps:
1. preparation of Cu-based HKUST-1 metal organic framework material:
as in example 1.
2. Preparation of Zn-Fe DMC@HKUST-1 catalyst:
s1, mixing deionized water (30 mL) and tertiary butanol (30 mL) to prepare a trichloro tertiary butanol organic ligand mixed solution;
3.75g ZnCl was weighed out 2 Dissolving in a mixed solution of trichloro organic ligand, fully stirring and mixing for 30min, adding 5g of Cu-based HKUST-1 metal organic framework material, oscillating for 30min, placing in an ultrasonic dispersing instrument for ultrasonic dispersion for 2 h with ultrasonic power of 100W, and standing for 8h to obtain ZnCl 2 Fully attached to the inside of the pore canal of the HKUST-1 material;
s2, weighing 1.55 and 1.55g K 3 [Fe(CN) 6 ]Dissolving in 10mL deionized water, slowly dripping into the S1 mixed solution, fully mixing and stirring for 2 hours, and filtering to separate a filter cake;
s3, washing and filtering the filter cake separated from the S2 by using the mixed solution of the chlorobutanol and the organic ligand for 3 times; further washing and filtering the filter cake by using 50mL of chlorbutanol solution for 2 times;
s4, slurrying the filter cake by using 20mL of chlorobutanol solution, adding polybutylene oxide polyether with the number average molecular weight of 5000, stirring and mixing for 30min, standing for 1 hour, filtering, and vacuum drying the obtained filter cake at 60 ℃ for 24 hours to prepare the Zn-Fe DMC@HKUST-1 catalyst.
Example 4: the preparation method of the bimetal (Zn-Ni) cyanide complex catalyst modified by the metal organic framework material comprises the following steps:
1. preparation of Cu-based HKUST-1 metal organic framework material:
as in example 1.
2. Preparation of Zn-Ni DMC@HKUST-1 catalyst:
s1, mixing deionized water (30 mL) and 2,2' -dichloro diethyl ether (30 mL) to prepare a dichloro diethyl ether organic ligand mixed solution;
3.75g ZnCl was weighed out 2 Dissolving in dichloro diethyl ether organic ligand mixture, stirring thoroughly for 30min, adding 5g Cu-based HKUST-1 metal organic framework material, oscillating for 30min, ultrasonic dispersing in ultrasonic dispersing instrument for 2 hr with ultrasonic power of 100W, standing for 8 hr to obtain ZnCl 2 The solution is fully adhered to the inside of the pore canal of the HKUST-1 material;
s2, weighing 1.72 and 1.72g K 2 [Ni(CN) 4 ]Dissolving in 10mL deionized water, slowly dripping into the S1 mixed solution, fully mixing and stirring for 2 hours, and filtering to separate a filter cake;
s3, washing and filtering the filter cake separated from the S2 by using a dichloro diethyl ether organic ligand mixed solution for 3 times; further washing and filtering the filter cake by using 50mL of 2,2' -dichloro diethyl ether solution for 2 times;
s4, slurrying a filter cake by using 20mL of 2,2' -dichloro diethyl ether solution, adding polytetrahydrofuran propoxyl polyether with a number average molecular weight of 3000, stirring and mixing for 30min, standing for 1 hour, filtering, and vacuum drying the obtained filter cake at 60 ℃ for 24 hours to prepare the Zn-Ni DMC@HKUST-1 catalyst.
Example 5: the preparation method of the bimetal (Fe-Co) cyanide complex catalyst modified by the metal organic framework material comprises the following steps:
1. preparation of Cu-based metal organic framework material HKUST-1:
as in example 1.
2. Preparation of Fe-Co DMC@HKUST-1 catalyst:
s1, mixing deionized water (30 mL) and tertiary butanol (30 mL) to prepare tertiary butanol organic ligand mixed solution;
weigh 3.55g FeCl 2 Dissolving in tertiary butanol organic ligand mixed solution, stirring thoroughly for 30min, adding 5g Cu-based HKUST-1 metal organic framework material, oscillating for 30min, and placing in an ultrasonic dispersing instrument for ultrasonic dispersion for 2 hr with ultrasonic power of 100WStanding for 8 hr to make ZnCl 2 The solution is fully adhered to the inside of the pore canal of the HKUST-1 material;
s2, weighing 1.72 and 1.72g K 3 [Co(CN) 6 ]Dissolving in 10mL deionized water, slowly dripping into the S1 mixed solution, fully mixing and stirring for 2 hours, and filtering to separate a filter cake;
s3, washing and filtering the filter cake separated from the S2 by using a tertiary butanol organic ligand mixed solution for 3 times; further washing and filtering the filter cake by using 50mL of tertiary butanol solution for 2 times;
s4, slurrying the filter cake by using 20mL of tertiary butanol solution, adding polytetrahydrofuran propoxyl polyether with the number average molecular weight of 3000, stirring and mixing for 30min, standing for 1 hour, filtering, and vacuum drying the obtained filter cake at 60 ℃ for 24 hours to prepare the Fe-Co DMC@HKUST-1 catalyst.
