CN112973797A - 金属配位三嗪聚离子液体催化剂及制备方法和应用 - Google Patents
金属配位三嗪聚离子液体催化剂及制备方法和应用 Download PDFInfo
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- triazine
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 239000007788 liquid Substances 0.000 title claims abstract description 47
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 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 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 claims description 5
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 claims description 5
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- 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 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- PMUKAEUGVCXPDF-UAIGNFCESA-L dilithium;(z)-but-2-enedioate Chemical compound [Li+].[Li+].[O-]C(=O)\C=C/C([O-])=O PMUKAEUGVCXPDF-UAIGNFCESA-L 0.000 claims description 3
- SHPKCSFVQGSAJU-UAIGNFCESA-L dipotassium;(z)-but-2-enedioate Chemical compound [K+].[K+].[O-]C(=O)\C=C/C([O-])=O SHPKCSFVQGSAJU-UAIGNFCESA-L 0.000 claims description 3
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000003505 polymerization initiator Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000007126 N-alkylation reaction Methods 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
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- 238000004817 gas chromatography Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006352 cycloaddition reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- -1 amidine hydrochloride Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及一种金属配位三嗪聚离子液体催化剂及制备方法和应用。所述金属配位三嗪聚离子液体催化剂的结构如式I所示。制备式I所示化合物的方法，其主要步骤是：先由1‑乙烯基咪唑和三聚氰氯通过N‑烷基化反应得到三嗪离子液体单体，再与顺丁烯二酸盐通过自由基共聚反应得到三嗪聚离子液体，最后将三嗪聚离子液体与羧酸金属盐进行配位自组装得到金属配位三嗪聚离子液体催化剂。本发明所提供的金属配位三嗪聚离子液体催化剂可以催化CO2、环氧化合物和甲醇一步合成碳酸二甲酯，在温和反应条件下展现出高催化活性、且催化剂具有易回收、重复使用性好等优势。
Description
技术领域
本发明涉及一种金属配位三嗪聚离子液体催化剂及制备方法和应用。
背景技术
碳酸二甲酯是一种重要的有机合成中间体，其分子结构中含有甲基(-CH3)、甲氧基 (CH3O-)和羰基(-CO-)等官能团，能够广泛用于甲基化、甲氧基化和羰基化等有机合成反应，替代有毒的硫酸二甲酯、氯甲酸甲酯等，也可以与醇、酯和氨基醇等进行反应，合成树脂、杀虫剂、农药、食品添加剂等精细化学产品。碳酸二甲酯也可以替代三氯乙烯、苯或二甲苯等作为油漆涂料、清洁溶剂等。碳酸二甲酯还可作为汽油添加剂取代甲基叔丁基醚，提高辛烷值和含氧量，增强燃烧效率，降低CO和含氮化合物的排放量。在锂电池电解液中加入碳酸二甲酯，能够提高导电性能、延长电池寿命(Green Chemistry,2018,20:28-85；Chemical Engineering Journal,2017,323:530-544)。因此，碳酸二甲酯应用潜能巨大，市场前景广阔，被称为新型基础化学原料。
