CN105381819B - The preparation method of support type bi-quaternary ammonium salt catalyst and preparation method thereof and cyclic carbonate - Google Patents
The preparation method of support type bi-quaternary ammonium salt catalyst and preparation method thereof and cyclic carbonate Download PDFInfo
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- CN105381819B CN105381819B CN201510916235.XA CN201510916235A CN105381819B CN 105381819 B CN105381819 B CN 105381819B CN 201510916235 A CN201510916235 A CN 201510916235A CN 105381819 B CN105381819 B CN 105381819B
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- quaternary ammonium
- ammonium salt
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- 239000003054 catalyst Substances 0.000 title claims abstract description 159
- 238000002360 preparation method Methods 0.000 title claims abstract description 59
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 47
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 33
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 30
- 238000005859 coupling reaction Methods 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims description 66
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 47
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 27
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- 150000002367 halogens Chemical class 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 150000001450 anions Chemical class 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 11
- 238000007265 chloromethylation reaction Methods 0.000 claims description 11
- 239000002808 molecular sieve Substances 0.000 claims description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 11
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 10
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- 229920002313 fluoropolymer Polymers 0.000 claims description 9
- 239000004811 fluoropolymer Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 abstract description 20
- 239000003426 co-catalyst Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- 229960004424 carbon dioxide Drugs 0.000 description 29
- 239000007791 liquid phase Substances 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 24
- 238000004587 chromatography analysis Methods 0.000 description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 239000012973 diazabicyclooctane Substances 0.000 description 10
- 230000005311 nuclear magnetism Effects 0.000 description 10
- 238000012797 qualification Methods 0.000 description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005349 anion exchange Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical class OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- -1 MgO Chemical class 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000007210 heterogeneous catalysis Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002431 aminoalkoxy group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- BCUPGIHTCQJCSI-UHFFFAOYSA-N chloromethanol Chemical compound OCCl BCUPGIHTCQJCSI-UHFFFAOYSA-N 0.000 description 2
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 150000002460 imidazoles Chemical group 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- IZQAUUVBKYXMET-UHFFFAOYSA-N 2-bromoethanamine Chemical class NCCBr IZQAUUVBKYXMET-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004927 clay Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- ADDQUOLYROTOKS-UHFFFAOYSA-N iodomethanol Chemical compound OCI ADDQUOLYROTOKS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003222 pyridines Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
-
- 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
- C07D317/38—Ethylene carbonate
-
- 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
- C07D317/44—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 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—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 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
-
- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of support type bi-quaternary ammonium salt catalyst of the present invention, formula (1) is bonded with the carrier of the support type bi-quaternary ammonium salt catalystThe bi-quaternary ammonium salt of expression.The present invention also provides a kind of preparation method of support type bi-quaternary ammonium salt catalyst and its obtained support type bi-quaternary ammonium salt catalyst.The present invention also provides a kind of using preparation method of the above-mentioned support type bi-quaternary ammonium salt catalyst as the cyclic carbonate of catalyst, and the cyclic carbonate is by formula (2)
Description
Technical field
Urged the present invention relates to support type bi-quaternary ammonium salt catalyst and preparation method thereof, and using the support type bi-quaternary ammonium salt
Method of the agent as catalyst preparation cyclic carbonate.
Background technology
Carbon dioxide is current most important greenhouse gases, but it is also a kind of critically important C1 resources simultaneously, and it absorbs
With utilization as one of problem of this century most huge challenge.Cyclic carbonate is a kind of important organic synthesis intermediate,
Medicine, fine chemistry industry synthetic intermediate, lithium battery, resins synthesis etc. have a wide range of applications.Carbon dioxide and epoxidation
Thing coupling prepares the reaction of cyclic carbonate, and its atom utilization is high, meets the direction of the development of Green Chemistry, and realizing
While carbon dioxide utilizes, reduce the discharge of greenhouse gases again.
The catalyst for carbon dioxide and the coupled reaction of epoxides is broadly divided into two classes, i.e. homogeneous catalyst at present
And heterogeneous catalysis.Wherein, homogeneous catalyst mainly includes：Alkali metal, organic phosphine, organic base, ionic liquid, metal combination
The catalyst such as thing；Catalyst synthesis condition is harsh, stability is poor, catalytic performance is not high, recovery often with having such as such catalyst
The defects of difficult and recycling number is not high.At present, more focuses have been placed on the research of heterogeneous catalysis by people
On, heterogeneous catalysis mainly includes：Metal oxide, such as MgO, Al2O3；Molecular sieve and clay class catalyst；Supported catalyst
Agent, such as support type organic base, load type gold metal complex, load-type ion liquid catalyst.Wherein, loaded catalyst by
In catalyst recovery problem can be efficiently solved, reduce the cost of catalyst so as to obtain more concerns.Catalyst
It is divided into physical load and chemical load according to its mode of loading, physical load is inhaled by the physics between functional group and carrier
What attached effect was realized, the stability of such a mode of loading is not relatively high, easily causes the loss of catalyst；And chemical load is logical
The effect realization of chemical bonding is crossed, there is higher stability, effectively reduce the loss of functional group.Change common at present
Learning load includes：Load quaternary amines, pyridines and imidazoles etc..But the heterogeneous catalysis of existing this kind of chemical load type
Still there is the defects of not high catalyst activity, severe reaction conditions, stability difference.
The content of the invention
It is an object of the invention to overcome the existing catalysis for being used to participate in the coupled reaction of carbon dioxide and epoxides
Agent activity is not high, recycles the defects of number is not high, there is provided and it is a kind of that there is higher catalytic activity, and after circulation repeatedly still
The support type bi-quaternary ammonium salt that carbon dioxide and epoxides synthesizing annular carbonate can be catalyzed with high selectivity, in high yield is urged
The preparation method of agent and preparation method thereof and cyclic carbonate.
To achieve these goals, the present invention provides a kind of support type bi-quaternary ammonium salt catalyst, the support type bi-quaternary ammonium salt
The bi-quaternary ammonium salt of formula (1) expression is bonded with the carrier of catalyst,：
Wherein, in formula (1), the X of 2 molecules—It is identical or different, selected from F-、Cl-、Br-、I-、CH3COO-、NO3 -、HSO4 -、
H2PO4 -、[OTf]-、[BF4]-、[SbF6]-、[PF6]-[NTf2]-；N is 1-6 integer；R1For H, OH, NH2Or COOH；Relatively
Molar content in the bi-quaternary ammonium salt part that the support type bi-quaternary ammonium salt catalyst described in 1g, formula (1) represent is 0.5-3mmol；
One or more of the described carrier in silica, mesopore molecular sieve and fluoropolymer resin；Described mesopore molecular sieve
For MCM-41 or SBA-15；Described fluoropolymer resin is styrene resin, chitosan or the Field resin of chloromethylation.
