CN108440485A - 一种环碳酸酯的生产方法 - Google Patents
一种环碳酸酯的生产方法 Download PDFInfo
- Publication number
- CN108440485A CN108440485A CN201710083633.7A CN201710083633A CN108440485A CN 108440485 A CN108440485 A CN 108440485A CN 201710083633 A CN201710083633 A CN 201710083633A CN 108440485 A CN108440485 A CN 108440485A
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- China
- Prior art keywords
- metalloporphyrin
- catalyst
- quaternary alkylphosphonium
- organic
- alkylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- -1 cyclic carbonate ester Chemical class 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 150000003839 salts Chemical class 0.000 claims abstract description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 31
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 23
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 20
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 239000011664 nicotinic acid Substances 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 239000002841 Lewis acid Substances 0.000 claims abstract description 4
- 230000004913 activation Effects 0.000 claims abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 150000002924 oxiranes Chemical class 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 150000004032 porphyrins Chemical class 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 150000007530 organic bases Chemical class 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 6
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 6
- 238000012719 thermal polymerization Methods 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- KIQQAJNFBLKFPO-UHFFFAOYSA-N magnesium;porphyrin-22,23-diide Chemical compound [Mg+2].[N-]1C(C=C2[N-]C(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 KIQQAJNFBLKFPO-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000007210 heterogeneous catalysis Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical group C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical class CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- RQFAJHPMHVKGHL-UHFFFAOYSA-N [Br-].[PH4+].C(=C)C1=CC=CC=C1 Chemical class [Br-].[PH4+].C(=C)C1=CC=CC=C1 RQFAJHPMHVKGHL-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 6
- 229910052786 argon Inorganic materials 0.000 claims 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims 2
- SEDICHOWWKGGFC-UHFFFAOYSA-N [Cl-].[PH4+].C(=C)C1=CC=CC=C1 Chemical class [Cl-].[PH4+].C(=C)C1=CC=CC=C1 SEDICHOWWKGGFC-UHFFFAOYSA-N 0.000 claims 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims 2
- MZHROOGPARRVHS-UHFFFAOYSA-N triacetylene Chemical group C#CC#CC#C MZHROOGPARRVHS-UHFFFAOYSA-N 0.000 claims 2
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- SIBLALJSAHLAGS-UHFFFAOYSA-N [I-].[PH4+].C(=C)C1=CC=CC=C1 Chemical class [I-].[PH4+].C(=C)C1=CC=CC=C1 SIBLALJSAHLAGS-UHFFFAOYSA-N 0.000 claims 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 235000013844 butane Nutrition 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims 1
- 238000005304 joining Methods 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- LSMAIBOZUPTNBR-UHFFFAOYSA-N phosphanium;iodide Chemical class [PH4+].[I-] LSMAIBOZUPTNBR-UHFFFAOYSA-N 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 12
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 2
- 150000002118 epoxides Chemical class 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- 229920002554 vinyl polymer Polymers 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000007306 functionalization reaction Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L Zinc bromide Inorganic materials Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QQGMRDZQQKVAIA-UHFFFAOYSA-N 1,2,3-triethynylbenzene Chemical compound C#CC1=CC=CC(C#C)=C1C#C QQGMRDZQQKVAIA-UHFFFAOYSA-N 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-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