Example 6: the DMC@HKUST-1 catalyst prepared in examples 1 to 5 was used in the copolymerization of alkylene oxide with carbon dioxide to prepare a polycarbonate-polyether system, and the specific procedures are as follows:
10g PPG-400 (polypropylene glycol-400) and DMC@HKUST-1 catalyst are added into a 500mL high-pressure reaction kettle to carry out high-temperature dehydration, and then 100mL propylene oxide is respectively added after the high-temperature dehydration is carried out through the replacement of dry carbon dioxide gas, and the carbon dioxide gas is pressed in;
keeping the pressure of the reaction kettle to be 2MPa, and reacting for 12 hours at the temperature of 80 ℃; releasing unreacted carbon dioxide gas, vacuumizing to remove micromolecular monomers, adding 100mL of methylene dichloride, filtering, distilling under reduced pressure, washing and drying to obtain the polycarbonate-polyether.
The DMC@HKUST-1 catalyst prepared in examples 1-5 catalyzes the copolymerization of carbon dioxide and propylene oxide, and the results are shown in Table 1.
Comparative example 1: preparation of Zn-Co DMC catalyst:
s1, mixing deionized water (30 mL) and tertiary butanol (30 mL) to prepare tertiary butanol organic ligand mixed solution;
3.75g ZnCl was weighed out 2 Dissolving in tertiary butanol organic ligand mixed solution, and fully stirring and mixing for 30min;
S2、weigh 1.41g K 3 [Co(CN) 6 ]Dissolving in 10mL deionized water, slowly dripping into the S1 mixed solution, fully mixing and stirring for 2 hours, and filtering to separate a filter cake;
s3, washing and filtering the filter cake separated from the S2 by using a tertiary butanol organic ligand mixed solution for 3 times; further washing and filtering the filter cake by using 50mL of tertiary butanol solution for 2 times;
s4, slurrying the filter cake by using 20mL of tertiary butanol solution, adding polytetrahydrofuran polyether with the number average molecular weight of 3000, stirring and mixing for 30min, standing for 1 hour, filtering, and vacuum drying the obtained filter cake at 60 ℃ for 24 hours to prepare the Zn-Co DMC catalyst. The reaction conditions were the same as in example 6, and the result of copolymerization of carbon dioxide and propylene oxide catalyzed by Zn-Co DMC catalyst is shown in Table 1.
Comparative example 2: preparation of Fe-Co DMC catalyst:
s1, mixing deionized water (30 mL) and tertiary butanol (30 mL) to prepare tertiary butanol organic ligand mixed solution;
weigh 3.55g FeCl 2 Dissolving in tertiary butanol organic ligand mixed solution, and fully stirring and mixing for 30min;
s2, weighing 1.72 and 1.72g K 3 [Co(CN) 6 ]Dissolving in 10mL deionized water, slowly dripping into the S1 mixed solution, fully mixing and stirring for 2 hours, and filtering to separate a filter cake;
s3, washing and filtering the filter cake separated from the S2 by using a tertiary butanol organic ligand mixed solution for 3 times; further washing and filtering the filter cake by using 50mL of tertiary butanol solution for 2 times;
s4, slurrying a filter cake by using 20mL of tertiary butanol solution, adding polytetrahydrofuran propoxyl polyether with a number average molecular weight of 3000, stirring and mixing for 30min, standing for 1 hour, filtering, and vacuum drying the obtained filter cake at 60 ℃ for 24 hours to prepare the Fe-Co DMC catalyst.
The reaction conditions were the same as in example 6, and the results of the copolymerization of carbon dioxide and propylene oxide catalyzed by the Fe-Co DMC catalyst are shown in Table 1.
Table 1: examples 1-5 and comparative examples 1, 2 catalyze the copolymerization of carbon dioxide and propylene oxide
As can be seen from Table 1, the double metal cyanide complex catalyst modified by the metal organic framework material provided by the invention is used for catalyzing the copolymerization reaction of carbon dioxide and propylene oxide, and compared with the double metal cyanide complex catalyst not modified by the metal organic framework material, the catalytic conversion rate of the double metal cyanide complex catalyst is obviously improved, and the prepared polycarbonate-polyether has higher carbonate unit content and lower cyclic carbonate content.
As can be seen from comparative example 1 and comparative example 1, the modified double metal cyanide complex catalyst catalyzes the copolymerization of propylene oxide and carbon dioxide, the conversion rate of propylene oxide is obviously improved, the content of carbonate units reaches 50.6%, and the content of by-product cyclocarbonates is as low as 5.8%; as can be seen from comparative example 5 and comparative example 2, the modified double metal cyanide complex catalyst catalyzes the copolymerization of propylene oxide and carbon dioxide, the conversion rate of propylene oxide is obviously improved, the content of carbonate units reaches 43.1%, and the content of by-product cyclocarbonates is as low as 6.1%.
In conclusion, comparison experiments prove that the double metal cyanide complex catalyst modified by the Cu-based HKUST-1 metal organic framework material has obviously improved reaction selectivity by introducing an organic active framework, and can better improve the copolymerization reaction effect of carbon dioxide and propylene oxide.