Present invention also offers the preparation method of above-mentioned support type bi-quaternary ammonium salt catalyst, this method includes：
(1) carrier and triethylene diamine are subjected to the first haptoreaction so that triethylene diamine is bonded with support chemistry
To the intermediate product for being connected with triethylene diamine；Described carrier and the usage ratio 1g of triethylene diamine:1-15mmol；It is described
Carrier be silica, mesopore molecular sieve, one kind in fluoropolymer resin and combinations thereof；Described reaction temperature is 10-50
DEG C, reaction time 1-24h；
(2) by intermediate product obtained by step (1) and Formula X '-(CH2)n-R1The second haptoreaction is carried out to obtain with triethylene
The support type bi-quaternary ammonium salt catalyst of diamine structures, triethylene diamine structure are the activearm of support type bi-quaternary ammonium salt catalyst
Point；X' is F-、Cl-、Br-Or I-, n be 1-6 integer, R1For H, OH, NH2Or COOH；Described triethylene diamine and Formula X '-
(CH2)n-R1Mole dosage ratio be 1：1-3；Described reaction temperature is 60-90 DEG C, reaction time 1-48h.
This method also includes, and the support type bi-quaternary ammonium salt catalyst that step (2) is obtained is with containing CH3COO-、NO3 -、
HSO4 -、H2PO4 -、[OTf]-、[BF4]-、[SbF6]-、[PF6]-[NTf2]-In one or more anion salt solution carry out
Contact, obtains anion X—For CH3COO-、NO3 -、HSO4 -、H2PO4 -、[OTf]-、[BF4]-、[SbF6]-、[PF6]-[NTf2]-
In one or more support type bi-quaternary ammonium salt catalyst.
The present invention also provides support type bi-quaternary ammonium salt catalyst made from the above method.
Present invention also offers a kind of method of above-mentioned support type bi-quaternary ammonium salt catalyst preparation cyclic carbonate, the ring
Shape carbonic ester is the compound shown in formula (2), wherein, this method includes：In the presence of support type bi-quaternary ammonium salt catalyst, by formula
(3) compound shown in carries out coupled reaction with carbon dioxide and obtains the cyclic carbonate shown in formula (2), described coupled reaction
Temperature is 80-160 DEG C, time 0.5-24h, pressure 0.3-10MPa；Wherein, the catalyst is above-mentioned support type double seasons
One in support type quaternary ammonium salt catalyst made from the preparation method of ammonium salt in catalysis agent or above-mentioned support type bi-quaternary ammonium salt catalyst
Kind is a variety of；Relative to the compound shown in 1mol formulas (3), the amount of active component is in the support type bi-quaternary ammonium salt catalyst
3-50mmol；
Wherein, R2And R3It is each independently hydrogen, C1-C6 alkyl, by halogen, C=C-, phenyl, hydroxyl, carboxyl and ammonia
The C1-C6 of one or more substitutions in base alkyl, C1-C6 alkoxy, by halogen, C=C-, phenyl, hydroxyl, carboxyl and
The C1-C6 of one or more substitutions in amino alkoxy, phenyl, by C1-C4 alkyl, halogen, hydroxyl, carboxyl and amino
In one or more substitutions phenyl, phenoxy group, by one kind in C1-C4 alkyl, halogen, hydroxyl, carboxyl and amino or
A variety of substituted phenoxy groups；
Or R2And R33-6 member cycloaliphatic rings are bonded together to form together, and the cycloaliphatic ring is optionally by selected from halogen, C=C-, benzene
One or more substituents in base, hydroxyl, carboxyl and amino are substituted.
By using support type bi-quaternary ammonium salt catalyst provided by the invention as carbon dioxide and epoxides (i.e. formula
(3) compound shown in) between coupled reaction catalyst, cyclic carbonate can be prepared with higher yields, more with high selectivity
Ester (compound i.e. shown in formula (2)), particularly by catalyst after being recycled for multiple times, still can with higher yields, compared with
Cyclic carbonate is prepared with high selectivity.Especially in a kind of preferred embodiment of the present invention, when using institute of the present invention
When the support type bi-quaternary ammonium salt catalyst stated is as catalyst, it can not adopted in the coupled reaction of carbon dioxide and epoxides
With any solvent so as to greatly reduce the cost of the reaction, and also reduce probability caused by side reaction.
Beneficial effects of the present invention are：Catalyst preparation process is simple, and yield is high, overcomes common catalyst and is difficult to separate
And the problems such as needing to add co-catalyst, under the conditions of it need not add any organic solvent, to epoxides and carbon dioxide
Reaction has higher catalytic activity, and catalyst has preferable stability and service life cycle.The catalyst is as two
The catalyst of coupled reaction between carbonoxide and epoxides, cyclic carbonate can be prepared with higher yields, more with high selectivity
Ester, particularly by catalyst after being recycled for multiple times, still it can prepare cyclic carbonate with higher yields, more with high selectivity
Ester.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of support type bi-quaternary ammonium salt catalyst, and the support type bi-quaternary ammonium salt catalyst uses polymer tree
Fat and molecular sieve do carrier, and the bi-quaternary ammonium salt of formula (1) expression is bonded with carrier：
Wherein, in formula (1), the X of 2 molecules—It is identical or different, selected from F-、Cl-、Br-、I-、CH3COO-、NO3 -、HSO4 -、
H2PO4 -、[OTf]-、[BF4]-、[SbF6]-、[PF6]-[NTf2]-；N is 1-6 integer；R1For H, OH, NH2Or COOH；It is described
One or more of the carrier in silica, mesopore molecular sieve and fluoropolymer resin, described mesopore molecular sieve are MCM-
41 or SBA-15；Described fluoropolymer resin is preferably selected from the styrene resin, chitosan and Field resin of chloromethylation
One kind, more preferably chloromethylation styrene resin.