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LYNGLDZGXGSGLA-UHFFFAOYSA-N benzene;magnesium Chemical compound [Mg].C1=CC=CC=C1 LYNGLDZGXGSGLA-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical class [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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Abstract
本发明涉及一种环碳酸酯的生产方法及应用,所使用的催化剂为基于金属卟啉和季鏻盐的有机多孔共聚物形成的多功能仿生多相催化剂。催化剂载体由烯烃基官能团化的金属卟啉与季鏻盐混聚而成,催化剂活性组分为金属卟啉(作为路易斯酸活化环氧化合物)和季鏻盐(作为开环亲核试剂)官能团。所得的多功能仿生多相催化剂适用于固定床、浆态床、釜式反应器和滴流床等反应器。本发明提供的多相催化剂在环氧化合物与二氧化碳生产环碳酸酯反应中有很好的表现,催化剂活性非常高(2000~6000h‑1),形成环碳酸酯的选择性好(>99%),底物适用性强,并且该多相催化剂稳定性好,催化剂与底物、产品分离简单而且高效。
Description
技术领域
本发明涉及一种环碳酸酸酯的生产方法及应用,具体指一种由环氧化物和二氧化碳在基于金属卟啉和季鏻盐的有机共聚物多功能仿生多相催化剂条件下,通过环加成反应制备环碳酸酯的方法及应用。
背景技术
CO2是目前地球上最主要的温室气体,同时也是地球上取之不尽用之不竭的C1资源。传统的碳资源如石油、煤、天然气等均属于不可再生资源。随着化石燃料的大量使用和能源需求量的不断上升,这些化石燃料正不断枯竭,造成“碳源危机”。因此,出于环保和能源的双重需求,CO2的转化与利用已经成为各国普遍关注的焦点。二氧化碳与环氧化物经加成反应可生成重要的化工原料环碳酸酯。这是一个100%原子经济性的反应,没有副产物生成,是CO2转化利用的重要途径。环碳酸酯具有强极性、高沸点、高闪点、低挥发速度、低毒性和生物可降解等优点,不仅可作为聚碳酸酯的原料,还是重要的精细化工品中间体。
已报道用于CO2与环氧化合物环加成反应的催化体系非常广泛,主要可以分为两类:均相催化剂和非均相催化剂。均相催化剂目前研究主要有碱金属(Chem.Rev.,2007,107:2365)、鏻盐、铵盐(J.Mol.Catal.A,2006,249:143)、有机碱、离子液体(J.Mol.Catal.A,2008,279:230)、金属配合物(J.Am.Chem.Soc.,2001,123:11498)等催化剂;此类催化剂存在的主要问题是催化剂的回收利用困难。所以,为了克服上述局限,人们更多的致力于非均相催化剂的研究开发,主要包括:金属氧化物催化剂、分子筛、负载型催化剂、有机聚合物催化剂等,但目前已报道的非多相催化剂仍普遍存在催化效率不高,反应条件苛刻,选择性差,制备工艺复杂,使用寿命短及需要加入助催化剂等问题。因此,开发一种反应条件温和,稳定性好,催化活性高,选择性好的催化剂仍是人们研究的重要目标。
2013年,邓伟侨等人(Nat.Commun.,2013,4:1960)发明了一种共轭微孔Salen配体聚合物。该聚合物自负载型的Co‐CMP和Al‐CMP催化剂可催化CO2与环氧丙烷的反应。但是反应工艺较复杂,需要添加四丁基溴化胺做助剂。环氧化合物底物只测试了环氧丙烷,反应工艺为釜式反应。
2015年,Yugen Zhang等人(Chem.Commun.,2015,51,15708)用付克交联的方法把季膦盐交联成了超交联共轭微孔聚合物,并且探究了这类催化剂在CO2与环氧化合物加成中的应用,发现加入ZnBr2助剂后催化剂活性明显提升,并且催化剂具有很好的底物适用性。但是催化剂活性还有待于进一步提升。
