CN114653404B - Ruthenium compound catalyst and application thereof in olefin metathesis - Google Patents
Ruthenium compound catalyst and application thereof in olefin metathesis Download PDFInfo
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- CN114653404B CN114653404B CN202210310631.8A CN202210310631A CN114653404B CN 114653404 B CN114653404 B CN 114653404B CN 202210310631 A CN202210310631 A CN 202210310631A CN 114653404 B CN114653404 B CN 114653404B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 150000003304 ruthenium compounds Chemical class 0.000 title claims abstract description 51
- 238000005865 alkene metathesis reaction Methods 0.000 title claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 48
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 59
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004913 cyclooctene Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- USPWUOFNOTUBAD-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(F)=C(C(F)(F)F)C(F)=C1F USPWUOFNOTUBAD-UHFFFAOYSA-N 0.000 claims description 4
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Chemical class CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 claims description 4
- YSGAFHSZSJFDNV-UHFFFAOYSA-N 3-(2,3,4,5,6-pentafluorophenyl)-2,1-benzoxazole Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C1=C2C=CC=CC2=NO1 YSGAFHSZSJFDNV-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001939 cyclooctenes Chemical class 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical class C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical class CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 claims description 2
- LUMNWCHHXDUKFI-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethanol Chemical class C1C2C(CO)CC1C=C2 LUMNWCHHXDUKFI-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- BMAXQTDMWYDIJX-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carbonitrile Chemical class C1C2C(C#N)CC1C=C2 BMAXQTDMWYDIJX-UHFFFAOYSA-N 0.000 claims description 2
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical class C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 claims description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 2
- 150000001941 cyclopentenes Chemical class 0.000 claims description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentenylidene Natural products C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 2
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical class C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 claims description 2
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 2
- 229940073769 methyl oleate Drugs 0.000 claims description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical class C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 229960002969 oleic acid Drugs 0.000 claims description 2
- 229940055577 oleyl alcohol Drugs 0.000 claims description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 20
- 239000002028 Biomass Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 description 11
- 239000011986 second-generation catalyst Substances 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 10
- -1 C-1 compound Chemical class 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 229910052707 ruthenium Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- CLFRCXCBWIQVRN-UHFFFAOYSA-N 2,5-dihydroxybenzaldehyde Chemical compound OC1=CC=C(O)C(C=O)=C1 CLFRCXCBWIQVRN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 description 1
- GNYSXVMNJXTLRL-UHFFFAOYSA-N C(C)(C)[Ru] Chemical compound C(C)(C)[Ru] GNYSXVMNJXTLRL-UHFFFAOYSA-N 0.000 description 1
- 238000010535 acyclic diene metathesis reaction Methods 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005686 cross metathesis reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011984 grubbs catalyst Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
-
- 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
- B01J31/1805—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 the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
- B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/419—Acyclic diene metathesis [ADMET]
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Abstract
The invention discloses a ruthenium compound catalyst and application thereof in olefin metathesis, and relates to the technical field of organic synthesis. The structural general formula of the ruthenium compound catalyst is shown as the formula (I):
(I) (ii) a Wherein R is 1 、R 2 Independently selected from H, C 1 ~C 6 Alkoxy, substituted C 1 ~C 6 Alkyl of (C) 1 ~C 6 Alkyl, dimethylamino, nitro or halogen; r 3 Is selected from C 1 ~C 6 One of alkyl and substituted isopropyl. The ruthenium compound catalyst provided by the invention has higher catalytic activity, and the yield of the catalytic olefin metathesis reaction product is obviously increased; and the catalyst has more excellent catalytic stability, is suitable for olefin metathesis reaction of various different monomers, and maintains the catalytic performance at a higher level.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a ruthenium compound catalyst and application thereof in olefin metathesis.