According to the present invention, support type bi-quaternary ammonium salt catalyst of the present invention is that ionic liquid is chemically bonded to by one kind
Material on carrier, it has two molecule N cations, subsidiary anion X—It can be added in structure as preparation
Anion that is reactant institute band or being got by ion exchange or being taken off on carrier, therefore, 2 points
The X of son—It is each identical or different.Such as can be represented by such as following formula (a)：In the formula (a)
Carrier, X, n and R1As herein to defined in formula (1).
For the raising support type bi-quaternary ammonium salt catalyst as the coupled reaction between carbon dioxide and epoxides
The stability of catalyst, consider in catalytic activity, it is preferable that in formula (1), X—Selected from Cl-、Br-、I-、NO3 -、HSO4 -、
H2PO4 -、[OTf]-[BF4]-.Preferably, n is 1-4 integer.It is highly preferred that the X of 2 molecules—It is identical, X—For Cl-、Br-、I-
Or [BF4]-；N is 1,2 or 3.
According to the present invention, due to double seasons that the support type bi-quaternary ammonium salt catalyst is actually carrier and formula (1) represents
The form being chemically bonded between ammonium salt, therefore the present invention is in dioxide/silica gel, mesopore molecular sieve and fluoropolymer resin
There is no particular limitation for a kind of carrier, as long as can be real above-mentioned purpose.
In a kind of preferred embodiment of the present invention, in formula (1), the X of 2 molecules—It is identical, X—For Cl-、Br-、I-Or
[BF4]-；N is 1,2 or 3；The carrier is in the styrene resin of chloromethylation, silica supports, MCM-41 and SBA-15
One kind.
In another preferred embodiment of the present invention, in formula (1), the X of 2 molecules—It is identical, X—For Cl-、Br-Or
I-；R1For OH, NH2Or COOH；N is 1,2 or 3；The carrier is styrene resin, silica supports, the MCM- of chloromethylation
One kind in 41 and SBA-15.
According to the present invention, although with the support type bi-quaternary ammonium salt catalyst as between carbon dioxide and epoxides
The catalyst of coupled reaction can just have higher activity, stability and circulation ability, but be to be able to obtain higher
Performance, it is preferable that in the support type bi-quaternary ammonium salt catalyst, relative to support type bi-quaternary ammonium salt catalyst described in 1g,
The molar content for the bi-quaternary ammonium salt part that formula (1) represents is 0.5-3mmol, more preferably 1-3mmol, still more preferably for
1.4-2.5mmol.Shown in formula (1)Part, the part grafting on carrier, it is also contemplated that
It is that functionalization has been carried out to carrier, therefore the support type bi-quaternary ammonium salt catalyst of the present invention can also be recognized as a kind of support type double seasons
The carrier mass of ammonium functionalization." bi-quaternary ammonium salt that formula (1) represents " in the present invention can also use english abbreviation " DABCO " to represent.
Present invention also offers present invention also offers a kind of preparation method of above-mentioned support type bi-quaternary ammonium salt catalyst, it is somebody's turn to do
Method includes：
(1) carrier and triethylene diamine are subjected to the first haptoreaction so that triethylene diamine is bonded with support chemistry
To the intermediate product for being connected with triethylene diamine；The carrier is in silica, mesopore molecular sieve and fluoropolymer resin
It is one or more；
(2) by intermediate product obtained by step (1) and Formula X '-(CH2)n-R1The second haptoreaction is carried out, obtains that there are three second
The support type bi-quaternary ammonium salt catalyst of alkene diamine structures, triethylene diamine structure are the activearm of support type bi-quaternary ammonium salt catalyst
Point；
X' is F-、Cl-、Br-Or I-, n be 1-6 integer, R1For H, OH, NH2Or COOH.
According to the present invention, in order to obtain X—The support type bi-quaternary ammonium salt catalyst of the invention of more horn of plenty, this method can
Also to include：By step (2) products therefrom and contain F-、Cl-、Br-、I-、CH3COO-、NO3 -、HSO4 -、H2PO4 -、[OTf]-、
[BF4]-、[SbF6]-、[PF6]-[NTf2]-In one or more anion salt solution contacted, to obtain anion
X—For F-、Cl-、Br-、I-、CH3COO-、NO3 -、HSO4 -、H2PO4 -、[OTf]-、[BF4]-、[SbF6]-、[PF6]-[NTf2]-In
One or more support type bi-quaternary ammonium salt catalyst.
, can triethylene diamine and support chemistry by first haptoreaction in step (1) according to the present invention
Bonding obtains being connected with the carrier of triethylene diamine, so as to be provided for the preparation of support type bi-quaternary ammonium salt catalyst above
Precursor.
Wherein, triethylene diamine has the structure shown in following formula (5)：Formula (5)The carrier is for example above
Described in select or preferably, will not be repeated here.
So that the carrier is the styrene resin of chloromethylation as an example, the function base of the styrene resin of the chloromethylation
Group's chloromethyl can be reacted with the N of triethylene diamine, obtain the single cropping ammonium that a molecule N cations and anion are chlorion
Salt structure.
According to the present invention, the dosage of triethylene diamine is not particularly limited, but in order to obtain above being retouched
(wherein, relative to support type bi-quaternary ammonium salt catalyst described in 1g, formula (1) represents double to the support type bi-quaternary ammonium salt catalyst stated
The molar content of quaternary ammonium moiety is 0.5-3mmol), it is preferable that relative to 1g carriers, the mole dosage of triethylene diamine is 1-
15mmol, preferably 2-10mmol, such as can be 2.2-9.6mmol, 4-9.6mmol etc..
According to the present invention, the described first catalytic condition is not particularly limited, can as long as can obtain
Precursor as the support type bi-quaternary ammonium salt catalyst of the present invention, it is preferable that the first catalytic condition includes：
Temperature is 10-50 DEG C, preferably 30-50 DEG C；Time is 1-24h, preferably 12-24h.
According to the present invention, first haptoreaction can be, for example, in acetonitrile, toluene and dichloroethanes using solvent
One or more, the capacity of solvent is not particularly limited, such as relative to 1g carriers, the dosage of solvent is 15-
100mL, preferably 18-50ml, more preferably 18-30ml.
According to the present invention, step (2) can be directly by the reaction system after step (1) haptoreaction without any processing
The second haptoreaction is directly carried out, of course for more pure support type bi-quaternary ammonium salt catalyst can be obtained, it is preferable that first
Precursor obtained by step (1) is extracted into the reaction for step (2), such extraction can for example include filtering described the
Mixture after one haptoreaction, filter cake is washed 2-4 times with ethyl acetate, then washed 2-4 times with ether, then vacuum is done
It is dry.