我国碳酸二甲酯生产始于20世纪末期，早期大多采用光气法，后多为甲醇氧化羰基化法、酯交换法和尿素法。其中酯交换法因反应条件温和，安全系数高而被大量使用，具体流程是由CO2和环氧化合物先经环加成反应生成环状碳酸酯，环状碳酸酯再与甲醇发生酯交换反应得到碳酸二甲酯。但该法操作复杂，设备投资高，经济效益差(CatalysisToday, 2018,316:2-12)。基于此流程改进的一步合成法是通过将CO2环加成反应与甲醇酯交换反应耦合，可极大简化工艺流程，降低设备投资与能耗，具有更加广阔的应用前景。然而，在专利申请号为201210321260.X(一种合成碳酸二甲酯的方法)和专利申请号为201510045056.3(一锅法以碳酸盐为催化剂制备碳酸二甲酯的工艺)的专利中产物收率较低，催化剂回收困难。因此，高效催化剂的设计与开发已成为催化CO2一步法制碳酸二甲酯工艺的关键。
发明内容
本发明的一个目的在于提供一种金属配位三嗪聚离子液体催化剂，本发明的另一目的是提供上述催化剂的制备方法，本发明还有一目的是提供上述催化剂在催化CO2、环氧化合物和甲醇一步合成碳酸二甲酯中的应用。
本发明的技术方案为：一种金属配位三嗪聚离子液体催化剂，其结构如式I所示：
其中，R选自烃类取代基中的任意一种，M为过渡金属中的任意一种。
优选取代基R选自甲基、乙基或苯基中的一种。优选金属M取自过渡金属Mn、Co、 Cu或Zn中的一种。
本发明还提供了一种制备上述的金属配位三嗪聚离子液体催化剂的方法，其具体步骤为：
(1)将三聚氰氯加入反应溶剂中搅拌至完全溶解，再加入1-乙烯基咪唑于60～80℃下搅拌12～24h；反应结束后过滤除去反应溶剂，真空干燥得到棕黄色三嗪离子液体单体(式Ⅱ所示化合物)；
(2)将三嗪离子液体单体和等摩尔量的顺丁烯二酸盐加入至乙醇水溶液中，搅拌下加入聚合引发剂，在氮气保护下于60～80℃反应24～36h；产物经过滤，真空干燥后得到三嗪聚离子液体(式III所示化合物)；
(3)将三嗪聚离子液体和羧酸金属盐混合分散于溶剂中，在70～120℃下搅拌24～48h；产物经过滤、洗涤、真空干燥后得到金属配位三嗪聚离子液体催化剂(式I所示化合物)。
优选步骤(1)中反应溶剂为二甲基亚砜、乙腈、四氢呋喃或三氯甲烷中的一种；三聚氰氯与1-乙烯基咪唑的摩尔比为1:(3～5)。
优选步骤(2)中顺丁烯二酸盐为顺丁烯二酸钠、顺丁烯二酸钾或顺丁烯二酸锂中的一种；乙醇水溶液中水与乙醇的体积比为1:(2～4)；引发剂为过氧化苯甲酰、偶氮二异丁基脒盐酸盐或偶氮二异丁腈中的一种；引发剂用量为三嗪离子液体单体摩尔量的5％～20％。
优选步骤(3)中三嗪聚离子液体与羧酸金属盐的质量比为1:(1～3)；羧酸金属盐为乙酸锰、乙酸钴、丙酸铜或苯甲酸锌中的一种；溶剂为丙酮、甲苯或N,N-二甲基甲酰胺中的一种。
本发明还提供了利用上述金属配位三嗪聚离子液体催化剂在催化合成碳酸二甲酯中的应用。
碳酸二甲酯的合成方法为：在反应釜中依次加入催化剂、环氧化合物和甲醇，通入CO2后开始反应，反应结束后过滤分离催化剂和产物。
优选上述通入CO2的初始压力5～15bar；反应温度60～120℃，反应时间1～6h；环氧化合物与甲醇质量比1:3～1:6；催化剂的加入质量为环氧化合物质量的5％～15％；环氧化合物为环氧丙烷、环氧氯丙烷、环氧溴丙烷或氧化苯乙烯中的一种。
有益效果：
以金属配位三嗪聚离子液体催化剂催化CO2、环氧化合物和甲醇一步合成碳酸二甲酯，无需在环加成反应和酯交换反应间分离、更换催化剂，使两步操作合为一步，极大地简化工艺流程，降低设备投资与能耗。且在金属配位三嗪聚离子液体催化剂中存在丰富的活性位点，大大提升催化效率(催化剂PTMnAc对碳酸二甲酯产率可达92.21％)，对碳酸二甲酯的工业产能提升具有重要意义。
具体实施方式
以下用实施例对本发明作更详细的描述。这些实施例仅是对本发明最佳实施方式的描述，并不对本发明的保护范围有任何限制。
实施例1
乙酸锰配位三嗪聚离子液体的制备
步骤1.将10mmol三聚氰氯加入到50mL二甲基亚砜中搅拌至完全溶解，再加入30mmol 1-乙烯基咪唑，所得溶液于60℃下搅拌24h。反应产物经过滤、溶剂洗涤、真空干燥得到棕黄色三嗪离子液体单体(式Ⅱ所示化合物)4.27g。
式Ⅱ所示化合物：1H NMR(300MHz,DMSO):δ＝8.92(s,3H),7.92(d,3H),7.75(d,3H), 5.45(d,3H),5.3(s,3H),5.20(d,3H)ppm.13C NMR(300MHz,DMSO):δ＝167.0,137.0,123.4,123.0,128.4,101.8ppm.