Background
Scholar (Richard) three french scientists, ivf (Yves Chauvin) and Robert, u.s.scientists, grabbs (Robert H Grubbs), richard Schrock (Richard R Schrock), share the 2005 nobel prize of chemistry for the development of the use of olefin metathesis in organic synthesis. Since then, the field of olefin metathesis has been hot of organic chemistry and polymer synthesis chemistry. Olefin metathesis refers to the process of cleaving and recombining carbon-carbon multiple bonds under metal catalysis. According to the change of molecular skeleton during the reaction, there are several cases such as ring-opening metathesis, ring-opening metathesis polymerization, acyclic diene metathesis polymerization, ring-closing metathesis, cross metathesis reaction, ethenolysis reaction, etc. From these results, it can be seen that the olefin metathesis reaction is of great significance in the fields of polymer material chemistry, organic synthetic chemistry, and the like.
Olefin metathesis catalysts are central to the art of unsaturated olefin polymerization, and it is therefore of great importance to design more efficient catalysts. Among the numerous catalysts, ruthenium catalysts are of interest due to their stable nature, including first generation Grubbs, second generation Grubbs, and third generation Grubbs catalysts. In particular, the Hoveyda-Grubbs second generation catalyst has excellent properties in terms of its stability in air and resistance to heteroatoms, etc. Therefore, our work has focused on the design of Hoveyda-Grubbs' second generation catalysts. In evaluating the performance of olefin metathesis catalysts, the initiation efficiency of the catalyst is generally considered, which is closely related to the catalytic activity, and therefore it is important to design a ruthenium catalyst having a high initiation efficiency. In the method, a class of olefin metathesis catalysts containing hydroxyl is designed, the influence of phenolic hydroxyl on catalytic activity is researched, and the catalytic behavior of ruthenium catalysts with different steric hindrance substituents in ethylene decomposition reaction and ring opening polymerization reaction is also investigated.
Disclosure of Invention
The invention aims to provide a ruthenium compound catalyst and application thereof in olefin metathesis, wherein the ruthenium compound catalyst has higher catalytic activity, and the yield of catalytic olefin metathesis reaction products is obviously increased; and the catalyst has more excellent catalytic stability, is suitable for olefin metathesis reaction of various different monomers, and maintains the catalytic performance at a higher level.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a ruthenium compound catalyst has a structural general formula shown in formula (I):
wherein R is 1 、R 2 Independently selected from H, C 1 ~C 6 Alkoxy, substituted C 1 ~C 6 Alkyl of (C) 1 ~C 6 Alkyl, dimethylamino, nitro or halogen;
R 3 is selected from C 1 ~C 6 One of alkyl and substituted isopropyl. The invention designs and synthesizes a series of ruthenium complexes containing hydroxyl, and on one hand, the ruthenium complexes pass through the hydroxyl and R 1 、R 2 、R 3 The substitution steric hindrance and the electronic effect of the ruthenium compound catalyst have beneficial effects on the catalytic active center of the ruthenium compound catalyst; on the other hand, the hydroxyl can form effective hydrogen bond action with Ru-Cl bond or polymerized monomer, the hydrogen bond effect can further influence the catalytic performance of the ruthenium catalyst, so that the catalytic activity of the ruthenium compound catalyst is effectively improved, the initiation efficiency is improved, the catalyst has more excellent catalytic stability, high-level catalytic activity can be kept for different reaction monomers, and the application range is wide. The ruthenium compound catalyst prepared by the invention can be well applied to catalyzing olefin metathesis reaction, namely ethylene metathesis reaction or ring-opening polymerization reaction, and the catalytic capability of the ruthenium compound catalyst is not transferred to Hoveyda-Grubbs second-generation catalyst. Wherein R in the formula (I) 1 And R 2 Are both methyl and R 3 The catalyst of the isopropyl ruthenium compound catalyzes olefin metathesis reaction, which can obviously improve the polymerization degree of polymerization reaction, so that the prepared polymerization product has narrower molecular weight distribution and higher molecular weight.
Preferably, R is as defined above 1 、R 2 Independently selected from H, methyl or isopropyl; r 3 Selected from methyl or isopropyl.