According to the present invention, in above-mentioned steps (2) by step (1) products therefrom and Formula X '-(CH2)n-R1Carry out the second contact
Reaction so that the support type bi-quaternary ammonium salt catalyst, which has, provides catalytic site-(CH2)n-R1Structure.Therefore, the present invention is right
Formula X '-(CH2)n-R1Dosage be not particularly limited, as long as the support type bi-quaternary ammonium salt catalyst can be obtained,
Preferably, triethylene diamine and Formula X '-(CH2)n-R1Mole dosage ratio be 1：1-3.
According to the present invention, to the described second catalytic condition, also there is no particular limitation, as long as can obtain described
Support type bi-quaternary ammonium salt catalyst, it is preferable that the second catalytic condition includes：Temperature is 60-90 DEG C, preferably
For 70-85 DEG C；Time is 1-48h, preferably 12-24h.
As Formula X of the present invention '-(CH2)n-R1It can be urged according to support type bi-quaternary ammonium salt provided by the present invention
Agent is selected, such as can be Br- (CH2)2- OH (2- bromoethanols), Br-CH2- COOH (3- monobromo-acetic acids), Br-
(CH2)2-NH2(2- bromoethylamines), Br- (CH2)3- OH (3- bromos propyl alcohol), Br-CH2- H (bromomethane), Br-CH2- OH (bromines
For methanol), I-CH2- OH (iodo methanol), Cl-CH2- OH (chloro methanol).It will be understood by those skilled in the art that
Because X' is F-、Cl-、Br-Or I-, the support type bi-quaternary ammonium salt catalyst of gained necessarily has F-、Cl-、Br-Or I-As the moon from
Son, in order to obtain the support type bi-quaternary ammonium salt catalyst of the anion with other species or single kind, optionally,
By step (2) products therefrom and contain F-、Cl-、Br-、I-、CH3COO-、NO3 -、HSO4 -、H2PO4 -、[OTf]-、[BF4]-、
[SbF6]-、[PF6]-[NTf2]-In one or more anion salt solution contacted, to obtain anion X—For F-、
Cl-、Br-、I-、CH3COO-、NO3 -、HSO4 -、H2PO4 -、[OTf]-、[BF4]-、[SbF6]-、[PF6]-[NTf2]-In one kind or
A variety of support type bi-quaternary ammonium salt catalyst.That is, the product obtained by step (2) can be used as the support type pair
Quaternary ammonium salt catalyst, but can also by the product obtained by step (2) by way of ion exchange, by anion exchange into its
His species, or by a variety of anion in the product obtained by script step (2) by being exchanged into single anion.Example
Such as, when need prepare X—For [BF4]-Formula (1) shown in structure support type bi-quaternary ammonium salt catalyst when, can be by step (2) institute
The product and NaBF obtained4Water dissolving contacted to carry out ion exchange, you can obtain.
According to the present invention, second haptoreaction can be, for example, in acetonitrile, toluene and dichloroethanes using solvent
One or more, the capacity of solvent is not particularly limited, such as (herein referred to relative to 1g steps (1) products therefrom
It is dry weight), the dosage of solvent is 10-100mL, preferably 10-50mL, more preferably 13-25mL.
According to the present invention it is possible to the support type bi-quaternary ammonium salt catalyst as the conventional extracting method in this area by obtained by walks
Suddenly extracted in the product obtained by (2), such as filter the mixture after second haptoreaction or filtering optionally process
Product mixtures after ion exchange, filter cake is washed 2-4 times with ethyl acetate, then washed 2-4 times with ether, then vacuum is done
It is dry.
Present invention also offers support type bi-quaternary ammonium salt made from the preparation method of above-mentioned support type bi-quaternary ammonium salt catalyst
Catalyst.Due to the preparation method of above-mentioned support type bi-quaternary ammonium salt catalyst can use variety carrier and/or a variety of Formula X '-
(CH2)n-R1Compound, therefore, the support type bi-quaternary ammonium salt catalyst of gained can presented hereinabove have a variety of knots
The mixture of a variety of support type bi-quaternary ammonium salt catalyst of structure.
Present invention also offers a kind of preparation method of cyclic carbonate, the cyclic carbonate is the change shown in formula (2)
Compound, wherein, this method includes：In the presence of a catalyst, the compound shown in formula (3) and carbon dioxide are subjected to coupled reaction
The cyclic carbonate shown in formula (2) is obtained, wherein, the catalyst is above-mentioned support type bi-quaternary ammonium salt catalyst or above-mentioned load
One or more in support type bi-quaternary ammonium salt catalyst made from the preparation method of type bi-quaternary ammonium salt catalyst；
Wherein, R2And R3It is each independently hydrogen, C1-C6 alkyl, by halogen, C=C-, phenyl, hydroxyl, carboxyl and ammonia
The C1-C6 of one or more substitutions in base alkyl, C1-C6 alkoxy, by halogen, C=C-, phenyl, hydroxyl, carboxyl and
The C1-C6 of one or more substitutions in amino alkoxy, phenyl, by C1-C4 alkyl, halogen, hydroxyl, carboxyl and amino
In one or more substitutions phenyl, phenoxy group, by one kind in C1-C4 alkyl, halogen, hydroxyl, carboxyl and amino or
A variety of substituted phenoxy groups；
Or R2And R33-6 member cycloaliphatic rings are bonded together to form together, and the cycloaliphatic ring is optionally by selected from halogen, C=C-, benzene
One or more substituents in base, hydroxyl, carboxyl and amino substitute that (this optionally means that can be substituted can not also be by
These substituents substitute).
According to the present invention, when described in one or more conducts using support type bi-quaternary ammonium salt catalyst provided by the invention
During catalyst, it is possible to which effectively the compound (i.e. epoxides) shown in catalysis type (3) and the coupling that carbon dioxide is carried out are anti-
Should, so as to which the cyclic carbonate shown in formula (2) be made, and the support type bi-quaternary ammonium salt catalyst can circulate multiple catalysis
The coupled reaction, and still can reach higher catalytic efficiency, the ring shown in formula (2) is made in high yield, with high selectivity
Shape carbonic ester.The preparation side as described above or above as the support type bi-quaternary ammonium salt catalyst of the catalyst
Method will not be repeated here made from carrying out.