2016年,肖丰收等人(Journal of Catalysis,2016,338,202)发明了一种乙烯基功能化的卟啉多孔有机聚合物。该聚合物自负载型的Co‐卟啉、Zn‐卟啉、Mg‐卟啉催化剂被用于探究二氧化碳与环氧化物的偶联反应。虽然Co‐卟啉催化剂在室温条件下取得了较高的转化率,循环次数可达18次,但是其反应工艺仍为釜式反应,且需要添加4‐正丁基溴化铵做助催化剂,这使得产物分离提纯困难。
发明内容
为了解决上述问题,本发明的目的在于提供一种新型的环碳酸酯的生产方法及应用。
本发明的技术方案
一种环碳酸酯的生产方法,所使用的催化剂为基于金属卟啉和季鏻盐的有机多孔共聚物形成的多功能仿生多相催化剂。催化剂载体由烯烃基官能团化的金属卟啉与季鏻盐混聚而成,催化剂活性组分为金属卟啉(作为路易斯酸活化环氧化合物)和季鏻盐(作为开环亲核试剂)官能团。所得的多功能仿生多相催化剂在环氧化合物与二氧化碳生产环碳酸酯反应中具有很好的表现。
烯烃基官能团化的金属卟啉的功能化官能团优选为四苯乙烯基官能团。所述的含有烯烃基的金属卟啉最佳为含有四苯乙烯基的镁‐卟啉,所述的季鏻盐最佳为乙基‐三(4‐乙烯苯)溴化鏻。所述的多功能仿生多相催化剂具有多级孔结构,比表面积为10~3000m2/g,同时含有大孔、中孔和微孔,孔容为0.1~5.0cm3/g,孔径分布在0.2~50.0nm。所述的多相催化剂是将含有烯烃基的金属卟啉与季鏻盐混合后,采用溶剂热聚合法,在添加或不添加交联剂的情况下,经自由基引发剂引发卟啉配体和季鏻盐中烯烃基发生聚合反应,生成具有多级孔结构既可以充当载体又是活性组分的多功能仿生多相催化剂。
催化剂的具体制备步骤为:
a)在273~473K,惰性气氛下,在有机溶剂中,加入四苯乙烯基官能团化的卟啉单体(附图1,图1‐L1),加入有机碱,再加入有路易斯酸性的金属前驱体,室温搅拌6~24h,得到的混合物过滤,水洗,25~100℃真空抽走溶剂。
b)在273~473K,惰性气氛下,在有机溶剂中,加入四苯乙烯基官能团化的金属卟啉(附图1,图1‐L2)和季鏻盐(附图1,图1‐L3),添加或不添加交联剂,再加入自由基引发剂,混合后,将混合物搅拌0.1~100h,优选的搅拌时间范围为0.1~1h。
c)将步骤b)制得的混合溶液转移至合成高压釜中,323~473K,惰性气氛下,采用溶剂热聚合法,静置1~100h(优选为20~80h)进行聚合反应,得到一种含金属卟啉和季鏻盐的有机共聚物。
d)将步骤b)得到的共聚物,在室温条件下真空抽除溶剂,即得到具有多级孔结构的含有金属卟啉和季鏻盐的有机共聚物,即作为催化环氧化合物与二氧化碳偶联反应的多功能仿生多相催化剂。
值得指出的是步骤a)中所述有机溶剂为二氯甲烷、三氯甲烷、苯、甲苯、甲醇、乙醇或四氢呋喃中的一种或两种以上;所述的有机碱为三乙胺、三乙烯二胺、1,8‐二氮杂二环[5,4,0]十一碳‐7‐烯和4‐二甲胺基吡啶中的一种或两种以上;所述的金属前驱体为溴化镁乙醚、水合醋酸锌、水合氯化钴、氯化铝和氯化铬中的一种或两种以上;步骤b)中所述的有机溶剂为苯、甲苯、甲醇、乙醇、四氢呋喃、二氯甲烷或三氯甲烷中一种或两种以上;所述的交联剂为苯乙烯、乙烯、丙烯、二乙烯基苯或1,3,5‐三乙炔基苯中的一种或两种以上;所述的自由基引发剂为过氧化环己酮、过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈或偶氮二异庚腈的一种或两种以上。步骤a)中所述的金属前驱体和四苯乙烯基官能团化的卟啉单体的摩尔比为1:1,有机碱与金属前驱体的摩尔比为10:1~1:1。步骤b)中所述的四苯乙烯基官能团化的金属卟啉和季鏻盐的摩尔比为0.01:1~100:1,在交联剂添加的情况下,金属卟啉与交联剂的摩尔比为0.01:1~10:1,金属卟啉与自由基引发剂的摩尔比为300:1~10:1,聚合成有机共聚物前,金属卟啉在有机溶剂中的浓度范围为0.01‐1000g/L。