Further, the ruthenium compound catalyst is preferably selected from compounds represented by the formulae (II) to (V):
a method for preparing a ruthenium compound catalyst represented by formula (I), comprising:
reacting a compound with a structure shown in a formula (VI) with a compound with a structure shown in a formula (VII) to obtain a compound with a structure shown in a formula (I);
wherein R is 1 、R 2 Independently selected from H and C 1 ~C 6 Alkoxy, substituted C 1 ~C 6 Alkyl of (C) 1 ~C 6 Alkyl, dimethylamino, nitro or halogen of (a); r is 3 Is selected from C 1 ~C 6 One of alkyl groups and substituted isopropyl groups.
Specifically, the preparation method of the ruthenium compound catalyst represented by the formula (I) comprises:
dissolving the compound with the structure of formula (VI) and the compound with the structure of formula (VII) and cuprous iodide in tetrahydrofuran at room temperature, and heating to 75 to 90 DEG o C, reacting for 12 to 169h, and performing column chromatography separation to obtain the target product ruthenium compound catalyst with the structure shown in the formula (I).
Further, the room temperature is preferably 20 to 35 ℃.
Further, the molar ratio of the compound with the structure of formula (VI) to the compound with the structure of formula (VII) to cuprous iodide is 1; preferably 1.
The column chromatography is not limited, and the method belongs to the conventional operation in the field and can be used for realizing the purpose of separation and purification.
The synthetic route of the compound with the structure of the formula (VII) is as follows:
specifically, the general synthetic route of the ruthenium compound catalyst is as follows:
the method for catalyzing olefin metathesis reaction by the ruthenium compound catalyst comprises the following steps:
performing ethylene decomposition reaction or ring opening polymerization reaction on an olefin monomer under the action of a catalyst; the catalyst is a ruthenium compound catalyst shown in a formula (I), and preferably a ruthenium compound catalyst with any structure shown in formulas (II) - (V).
The parameters of the olefin metathesis reaction are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and use requirements, as long as the reaction parameters of such reactions are well known to those skilled in the art.
The amount of the olefin metathesis feedstock is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and use requirements, as is conventional for such reactions and is well known to those skilled in the art.
The specific selection of the above olefin monomers is not particularly limited in the present invention, and can be selected and adjusted by those skilled in the art according to the practical application, product requirements and performance requirements.
Further, the olefin monomer is preferably one or more selected from non-polar cyclic and chain monomers or polar cyclic and chain monomers.
Further, the nonpolar cyclic, chain monomers are preferably selected from: cyclooctene, substituted cyclooctene, cyclooctadiene, norbornene, 2-hexene, 3-hexene.
Further, the polar cyclic, chain monomer is preferably selected from: polar substituted cyclooctene, polar substituted cyclopentene, methyl 5-norbornene-2-carboxylate, 5-norbornene-2-carboxylic acid, 2-cyano-5-norbornene, 5-norbornene-2-methanol, 5-norbomen-2-yl acetate, methyl oleate, oleic acid or oleyl alcohol.
Further, the ethenolysis reaction and the ring-opening polymerization reaction are carried out in the presence of an organic solvent.
Further, the organic solvent is selected from one or more of dichloromethane, chloroform, benzene, toluene, chlorobenzene and ethyl acetate.
Further, the reaction temperature of the ethenolysis reaction and the ring opening polymerization is 0 to 100 ℃, and preferably 20 to 50 ℃; the reaction time is 0.1 to 24h, preferably 0.5 to 2h.
The pressure of the olefin metathesis reaction is not particularly limited in the present invention, and may be a pressure of a conventional catalytic reaction well known to those skilled in the art, and those skilled in the art may select and adjust the pressure according to actual production conditions, product requirements and performance requirements, and the pressure of the catalytic polymerization reaction in the present invention is preferably 0.1 to 3mpa, and more preferably 0.5 to 2mpa.
It is still another object of the present invention to disclose the above process for preparing ethylene hydrolyzate and unsaturated ring-opened polymer.