步骤2.将5mmol三嗪离子液体单体和5mmol顺丁烯二酸钠加入10mL水/20mL乙醇的混合溶剂中，搅拌下加入引发剂过氧化苯甲酰0.25mmol，在氮气保护下于80℃反应 24h。产物经过滤收集，干燥后得到三嗪聚离子液体(式III所示化合物)2.12g。
步骤3.将1g三嗪聚离子液体单体和1g乙酸锰混合加入100mL丙酮中，70℃下搅拌48h。产物经过滤、溶剂洗涤、真空干燥后得到乙酸锰配位三嗪聚离子液体催化剂(式 Ia所示化合物)1.04g，所得催化剂标记为PTMnAc。
实施例2
乙酸钴配位三嗪聚离子液体的制备
步骤1.将10mmol三聚氰氯加入到50mL乙腈中搅拌至完全溶解，再加入30mmol 1-乙烯基咪唑，所得溶液于80℃下搅拌12h。反应产物经过滤、溶剂洗涤、真空干燥得到棕黄色三嗪离子液体单体(式Ⅱ所示化合物)4.02g。
步骤2.将5mmol三嗪离子液体单体和5mmol顺丁烯二酸钾加入10mL水/30mL乙醇的混合溶剂中，搅拌下加入引发剂偶氮二异丁基脒盐酸盐0.5mmol，在氮气保护下于 70℃反应24h。产物经过滤收集，干燥后得到三嗪聚离子液体(式III所示化合物)2.08g。
步骤3.将1g三嗪聚离子液体单体和1.5g乙酸钴混合加入100mL甲苯中，100℃下搅拌36h。产物经过滤、溶剂洗涤、真空干燥后得到乙酸钴配位三嗪聚离子液体催化剂(式 Ib所示化合物)1.01g，所得催化剂标记为PTCoAc。
实施例3
丙酸铜配位三嗪聚离子液体的制备
步骤1.将10mmol三聚氰氯加入到50mL四氢呋喃中搅拌至完全溶解，再加入40mmol 1-乙烯基咪唑，所得溶液于70℃下搅拌12h。反应产物经过滤、溶剂洗涤、真空干燥得到棕黄色三嗪离子液体单体(式Ⅱ所示化合物)3.85g。
步骤2.将5mmol三嗪离子液体单体和5mmol顺丁烯二酸锂加入10mL水/40mL乙醇的混合溶剂中，搅拌下加入引发剂偶氮二异丁腈0.75mmol，在氮气保护下于60℃反应 36h。产物经过滤收集，干燥后得到三嗪聚离子液体(式III所示化合物)2.18g。
步骤3.将1g三嗪聚离子液体单体和2g丙酸铜混合加入100ml N,N-二甲基甲酰胺中， 120℃下搅拌24h。产物经过滤、溶剂洗涤、真空干燥后得到丙酸铜配位三嗪聚离子液体催化剂(式Ic所示化合物)1.08g，所得催化剂标记为PTGuPc。
实施例4
苯甲酸锌配位三嗪聚离子液体的制备
步骤1.将10mmol三聚氰氯加入到50mL三氯甲烷中搅拌至完全溶解，再加入50mmol 1-乙烯基咪唑，所得溶液于70℃下搅拌24h。反应产物经过滤、溶剂洗涤、真空干燥得到棕黄色三嗪离子液体单体(式Ⅱ所示化合物)3.95g。
步骤2.将5mmol三嗪离子液体单体和5mmol顺丁烯二酸钠加入10mL水/40mL乙醇的混合溶剂中，搅拌下加入引发剂偶氮二异丁腈1mmol，在氮气保护下于70℃反应32h。产物经过滤收集，干燥后得到三嗪聚离子液体(式III所示化合物)2.09g。
步骤3.将1g三嗪聚离子液体单体和3g苯甲酸锌混合加入100mLN,N-二甲基甲酰胺中，120℃下搅拌24h。产物经过滤、溶剂洗涤、真空干燥后得到苯甲酸锌配位三嗪聚离子液体催化剂(式Id所示化合物)1.07g，所得催化剂标记为PTZnBc。
以金属配位三嗪聚离子液体催化剂催化CO2、环氧化合物和甲醇一步合成碳酸二甲酯：
实施例1
于50mL反应釜中依次加入PTMnAc(0.05g)，环氧丙烷(1g)，甲醇(3g)，通入 CO2(5bar)，在60℃反应1h。将所得产物经过滤取清液进行气相色谱分析，选择性为94.10％，产率为92.21％。
实施例2
于50mL反应釜中依次加入PTCoAc(0.1g)，环氧氯丙烷(1g)，甲醇(4g)，通入 CO2(10bar)，在80℃反应4h。将所得产物经过滤取清液进行气相色谱分析，选择性为 87.03％，产率为85.33％。
实施例3