反应过程为将制备得到的催化剂装入反应器中,通入原料气,原料气的主要组分为CO2,CO2的体积含量为20~70%(其余为氮气)。原料环氧化合物纯度为20~100%,反应温度323~573K,反应压力0.1~10.0MPa,气体空速100~20000h‐1,液时空速0.01~10.0h‐1条件下进行环氧化物与二氧化碳的偶联反应,所述的反应器为固定床,浆态床,滴流床或釜式反应器。反应原料底物环氧化合物的分子结构为S1、S2、S3、S4、S5、S6、S7中的一种或二种以上。
本发明的反应原理
本发明将典型的卟啉单体(porphyrin)上引入四苯乙烯基(vinyl),将其金属化后,再将季鏻盐也引入乙烯基,在高压釜中利用溶剂热聚合法,使之聚合形成高比表面积和多级孔道结构的有机共聚物,充分综合了金属卟啉(作为路易斯酸活化环氧化合物)和季鏻盐(作为开环亲核试剂))的各自优势。值得一提的是,该聚合物骨架中丰富的N、P原子可以增加CO2的吸附,即增加“CO2捕获能力”;多孔有机聚合物材料能将反应底物封存并限制在纳米级的孔中,增加催化位点上的底物浓度;通过溶剂热聚合合成的乙烯基多孔有机聚合物表现出了较好的溶胀特性。上述这些有利的特性,使得该催化剂既具有极高的活性,又具有较高的稳定性的双重优势。
本发明的有益效果
本发明所述的多相催化剂骨架中含有金属卟啉和季鏻盐结构单元,其中金属卟啉中金属与卟啉分子形成的共价键有利于活性金属的高分散,提高了金属的利用效率,且不易流失,共聚物具有高比表面积多孔级结构,具备载体和配体的双重功能,活性金属组分和聚合物中另一功能组分季鏻盐形成协同催化作用,极大地提高了催化活性。此类多功能仿生多相催化剂适用于固定床、浆态床、釜式反应器和滴流床等反应工艺,本发明所提供的多级孔结构含金属卟啉和季鏻盐有机共聚物多功能仿生多相催化剂应用于二氧化碳和环氧乙烷的偶联加成反应合成环状碳酸酯之中,能够显著提高催化反应活性。也可以在室温下利用二氧化碳合成出环状碳酸酯。降低了环碳酸酯工业生产的成本,催化剂稳定性好,产品和催化剂的分离简单高效,为环碳酸酯的生产提供了新的工业催化剂。
本发明提供的多相催化剂在环氧化合物与二氧化碳生产环碳酸酯反应中有很好的表现,催化剂活性非常高(2000~6000h‐1),形成环碳酸酯的选择性好(>99%),底物适用性强,并且该多相催化剂稳定性好,催化剂与底物、产品分离简单而且高效。
附图说明
图1为典型的烯烃基功能化的卟啉单体、金属化的卟啉和季鏻盐。
图2是聚合技术路线示意图。
图3是聚合中用到的交联剂。
图4是实施例1乙烯基官能团化的Vinyl PILC2Br的1H谱。
图5是实施例1乙烯基官能团化的Vinyl PILC2Br的13C谱。
图6是实施例1Mg‐porphyrin&phos@POP固体13C谱。
图7是实施例1在N2氛围下催化剂热重曲线。
图8是实施例1Mg‐porphyrin&phos@POP催化剂的N2吸脱附等温曲线和孔径分布曲线图。
图9是反应原料底物环氧化合物的分子结构示意图。
具体实施方式
下述实施例对本发明进行更好的说明,不限制本发明所要保护的范围。
实施例1
在298K和惰性气体保护氛围下,将1.0g四苯乙烯基卟啉单体溶于150.0mL二氯甲烷溶剂中,同时加入18.1ml三乙胺和113mg MgBr2·Et2O,搅拌12h,混合物过滤,水洗,干燥,经索氏提取72h,之后40℃真空干燥24h,得到四苯乙烯基功能化的镁卟啉单体(附图1,L4)。在298K和惰性气体保护氛围下,取上述乙烯基功能化的镁卟啉单体0.1g溶于12ml N,N‐二甲基甲酰胺中,再加入1.0g乙基‐三(4‐乙烯苯)溴化鏻(附图1,L5),向上述溶液中加入55mg自由基引发剂偶氮二异丁腈,搅拌2小时。将搅拌好的溶液移至高压釜中,于473K利用溶剂热聚合法聚合72h。待上述聚合后的溶液冷却至室温,40℃条件真空抽走溶剂,即得到由四苯乙烯基功能化的金属镁卟啉和乙基‐三(4‐乙烯苯)溴化鏻单体共聚的有机多孔聚合物多功能多相催化剂,命名为Mg‐porphyrin&phos@POP,经氮气吸脱附测试表征,其比表面积为558m2/g,总孔容为0.55cm3/g,根据图8(B)孔径分布曲线(由非定域密度函数理论计算所得),得知其孔径分布为0.84nm、1.43nm、2.40nm和4.14nm,主要为微孔区域和部分介孔范围内,即应用于二氧化碳和环氧化合物的偶联加成反应之中。图2是聚合技术路线示意图。
实施例2
在实施例2中,除了称取20.6mg CoCl2·6H2O,替代金属盐MgBr2·Et2O,其余的催化剂合成过程与实施例1相同。
实施例3