According to the present invention, the compound shown in formula (3) is a kind of epoxides, from preferably can matching somebody with somebody with the catalyst
From the aspect of closing, it is preferable that in above-mentioned formula (3), R2And R3It is each independently hydrogen, C1-C4 alkyl, by halogen, C=C-
With the C1-C4 of one or more substitutions in phenyl alkyl, phenyl, by the one or more in C1-C4 alkyl and halogen
Substituted phenyl, phenoxy group, by one or more phenoxy groups substituted in C1-C4 alkyl and halogen；Or R2And R3One
Rise and bond together to form 3-6 member cycloaliphatic rings, the cycloaliphatic ring is optionally substituted by the one or more in halogen, C=C- and phenyl
Base is substituted.
It is highly preferred that R2And R3It is each independently hydrogen, methyl, ethyl, propyl group, isopropyl, chloromethyl, pi-allyl, benzene
Base, benzyl, p-methylphenyl and phenoxy group；Or R2And R3Bond together to form 5-6 member cycloaliphatic rings together, the cycloaliphatic ring optionally by
One or more substituents in halogen, C=C- and phenyl are substituted.
It is further preferred that R2And R3All it is hydrogen；Or R2And R3In one of them be hydrogen, another be selected from methyl,
Ethyl, propyl group, chloromethyl, pi-allyl, phenyl, benzyl and phenoxy group；Or R2And R36 yuan of cycloaliphatic rings are bonded together to form together.
Compound shown in formula (3) is selected from one kind in structure shown in following formula：
According to the present invention, below by way of specific preparating mechanism to catalyst formula (3) provided by the present invention Suo Shi
Compound and carbon dioxide carry out the process of coupled reaction and carry out explanation in mechanism：
According to the present invention, to the dosage of the catalyst, there is no particular limitation, as long as above-mentioned catalytic process can be completed
, it is preferable that relative to the compound shown in 1mol formulas (3), the dosage of the catalyst causes with triethylene diamine knot
The amount of the bi-quaternary ammonium salt (formula (1) represent bi-quaternary ammonium salt part) of structure is 3-50mmol, more preferably 5-45mmol, further
Preferably 6-20mmol, most preferably 9-16mmol.It is usually, double using the support type of the present invention in the case where meeting above-mentioned condition
In the case that quaternary ammonium salt catalyst is as catalyst, relative to the compound shown in 1mol formulas (3), the dosage of the catalyst can
Think 1-25g, preferably 5-20g, more preferably 10-20g.
According to the present invention, to the dosage of carbon dioxide, there is no particular limitation, can be the conventional amount used of this area.Generally
Carbon dioxide is in addition to as reactant, and also one acts on the pressure for being to maintain reaction system, therefore, the use of carbon dioxide
Amount can determine according to the pressure of reaction system, for example with the carbon dioxide of 0.3-10MPa (being preferably 0.3-5MPa).This
In the pressure (referring to absolute pressure) of carbon dioxide reaction environment when referring to initial carbon dioxide partial pressure, art technology
Personnel will be apparent to the skilled artisan that carrying out coupled reaction in the compound shown in common formula (3) and carbon dioxide obtains the ring shown in formula (2)
In the case of shape carbonic ester, partial pressure as carbon dioxide holding is to be enough to provide make it that the compound shown in formula (3) is completely anti-
The amount for the carbon dioxide answered, therefore, the bigger effect of carbon dioxide is to provide the pressure needed for reaction, certainly due to reacting
During the amount of carbon dioxide that reacts away also will not build-up of pressure loss it is too big.
According to the present invention, to the condition of the coupled reaction, also there is no particular limitation, and this area can be used conventional
Condition, it is contemplated that being more suitable for catalyst of the present invention plays more preferable catalytic activity, it is preferable that the coupling is anti-
The condition answered includes：Temperature is 80-160 DEG C (being preferably 90-130 DEG C), and the time is 0.5-24h (being preferably 4-12h), and pressure is
0.3-10MPa。
According to the present invention, because catalyst of the present invention has the performance of preferable reusable edible, it is preferable that
It is catalyst that this method, which also includes the reactant mixture after the coupled reaction being filtrated to get solid phase, will filter urging for gained
Agent uses as the part or all of catalyst of the coupled reaction of a new round.
According to the present invention, because catalyst of the present invention has higher catalytic activity, shown in above-mentioned formula (2)
The preparation method of cyclic carbonate can not use solvent, so as to reduce cost to a greater extent, and it also avoid solvent
Caused side reaction.
According to the present invention, using the support type bi-quaternary ammonium salt catalyst of the present invention as above-mentioned formula (2) shown in ring-type carbon
Catalyst in the preparation method of acid esters, can with higher yields, cyclic carbonate is made more with high selectivity, such as yield can
Reach more than 85%, preferably reach more than 95%.Selection rate can reach more than 90%, preferably can reach more than 99%.Particularly
Recycled more than 10 times by catalyst, may also reach up more than 95% yield and more than 99% selection rate.
The present invention will be described in detail by way of examples below.In following examples and comparative example：Yield refers to produce
Weight × 100% of weight/raw material of thing.Selection rate is weight × 100% of weight/whole products of target compound.
In the support type bi-quaternary ammonium salt catalyst of gained (i.e. shown in formula (1)Part,
Also refer to DABCO) content be to detect what is obtained by way of elementary analysis.
H1- NMR and C13- NMR is measured by the nuclear magnetic resonance spectrometer of AVANCE III 500MHz models.
Embodiment 1
The present embodiment is used to illustrate support type bi-quaternary ammonium salt catalyst of the present invention and preparation method thereof.
(1) styrene resin of 2g chloromethylation (is purchased from the chlorine ball of company of Chemical Plant of Nankai Univ., has 7%DVB
Crosslinking, chlorinity is 17 weight %, as follows) and 19.2mmol triethylene diamine be added in 50mL acetonitrile, stir simultaneously
24h is reacted at 35 DEG C, is filtered, filter cake is obtained into solid 3g with respectively washing 3 times of ethyl acetate and ether, vacuum drying respectively.