于50mL反应釜中依次加入PTGuPc(0.1g)，环氧溴丙烷(1g)，甲醇(4g)，通入 CO2(10bar)，在100℃反应2h。将所得产物经过滤取清液进行气相色谱分析，选择性为89.47％，产率为87.36％。
实施例4
于50mL反应釜中依次加入PTZnBc(0.15g)，氧化苯乙烯(1g)，甲醇(6g)，通入 CO2(15bar)，在120℃反应6h。将所得产物经过滤取清液进行气相色谱分析，选择性为81.85％，产率为79.57％。
实施例5
过滤收集应用例1反应后的催化剂PTMnAc，将催化剂在80℃下真空干燥，测试催化剂的循环使用性能。循环使用结果如表1所示。
表1催化剂PTMnAc的循环使用情况
由表1可知：本发明提供的乙酸锰配位三嗪聚离子液体催化剂(如式Ia所示化合物) 可以CO2为原料一步合成碳酸二甲酯，具有催化活性高、反应条件温和、催化剂易回收、重复使用性高等优点。
Claims (10)
1.一种金属配位三嗪聚离子液体催化剂，其结构如式I所示：
其中，R选自烃类取代基中的任意一种，M为过渡金属中的任意一种。
2.如权利要求1所述的金属配位三嗪聚离子液体催化剂，其特征在于，取代基R选自甲基、乙基或苯基中的一种。
3.如权利要求1所述的金属配位三嗪聚离子液体催化剂，其特征在于，金属M取自过渡金属Mn、Co、Cu或Zn中的一种。
4.一种制备如权利要求1中所述的金属配位三嗪聚离子液体催化剂的方法，其具体步骤为：
(1)将三聚氰氯加入反应溶剂中搅拌至完全溶解，再加入1-乙烯基咪唑于60～80℃下搅拌12～24h；反应结束后过滤除去反应溶剂，真空干燥得到棕黄色三嗪离子液体单体；
(2)将三嗪离子液体单体和等摩尔量的顺丁烯二酸盐加入至乙醇水溶液中，搅拌下加入聚合引发剂，在氮气保护下于60～80℃反应24～36h；产物经过滤，真空干燥后得到三嗪聚离子液体；
(3)将三嗪聚离子液体和羧酸金属盐混合分散于溶剂中，在70～120℃下搅拌24～48h；产物经过滤、洗涤、真空干燥后得到金属配位三嗪聚离子液体催化剂。
5.如权利要求4所述的制备方法，其特征在于：步骤(1)中反应溶剂为二甲基亚砜、乙腈、四氢呋喃或三氯甲烷中的一种；三聚氰氯与1-乙烯基咪唑的摩尔比为1:(3～5)。
6.如权利要求4所述的制备方法，其特征在于：步骤(2)中顺丁烯二酸盐为顺丁烯二酸钠、顺丁烯二酸钾或顺丁烯二酸锂中的一种；乙醇水溶液中水与乙醇的体积比为1:(2～4)；引发剂为过氧化苯甲酰、偶氮二异丁基脒盐酸盐或偶氮二异丁腈中的一种；引发剂用量为三嗪离子液体单体摩尔量的5％～20％。
7.如权利要求4所述的制备方法，其特征在于：步骤(3)中三嗪聚离子液体与羧酸金属盐的质量比为1:(1～3)；羧酸金属盐为乙酸锰、乙酸钴、丙酸铜或苯甲酸锌中的一种；溶剂为丙酮、甲苯或N,N-二甲基甲酰胺中的一种。
8.一种如权利要求1所述的金属配位三嗪聚离子液体催化剂在催化合成碳酸二甲酯中的应用。
9.根据权利要求8所述的应用，其特征在于碳酸二甲酯的合成方法为：在反应釜中依次加入催化剂、环氧化合物和甲醇，通入CO2后开始反应，反应结束后过滤分离催化剂和产物。
10.根据权利要求9所述的应用，其特征在于：通入CO2的初始压力5～15bar；反应温度60～120℃，反应时间1～6h；环氧化合物与甲醇质量比1:3～1:6；催化剂的加入质量为环氧化合物质量的5％～15％；环氧化合物为环氧丙烷、环氧氯丙烷、环氧溴丙烷或氧化苯乙烯中的一种。
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| CN114797978A (zh) * | 2022-05-07 | 2022-07-29 | 南京工业大学 | 羧基化三嗪聚离子液体催化剂及其制备方法和应用 |
| CN114797978B (zh) * | 2022-05-07 | 2023-09-26 | 南京工业大学 | 羧基化三嗪聚离子液体催化剂及其制备方法和应用 |
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