在实施例3中,除了称取17.1mg Zn(OAc)2·2H2O,替代金属盐MgBr2·Et2O,其余的催化剂合成过程与实施例1相同。
实施例4
在实施例4中,除了称取46.8mg AlCl3·6H2O,替代金属盐MgBr2·Et2O,其余的催化剂合成过程与实施例1相同。
实施例5
在实施例5中,除了称取20.4mg Cr(OAc)2·2H2O,替代金属盐MgBr2·Et2O,其余的催化剂合成过程与实施例1相同。
实施例6
在实施例6中,除了称取1.0克甲基‐三(4‐乙烯苯)溴化鏻单体,替代乙基‐三(4‐乙烯苯)溴化鏻单体,其余的催化剂合成过程与实施例1相同。
实施例7
在实施例7中,除了用12.0mL四氢呋喃溶剂替代12.0mL N,N‐二甲基甲酰胺溶剂外,其余的催化剂制备过程与实施例1相同。
实施例8
在实施例8中,除了用12.0mL N‐甲基吡咯烷酮溶剂替代12.0mL N,N‐二甲基甲酰胺溶剂溶剂外,其余的催化剂制备过程与实施例1相同。
实施例9
在实施例9中,除了用423K聚合温度替代473K聚合温度外,其余的催化剂制备过程与实施例1相同。
实施例10
在实施例10中,除了用48h聚合时间替代72h聚合时间外,其余的催化剂制备过程与实施例1相同。
实施例11
在实施例11中,除了再加入12.0克二乙烯基苯(附图3,L1),其余的催化剂制备过程与实施例1相同。
实施例12
将上述制备的催化剂0.5g装入到固定床反应器中,两端装入石英砂。原料气CO2(体积浓度为100%)空速选为2000h‐1,液体原料环氧丙烷(图9,S1)液体时速为5h‐1,在393K,2.0MPa下进行CO2与环氧丙烷的加成反应。生成物经一个60ml的恒温(273K)收集罐收集。所获得产品采用配有HP‐5毛细管柱和FID检测器的HP‐7890N气相色谱分析,采用正丁醇作内标。反应结果列于表1。
实施例13
将实施例1制备的催化剂0.5g装入到50ml容量的浆态床反应器中,并加入30ml碳酸丙烯酯为浆态液。反应条件为393K,2.0MPa,原料气CO2空速选为2000h‐1,液体原料环氧丙烷(图9,S1)液体时速为5h‐1,浆态床搅拌速率为750转/分钟。产物经一个60ml的恒温(273K)收集罐收集,随尾气夹带的反应产物和浆态液全部收集在收集罐中。其它同实施例12,数据列于表1
实施例14
除了用环氧氯丙烯(图9,S2)底物替代环氧丙烷做反应底物外,其余同实施例12,反应结果列于表1。
表1实施例1‐14中合成的催化剂比表面积和环氧化物与二氧化碳偶联反应数据
*实验条件:120℃,2MPa,原料气CO2空速为2000h-1,液体原料环氧丙烷(图9,S1)液体时速5h-1。TOF计算是以金属卟啉中的金属作为活性位点计算(金属含量通过ICP—OES测得)。
Claims (10)
1.一种环碳酸酯的生产方法,特征在于:以环氧化合物和二氧化碳主原料生产环碳酸酯,使用的催化剂为基于金属卟啉和季鏻盐的有机多孔共聚物形成的多功能仿生多相催化剂,催化剂载体由烯烃基官能团化的金属卟啉与含有烯烃基的季鏻盐混聚而成有机多孔聚合物,催化剂活性组分为有机多孔聚合物中的金属卟啉(作为路易斯酸活化环氧化合物)和季鏻盐(作为开环亲核试剂)官能团;所得的多功能仿生多相催化剂在反应中具有很好的表现。
2.按照权利要求1所述的生产方法,其特征在于:所述多相催化剂中通过烯烃基化金属卟啉和含有烯烃基的季鏻盐单体,按照摩尔比1:1~1:50共聚得到的有机共聚物,其作为载体,而其中的金属卟啉和季鏻盐官能团作为活性组分,即有机共聚物即作为载体又作为活性组分。
3.按照权利要求1或2所述的生产方法,其特征在于:烯烃基官能团化的金属卟啉的功能化官能团优选为四苯乙烯基官能团,金属可为镁,钴,锌,铝或铬等中的一种或二种以上;金属卟啉优选镁‐卟啉,其结构简式如下:
所述的含有烯烃基的季鏻盐优选为甲基‐三(4‐乙烯苯)氯化鏻,甲基‐三(4‐乙烯苯)溴化鏻,甲基‐三(4‐乙烯苯)碘化鏻,乙基‐三(4‐乙烯苯)氯化鏻,乙基‐三(4‐乙烯苯)溴化鏻,乙基‐三(4‐乙烯苯)碘化鏻中的一种或二种以上;所述的季鏻盐最佳为乙基‐三(4‐乙烯苯)溴化鏻。
4.按照权利要求1或2所述的生产方法,其特征在于:所述的多功能仿生多相催化剂具有多级孔结构,比表面积为10~3000m2/g,同时含有大孔、中孔和微孔,孔容为0.1~5.0cm3/g,孔径分布在0.2~50.0nm。