It is still another object of the present invention to provide a ruthenium compound catalyst as an olefin metathesis catalyst and to study the use thereof in an ethenolysis reaction and a ring-opening polymerization reaction.
The invention also discloses application of the ruthenium compound catalyst in catalyzing olefin metathesis reaction.
Compared with the prior art, the invention has the following beneficial effects:
the ruthenium compound containing a hydroxyl structure of the formula (I) of the invention contains a para-R 1 、R 2 And R 3 Due to the adjustment of steric effect or electronic effect of the group, the hydroxyl and Ru-Cl bond or polymerized monomer form effective hydrogen bond action, so that the olefin metathesis catalyst with high activity and high stability is prepared, is used for catalyzing vinyl decomposition reaction, ring opening polymerization reaction and the like of olefin monomers, has better catalytic activity, and obviously increases the yield of products. The series of ruthenium compound catalysts prepared by the invention can obtain final products with excellent yield by using less catalyst even under short reaction time and low to medium reaction temperature, and the intermediate products of the catalyst with the new structure have higher purity and yield in the preparation process, thereby being more beneficial to the economic production on an industrial scale.
Therefore, the invention provides a ruthenium compound catalyst and application thereof in olefin metathesis, wherein the ruthenium compound catalyst has higher catalytic activity and obviously increases the yield of catalytic olefin metathesis reaction products; and the catalyst has more excellent catalytic stability, is suitable for olefin metathesis reaction of various different monomers, and maintains the catalytic performance at a higher level.
Drawings
FIG. 1 is an ORTEP diagram showing the crystal structure of a ruthenium compound catalyst (Ru-1) prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of the compound B prepared in example 1 of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum of the C-1 compound prepared in example 1 of the present invention;
FIG. 4 is a nuclear magnetic hydrogen spectrum of a D-1 compound prepared in example 1 of the present invention;
FIG. 5 is a nuclear magnetic hydrogen spectrum of the E-1 compound prepared in example 1 of the present invention;
FIG. 6 is a nuclear magnetic hydrogen spectrum of the Ru-1 compound prepared in example 1 of the invention.
Detailed Description
The technical solutions of the present invention will be described in further detail below with reference to the detailed description and the accompanying drawings, but it should be understood that these examples are only for illustrating the disclosure of the present invention to assist understanding, and are not intended to limit the scope of the present invention, and the scope of the present invention is not limited to the following examples.
The present invention is not particularly limited with respect to the sources of the raw materials in the following examples, and they may be prepared by a preparation method known to those skilled in the art or may be commercially available.
The data given in the examples include the synthesis of ligands, the synthesis of metal compounds, olefin metathesis process, all sensitive materials stored in a glove box refrigerator at-30 ℃ without specific reference, all raw materials purchased and used directly.
Silica gel column is treated by 200 to 300 mesh silica gel, and nuclear magnetism is carried out by a Bruker 400MHz nuclear magnetism instrument. The molecular weight and molecular weight distribution of the amorphous polymer were determined by GPC (polystyrene type column, HR2 and HR4, box temperature 45 ℃ C., using Water 1515 and Water 2414 pumps, mobile phase tetrahydrofuran, flow rate 1.0 mL/min, using polydispersed polystyrene as standard). Single crystal X-ray Diffraction analysis was performed using an Oxford Diffraction Gemini S Ultra CCD single crystal Diffraction instrument with Cu ka (λ =1.54184 a) radiated at room temperature.