(2) solid obtained by step (1) is added in 50mL acetonitrile, stirs the lower 2- bromo second for adding 19.2mmol
Alcohol, and 24h is reacted at 75 DEG C, filter, filter cake is consolidated with respectively washing 3 times of ethyl acetate and ether, vacuum drying respectively
Body 4.1g, the solid is filtered solid with 100mL 1mol/L kbr aqueous solution mixing 12h with carrying out anion exchange
Dry, so as to obtain n=2, R in formula (1)1=OH and X—=Br-Support type bi-quaternary ammonium salt catalyst 4.2g of the invention, warp
It is 2.3mmol/g to determine wherein DABCO content.
Embodiment 2
The present embodiment is used to illustrate support type bi-quaternary ammonium salt catalyst of the present invention and preparation method thereof.
(1) triethylene diamine of the styrene resin of 1g chloromethylation and 4.8mmol is added in 30mL acetonitrile,
Stir and react 12h at 35 DEG C, filter, filter cake is consolidated with respectively washing 3 times of ethyl acetate and ether, vacuum drying respectively
Body 1.3g.
(2) solid obtained by step (1) is added in 30mL acetonitrile, stirs the lower 2- bromo second for adding 4.8mol
Acid, and 20h is reacted at 80 DEG C, filter, filter cake is consolidated with respectively washing 3 times of ethyl acetate and ether, vacuum drying respectively
Body 1.9g, the solid is filtered to carry out anion exchange with 50mL 1mol/L kbr aqueous solution mixing 12h and does solid
It is dry, so as to obtain n=1, R in formula (1)1=COOH and X—=Br-Support type bi-quaternary ammonium salt catalyst 2g of the invention, through survey
Fixed wherein DABCO content is 2mmol/g.
Embodiment 3
The present embodiment is used to illustrate support type bi-quaternary ammonium salt catalyst of the present invention and preparation method thereof.
(1) triethylene diamine of the styrene resin of 4g chloromethylation and 9.6mol is added to 75mL dichloroethanes
In, stir and react 20h at 40 DEG C, filter, by filter cake respectively with respectively washing 3 times of ethyl acetate and ether, be dried in vacuo
To solid 5.0g.
(2) solid obtained by step (1) is added in 75mL dichloroethanes, stirs the lower 2- bromines for adding 19.2mmol
For ethamine, and 12h is reacted at 75 DEG C, filtered, by filter cake respectively with respectively washing 3 times of ethyl acetate and ether, is dried in vacuo
To solid 6.1g, by the solid with 100mL 1mol/L kbr aqueous solution mixing 12h to carry out anion exchange, filtering will
Solid is dried, so as to obtain n=2, R in formula (1)1=NH2And X—=Br-Support type bi-quaternary ammonium salt catalyst of the invention
6.2g, wherein DABCO content is 1.4mmol/g after measured.
Embodiment 4
The present embodiment is used to illustrate support type bi-quaternary ammonium salt catalyst of the present invention and preparation method thereof.
According to the method described in embodiment 1, except that, 2- bromoethanols are replaced using 3- bromos propyl alcohol, so as to
N=3, R into formula (1)1=OH and X—=Br-Support type bi-quaternary ammonium salt catalyst 4.3g of the invention, after measured wherein
DABCO content is 2.2mmol/g.
Embodiment 5
The present embodiment is used to illustrate support type bi-quaternary ammonium salt catalyst of the present invention and preparation method thereof.
According to the method described in embodiment 1, except that, 2- bromoethanols are replaced using bromomethane, so as to obtain
N=1, R in formula (1)1=H and X—=Br-Support type bi-quaternary ammonium salt catalyst 4.1g of the invention, after measured wherein DABCO
Content is 2.4mmol/g.
Embodiment 6
The present embodiment is used to illustrate support type bi-quaternary ammonium salt catalyst of the present invention and preparation method thereof.
According to the method described in embodiment 1, except that, 2- bromoethanols are replaced using chloro methanol, be not required to by
Ion-exchange step, so as to obtain n=1, R in formula (1)1=OH and X—=Cl-Support type bi-quaternary ammonium salt catalyst of the invention
4.1g, wherein DABCO content is 2.35mmol/g after measured.
Embodiment 7
The present embodiment is used to illustrate support type bi-quaternary ammonium salt catalyst of the present invention and preparation method thereof.
NaI aqueous solution mixing 12h by the support type bi-quaternary ammonium salt catalyst of the gained of embodiment 6 with 100mL 1mol/L
To carry out anion exchange, filter and dry solid, so as to obtain n=1, R in formula (1)1=OH and X—=I-It is of the invention negative
Load type bi-quaternary ammonium salt catalyst 5.7g, wherein DABCO content is 2mmol/g after measured.
Embodiment 8
The present embodiment is used to illustrate support type bi-quaternary ammonium salt catalyst of the present invention and preparation method thereof.
By the support type bi-quaternary ammonium salt catalyst of the gained of embodiment 6 and 100mL 1mol/L NaBF4The aqueous solution mixes
12h is filtered to carry out anion exchange and is dried solid, so as to obtain n=1, R in formula (1)1=OH and X—=[BF4]-Sheet
The support type bi-quaternary ammonium salt catalyst 4.25g of invention, wherein DABCO content is 2.25mmol/g after measured.
Product embodiments 1
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
In closed autoclave, support type bi-quaternary ammonium salt catalyst and formula made from 0.2g embodiment 1 are added
Epoxides (41.5mmol) shown in (3-2), and the carbon dioxide of 1.2MPa pressure is filled with, 2h then is reacted at 120 DEG C,
Reaction is cooled to -10 DEG C after terminating, and releases excessive carbon dioxide, filters to isolate support type bi-quaternary ammonium salt catalyst, gained
Liquid phase gas chromatographic analysis, selection rate 99.8%, yield 99%, nuclear-magnetism qualification result：1H NMR(500MHz,
CDCl3) δ=4.89 (m, 1H), 4.44 (m, 1H), 4.12 (m, 1H), 1.64 (d, 3H)13C NMR(125MHz,CDCl3) δ=
157.13,74.74,72.07,17.30.
Product embodiments 2
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, it is double using the support type obtained by embodiment 2
Quaternary ammonium salt catalyst is replaced made from embodiment 1, the liquid phase gas chromatographic analysis of gained, selection rate 99.8%, and yield is
99%.
Product embodiments 3
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, it is double using the support type obtained by embodiment 3
Quaternary ammonium salt catalyst is replaced made from embodiment 1, the liquid phase gas chromatographic analysis of gained, selection rate 99.8%, and yield is
98%.