5.按照权利要求1‐4任一所述的生产方法,其特征在于:所述的多相催化剂是将含有烯烃基的金属卟啉与季鏻盐混合后,采用溶剂热聚合法,在添加或不添加交联剂的情况下,经自由基引发剂引发卟啉配体和季鏻盐中烯烃基发生聚合反应,生成具有多级孔结构既可以充当载体又是活性组分的多功能仿生多相催化剂;
催化剂的具体制备步骤为:
a)在273~473K(优选为298K~373K),惰性气氛(氩气和/或氮气)下,在有机溶剂中,加入烯烃基官能团化的卟啉单体,加入有机碱,再加入有路易斯酸性的金属前驱体,室温搅拌6~24h,得到的混合物过滤,水洗,25~100℃真空抽走溶剂;
b)在273K~473K(优选为298K~373K),惰性气氛(氩气和/或氮气)下,在有机溶剂中,加入烯烃基官能团化的金属卟啉和含有烯烃基的季鏻盐,添加或不添加交联剂,再加入自由基引发剂,混合后,将混合物搅拌0.1~100h,优选的搅拌时间范围为0.1~1h;
c)将步骤b)制得的混合溶液转移至合成高压釜中,323~473K,惰性气氛(氩气和/或氮气)下,采用溶剂热聚合法,静置1~100h(优选为20~80h)进行聚合反应,得到一种含金属卟啉和季鏻盐的有机共聚物;
d)将步骤b)得到的共聚物,在室温条件下真空抽除溶剂,即得到具有多级孔结构的含有金属卟啉和季鏻盐的有机共聚物,即作为催化环氧化合物与二氧化碳偶联反应的多功能仿生多相催化剂。
6.按照权利要求5所述的生产方法,其特征在于:步骤a)中所述有机溶剂为二氯甲烷、三氯甲烷、苯、甲苯、甲醇、乙醇或四氢呋喃中的一种或两种以上;所述的有机碱为三乙胺、三乙烯二胺、1,8‐二氮杂二环[5,4,0]十一碳‐7‐烯和4‐二甲胺基吡啶中的一种或两种以上;所述的金属前驱体为溴化镁乙醚、水合醋酸锌、水合氯化钴、氯化铝和氯化铬中的一种或两种以上;步骤b)中所述的有机溶剂为苯、甲苯、甲醇、乙醇、四氢呋喃、二氯甲烷或三氯甲烷中一种或两种以上;所述的交联剂为苯乙烯、乙烯、丙烯、二乙烯基苯或1,3,5‐三乙炔基苯中的一种或两种以上;所述的自由基引发剂为过氧化环己酮、过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈或偶氮二异庚腈的一种或两种以上。
7.按照权利要求5所述的生产方法,其特征在于:步骤a)中所述的金属前驱体和烯烃基官能团化的卟啉单体的摩尔比为1:1,有机碱与金属前驱体的摩尔比为10:1~1:1(优选为3:1~1:1)。
8.按照权利要求5或6所述的生产方法,其特征在于:步骤b)中所述的烯烃基官能团化的金属卟啉和含有烯烃基的季鏻盐的摩尔比为0.01:1~100:1(优选为0.1:1~1:1),在交联剂添加的情况下,金属卟啉与交联剂的摩尔比为0.01:1~10:1(优选为0.1:1~1:1),金属卟啉与自由基引发剂的摩尔比为300:1~10:1(优选为50:1~10:1),聚合成有机共聚物前,金属卟啉在有机溶剂中的浓度范围为0.01‐1000g/L(优选为0.1~10g/L);聚合成有机共聚物后,金属的担载量为0.01~10wt%(优选为0.01~0.2wt%)。
9.按照权利要求1‐8任一所述的一生产方法,其特征在于:反应过程为将制备得到的催化剂装入反应器中,通入原料气,原料气为含有CO2的气体;液体原料为环氧化合物,反应温度323~573K(优选为373K~413K),反应压力0.1~10.0MPa(优选为1~4MPa),气体空速100~20000h‐1(优选为1000~3000h‐1),液时空速0.01~10.0h‐1(优选为0.5~5h‐1)条件下进行环氧化物与二氧化碳的偶联反应,所述的反应器为固定床,浆态床,滴流床或釜式反应器。
10.按照权利要求9所述的生产方法,其特征在于:所述的反应器为固定床,浆态床,滴流床或釜式反应器;原料气的主要组分为CO2,CO2的体积含量为20~100%(其余为氮气或惰性气体中的一种或二种以上,优选为CO2的体积含量为95~100%);液体原料环氧化合物纯度为20~100%(其余为溶解烃、氯乙烷、氯丙烷、乙醛、丙醛、环氧乙烷、1‐氯丙烷、2‐氯丙烷及1,2‐环氧丁烷中的一种或二种以上,优选纯度为99~100%的环氧化合物原料)。
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