The invention and its embodiments have been described above with no limitation, but the examples shown are only one of the embodiments of the invention, and the actual structure is not limited thereto. In summary, if one of ordinary skill in the art is informed by this disclosure, a structural manner and an embodiment similar to the technical solution should not be creatively devised without departing from the gist of the present invention.
Claims (10)
1. A double metal cyanide complex catalyst modified with a metal organic framework material, characterized in that its composition can be represented by the chemical formula of formula (1):
M 1 a [M 2 b (CN) c ] d ·wM 1 X 2 ·xL 1 ·yL 2 ·zH 2 O@HKUST-1(1)
wherein M is 1 Is a divalent metal ion; m is M 2 Is a divalent or trivalent metal ion; x is a halide anion;
L 1 is an organic ligand of alcohols, ketones and ethers;
L 2 is an organic ligand;
in the formula (1), a, b, c, d is a positive integer; w, x, y, z is zero or positive.
2. The metal-organic framework material modified double metal cyanide complex catalyst of claim 1,
the M is 1 Selected from Zn 2+ 、Fe 2+ 、Cu 2+ 、Co 2+ 、Ni 2+ One of the following;
the M is 2 Selected from Ni 2+ 、Cu 2+ 、Fe 3+ 、Co 3+ One of the following;
x is selected from halogen anions, F — 、Cl — 、Br — 、I — One of the following;
the L is 1 One selected from propanol, n-butanol, isopropanol, tert-butanol, chlorobutanol, 2, 3-pentanedione, 2, 5-hexanedione, 2' -dichloro diethyl ether and dioxane;
the L is 2 One selected from polytetrahydrofuran polyether, polytetrahydrofuran propoxylene polyether, polytetrahydrofuran ethoxylene polyether, polytetrahydrofuran propoxylene block polyether and polybutylene oxide polyether.
3. The metal organic framework material modified double metal cyanide complex catalyst according to claim 1 or 2, wherein the metal organic framework material used for modification is selected from Cu-based HKUST-1 metal organic framework materials.
4. A process for the preparation of a metal-organic framework material-modified double metal cyanide complex catalyst as claimed in any one of claims 1 to 3,
the method comprises the following steps:
s1, taking deionized water and L 1 Mixing organic ligand solution to prepare L 1 An organic ligand mixed solution;
dissolving water-soluble halogenated metal salt in L 1 Adding Cu-based HKUST-1 metal organic framework material into the organic ligand mixed solution after fully stirring and mixing, fully dispersing, and standing to enable halogenated metal salt to be fully attached to the inside of a pore canal of the HKUST-1 metal organic framework material;
s2, dissolving cyanide metal salt in deionized water, slowly adding the cyanide metal salt into the S1 mixed solution, fully stirring, filtering and separating, and taking a filter cake;
s3, use L 1 Washing the filter cake separated by the S2 by the organic ligand mixed solution, and then filtering and separating to obtain a filter cake;
continue to use L after 1 Further washing the filter cake by the organic ligand solution, filtering and separating to obtain the filter cake;
s4, use L 1 Slurrying the filter cake obtained in the step S3 by using an organic ligand solution, and adding L 2 And (3) stirring and mixing the organic ligand, filtering, and vacuum drying the obtained filter cake to obtain the double metal cyanide complex catalyst modified by the metal organic framework material.
5. The method for preparing a metal-organic framework material modified double metal cyanide complex catalyst according to claim 4,
the mass ratio of the water-soluble halogenated metal salt to the Cu-based HKUST-1 metal organic framework material used in the step S1 is 0.05-10:1.
6. The method for preparing a metal-organic framework material modified double metal cyanide complex catalyst according to claim 4,
the mass ratio of the water-soluble halogenated metal salt to the cyanide metal salt used in the steps S1 and S2 is 0.5-20:1.
7. A method for preparing polycarbonate-polyether, which is characterized in that the polycarbonate-polyether is prepared by copolymerization reaction by using the double metal cyanide complex catalyst modified by the metal organic framework material as defined in any one of claims 1 to 7 as a catalyst.
8. The method for producing a polycarbonate-polyether according to claim 7, wherein,
the method comprises the following steps:
(1) Adding an initiator and a catalyst into a high-pressure reaction kettle to carry out high-temperature dehydration; then introducing carbon dioxide gas for replacement;
(2) Propylene oxide or ethylene oxide is added, carbon dioxide gas is pressed in, a certain pressure of a reaction kettle is maintained, and the reaction is carried out at a certain temperature;
(3) Releasing unreacted carbon dioxide gas;
vacuumizing the product to remove small molecular monomers, adding a solvent for dilution, and filtering to obtain filtrate;
and (3) sequentially carrying out reduced pressure distillation, washing and drying on the filtrate to obtain the polycarbonate-polyether.
9. The method for preparing polycarbonate-polyether according to claim 8, wherein the initiator is one or more selected from the group consisting of small molecule alcohols, polyether polyols, carboxylic acids and phenols.
10. The method for producing a polycarbonate-polyether according to claim 8, wherein the reaction temperature in the step (2) is controlled to 30 to 160℃and the pressure is controlled to 0.5 to 5MPa.
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