Product embodiments 4
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, it is double using the support type obtained by embodiment 4
Quaternary ammonium salt catalyst is replaced made from embodiment 1, the liquid phase gas chromatographic analysis of gained, selection rate 99.8%, and yield is
99%.
Product embodiments 5
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, it is double using the support type obtained by embodiment 5
Quaternary ammonium salt catalyst is replaced made from embodiment 1, the liquid phase gas chromatographic analysis of gained, selection rate 99.8%, and yield is
97%.
Product embodiments 6
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, it is double using the support type obtained by embodiment 6
Quaternary ammonium salt catalyst is replaced made from embodiment 1, the liquid phase gas chromatographic analysis of gained, selection rate 99.8%, and yield is
93%.
Product embodiments 7
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, it is double using the support type obtained by embodiment 7
Quaternary ammonium salt catalyst is replaced made from embodiment 1, the liquid phase gas chromatographic analysis of gained, selection rate 99.8%, and yield is
99%.
Product embodiments 8
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, it is double using the support type obtained by embodiment 8
Quaternary ammonium salt catalyst is replaced made from embodiment 1, the liquid phase gas chromatographic analysis of gained, selection rate 99.8%, and yield is
87%.
Product embodiments 9
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, it is passed through 0.3MPa CO2, that is, the pressure reacted is
0.3MPa, reaction time 4h, the liquid phase gas chromatographic analysis of gained, selection rate 99.5%, yield 99%.
Product embodiments 10
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, it is passed through 3MPa CO2, that is, the pressure reacted is
3MPa, the liquid phase gas chromatographic analysis of gained, selection rate 99.5%, yield 99%.
Product embodiments 11
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, it is passed through 10MPa CO2, that is, the pressure reacted is
10MPa, reaction time 4h, the liquid phase gas chromatographic analysis of gained, selection rate 99.5%, yield 87%.
Product embodiments 12
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, the temperature of reaction is 90 DEG C, and the pressure of reaction is
2MPa, reaction time 12h, the liquid phase gas chromatographic analysis of gained, selection rate 99.5%, yield 98%.
Product embodiments 13
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, the temperature of reaction is 160 DEG C, and the reaction time is
0.5h, the liquid phase gas chromatographic analysis of gained, selection rate 99.5%, yield 98%.
Product embodiments 14
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, using the catalyst used after 10 times (i.e.
After support type bi-quaternary ammonium salt catalyst has used 10 times as catalyst made from embodiment 1), the liquid phase gas phase color of gained
Spectrum analysis, selection rate 99.8%, yield 96%.
Product embodiments 15
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, using the ring shown in 30mmol formula (3-1)
Oxide replaces the epoxides shown in the formula (3-2) employed in product embodiments 1, the liquid phase gas-chromatography point of gained
Analysis, selection rate 99.8%, yield 99.2%, nuclear-magnetism qualification result：1H NMR(500MHz,CDCl3) δ=4.40 (s, 4H)
.13C NMR(125MHz,CDCl3) δ=158.08,66.21.
Product embodiments 16
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, using the ring shown in 30mmol formula (3-3)
Oxide replaces the epoxides shown in the formula (3-2) employed in product embodiments 1, reaction time 4h, the liquid phase of gained
With gas chromatographic analysis, selection rate 99%, yield 97%, nuclear-magnetism qualification result：1H NMR(500MHz,CDCl3) δ=
4.66(m,1H),4.42(m,1H),4.14(m,1H),1.42(m,2H),0.98(t,3H).13C NMR(125MHz,CDCl3)δ
=156.71,78.41,71.52,24.08,9.65.
Product embodiments 17
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, using the ring shown in 25mmol formula (3-4)
Oxide replaces the epoxides shown in the formula (3-2) employed in product embodiments 1, reaction time 4h, the liquid phase of gained
With gas chromatographic analysis, selection rate 99%, yield 96%, nuclear-magnetism qualification result：1H NMR(500MHz,CDCl3) δ=
5.11(m,1H),4.49(m,1H),4.24(m,1H),3.95(m,1H),3.64(m,1H).13C NMR(125MHz,CDCl3)δ
=156.71,78.47,71.27,43.35.
Product embodiments 18
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, using the ring shown in 25mmol formula (3-5)
Oxide replaces the epoxides shown in the formula (3-2) employed in product embodiments 1, reaction time 8h, the liquid phase of gained
With gas chromatographic analysis, selection rate 98%, yield 95%, nuclear-magnetism qualification result：1H NMR(500MHz,CDCl3) δ=
7.27-7.29(m,4H),7.10(m,1H),5.31(t,1H),4.79(m,1H),4.57(m,1H).13C NMR(125MHz,
CDCl3) δ=158.25,137.61,128.74,128.21,126.77,80.90,73.04.
Product embodiments 19
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, using the ring shown in 30mmol formula (3-6)
Oxide replaces the epoxides shown in the formula (3-2) employed in product embodiments 1, reaction pressure 2MPa, reaction time
For 8h, the liquid phase gas chromatographic analysis of gained, selection rate 95%, yield 80%, nuclear-magnetism qualification result：1H NMR
(500MHz,CDCl3) δ=4.33 (m, 2H), 2.08 (m, 2H), 1.82 (m, 2H), 1.57-1.64 (m, 2H)13C NMR
(125MHz,CDCl3) δ=154.94,77.82,26.80,24.51.
Product embodiments 20
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, using the ring shown in 35mmol formula (3-7)
Oxide replaces the epoxides shown in the formula (3-2) employed in product embodiments 1, reaction pressure 2MPa, reaction time
For 8h, the liquid phase gas chromatographic analysis of gained, selection rate 98%, yield 93%, nuclear-magnetism qualification result：1H NMR
(500MHz,CDCl3) δ=7.25 (t, 2H), 6.92-6.94 (m, 3H), 6.40 (t, 3H), 4.74 (m, 1H), 4.58 (m, 1H)
.13C NMR(125MHz,CDCl3) δ=156.55,154.15,129.76,122.70,118.73,100.55,70.63.
Product embodiments 21
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, using the ring shown in 30mmol formula (3-8)
Oxide replaces the epoxides shown in the formula (3-2) employed in product embodiments 1, reaction pressure 2MPa, reaction time
For 8h, the liquid phase gas chromatographic analysis of gained, selection rate 98%, yield 94%, nuclear-magnetism qualification result：1H NMR
(500MHz,CDCl3) δ=5.76 (m, 1H), 4.97-4.99 (m, 2H), 4.62 (m, 1H), 4.44 (m, 1H), 4.18 (m, 1H),
2.64(m,1H),2.39(m,1H).13C NMR(125MHz,CDCl3) δ=156.71,135.21,117.03,78.56,
71.49,34.39。
Product embodiments 23
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, reaction temperature is 80 DEG C, the liquid phase gas phase of gained
Chromatography, selection rate 99.5%, yield 89%, nuclear-magnetism qualification result：1H NMR(500MHz,CDCl3) δ=4.89 (m,
1H),4.44(m,1H),4.12(m,1H),1.64(d,3H).13C NMR(125MHz,CDCl3) δ=157.13,74.74,
72.07,17.30。
Product embodiments 24
The present embodiment is used for the preparation method for illustrating the cyclic carbonate of the present invention.
According to the method described in product embodiments 1, except that, catalyst amount 0.1g, the liquid phase gas of gained
Analysis of hplc, selection rate 99.5%, yield 90%, nuclear-magnetism qualification result：1H NMR(500MHz,Chloroform)δ
=δ=4.89 (m, 1H), 4.44 (m, 1H), 4.12 (m, 1H), 1.64 (d, 3H)13C NMR(125MHz,Common NMR
Solvents) δ=157.13,74.74,72.07,17.30.
Comparative example 1
According to the method described in product embodiments 1, except that, the 1- first loaded using 0.2g styrene resins
Born made from the embodiment 1 that base imidazole salts (1- methylimidazole salts load capacity is 2.1mmol/g) replace using in product embodiments 1
Load type bi-quaternary ammonium salt catalyst, the liquid phase gas chromatographic analysis of gained, selection rate 98%, yield 80%.
Comparative example 2
According to the method described in comparative example 1, except that, loaded using the styrene resin for having used 10 times
1- methylimidazole salts (the 1- methylimidazole salts that the load of the styrene resin after 10 times has been catalyzed according to the method for comparative example 1),
The liquid phase gas chromatographic analysis of gained, selection rate 98%, yield 70%.
Claims (6)
1. a kind of support type bi-quaternary ammonium salt catalyst, it is characterised in that be bonded on the carrier of the support type bi-quaternary ammonium salt catalyst
There is the bi-quaternary ammonium salt that formula (1) represents：
Formula (1)
Wherein, X—It is identical or different, X—For F-、Cl-、Br-、I-、CH3COO-、NO3 -、HSO4 -、H2PO4 -、[OTf]-、[BF4]-、
[SbF6]-、[PF6]-Or [NTf2]-；N is 1-6 integer；R1For H, OH, NH2Or COOH；
Described carrier is one kind in silica, mesopore molecular sieve, fluoropolymer resin and combinations thereof；Described mesoporous molecular
Sieve as MCM-41 or SBA-15；Described fluoropolymer resin is styrene resin, chitosan or the Field resin of chloromethylation.
2. support type bi-quaternary ammonium salt catalyst according to claim 1, it is characterised in that described support type bi-quaternary ammonium salt
When catalyst is 1g, the molar content for the bi-quaternary ammonium salt part that formula (1) represents is 0.5-3mmol.
A kind of 3. preparation method of the support type bi-quaternary ammonium salt catalyst described in claim 1 or 2, it is characterised in that including with
Lower step：
(1) carrier and triethylene diamine are subjected to the first haptoreaction so that triethylene diamine is bonded in obtaining with support chemistry
Between product；Reaction temperature is 10-50 DEG C, reaction time 1-24h；Described carrier and the usage ratio 1g of triethylene diamine:
1-15mmol；
(2) by intermediate product obtained by step (1) and Formula X '-(CH2)n-R1The second haptoreaction is carried out to obtain with triethylene diamine
The support type bi-quaternary ammonium salt catalyst of structure, triethylene diamine structure are the active component of support type bi-quaternary ammonium salt catalyst；Institute
The X' stated is F-、Cl-、Br-Or I-, n be 1-6 integer, R1For H, OH, NH2Or COOH；Described triethylene diamine and Formula X '-
(CH2)n-R1Mole dosage ratio be 1：1-3；Reaction temperature is 60-90 DEG C, reaction time 1-48h.
4. the preparation method of support type bi-quaternary ammonium salt catalyst according to claim 3, it is characterised in that this method is also wrapped
Include, the support type bi-quaternary ammonium salt catalyst that step (2) is obtained is with containing CH3COO-、NO3 -、HSO4 -、H2PO4 -、[OTf]-、
[BF4]-、[SbF6]-、[PF6]-[NTf2]-In one or more anion salt solution contacted, obtain anion X—
For CH3COO-、NO3 -、HSO4 -、H2PO4 -、[OTf]-、[BF4]-、[SbF6]-、[PF6]-[NTf2]-In it is one or more negative
Load type bi-quaternary ammonium salt catalyst.
5. a kind of method of support type bi-quaternary ammonium salt catalyst preparation cyclic carbonate using described in claim 1 or 2, it is special
Sign is, in the presence of support type bi-quaternary ammonium salt catalyst, the compound shown in formula (3) and carbon dioxide are carried out into coupled reaction
The cyclic carbonate shown in formula (2) is obtained, described coupled reaction temperature is 80-160 DEG C, time 0.5-24h, and pressure is
0.3-10MPa；
Formula (2)Formula (3)
Wherein, R2And R3It is each independently hydrogen, C1-C6 alkyl, by halogen, C=C-, phenyl, hydroxyl, carboxyl and amino
One or more substitutions C1-C6 alkyl, C1-C6 alkoxy, by halogen, C=C-, phenyl, hydroxyl, carboxyl and amino
In one or more substitutions C1-C6 alkoxy, phenyl, by C1-C4 alkyl, halogen, hydroxyl, carboxyl and amino
The phenyl of one or more substitution, phenoxy group, by the one or more in C1-C4 alkyl, halogen, hydroxyl, carboxyl and amino
Substituted phenoxy group；
Or R2And R33-6 member cycloaliphatic rings are bonded together to form together, and the cycloaliphatic ring is optionally by selected from halogen, C=C-, phenyl, hydroxyl
One or more substituents in base, carboxyl and amino are substituted.
6. the method according to claim 5 for preparing cyclic carbonate, it is characterised in that the compound shown in formula (3)
During 1mol, the amount of active component is 3-50mmol in described support type bi-quaternary ammonium salt catalyst.
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