Example 1:
preparation of ruthenium compound catalyst (Ru-1) having the structure represented by formula (II):
the reaction scheme is as follows, wherein R 1 、R 2 Are each methyl, R 3 Is an isopropyl group:
wherein, the GII structure is as follows:
the preparation method comprises the following specific steps:
a mixed solution of DMF (41.40 ml) and 2, 5-dihydroxybenzaldehyde A (1.38 g,10.0 mmol) was placed in an ice-water bath at 0 ℃ and pivaloyl chloride (1.21 g,10.0 mmol) and Et 3 N (1.66 mL,12.0 mmol), stirred at room temperature for 12 h, quenched with water (100 mL), the organics extracted with ethyl acetate (3X 50 mL), the organic mixture washed with brine, anhydrous Na 2 SO 4 Drying and vacuum concentrating; then purified by column chromatography in ethyl acetate/n-hexane (EA/Hex = 1/10) to give B as a viscous oil (1.85 g, 78.5% yield); 1 H NMR (400 MHz, CDCl 3 ) δ 9.97 (s, 1H), 7.17 (d, J = 3.0 Hz, 1H), 6.99 (dd, J = 8.8, 3.0 Hz, 1H), 6.93 (d, J = 8.7 Hz, 1H), 1.40 (s, 9H).
to a solution of B (1.49 g,6.70 mmol) and 2-iodopropane (1.7 g,1.0 mL,10.0 mmol) in anhydrous DMF (30 mL) was added Cs 2 CO 3 (437 mg,1.34 mmol) and K 2 CO 3 (1.38 g,10 mmol), after stirring at room temperature for 10 h, the reaction mixture was poured into water (100 mL), extracted with ethyl acetate (3X 50 mL), the organic extracts washed with brine, na 2 SO 4 Drying and vacuum concentrating; purification by column chromatography (EA/Hex = 1/3) gave C-1 as an oil (1.61 g, 91%); 1 H NMR (400 MHz, CDCl 3 ) δ 10.44 (s, 1H), 7.48 (s, 1H), 7.21 (dd, J = 9.0, 3.0 Hz, 1H), 6.98 (d, J = 9.0 Hz, 1H), 1.40 (d, J = 6.1 Hz, 6H), 1.34 (s, 9H).
in N 2 Under protection, 0 o C to dissolved Ph 3 P + CH 3 Br - (22.36 g,62.58 mmol) in 63 mL of anhydrous THF 3 Si) 2 NLi (1M in THF), after 0.5h of reaction at room temperature, the clear solution was transferred by syringe into a solution of C-1 (13.18 g,50.00 mmol) in 30 mL THF; the reaction mixture was stirred at room temperature for 12 h, then the insoluble material was filtered off and the filtrate was concentrated under vacuum; the crude product was purified by column chromatography over silica (EA/Hex = 1) to give D-1 (11.8 g, 90.0%) as a light yellow oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.15 (s, 1H), 7.02 (dd, J = 17.8, 11.1 Hz, 1H), 6.92 – 6.83 (m, 2H), 5.71 (dd, J = 17.8, 1.3 Hz, 1H), 5.26 (dd, J = 11.1, 1.2 Hz, 1H), 1.36 (s, 9H), 1.34 (d, J = 6.1 Hz, 6H).
at 0 o C to a solution of methanol (200 mL) was added sodium tert-butoxide (2.88 g,30 mmoL), D-1 (2.62 g,10.00 mmoL). Stirring at room temperature for 4h, vacuum concentrating, dichloromethane (3X 100 mL) extraction, brine washing, anhydrous Na 2 SO 4 Drying and vacuum concentrating to obtain organic extract; purification by column chromatography (EA/Hex = 1/10) gave the target product E-1 (1.33 g, 98%) as an oil; 1 H NMR (CDCl 3 ): δ 7.04 (dd, J = 11.1, 17.8 Hz, 1H), 6.95 (d, J = 3.0 Hz, 1H), 6.79 (d, J = 8.7 Hz, 1H), 6.69 (dd, J = 3.0, 8.7 Hz, 1H), 5.64 (dd, J = 1.3, 17.8Hz, 1H), 5.22 (dd, J = 1.3, 11.1 Hz, 1H), 4.37 (sept, J = 6.1 Hz, 1H), 1.30 (d, J = 6.1 Hz, 6H).
in N 2 E-1 (178 mg,1.0 mmol), GII (from Energy Chemical) (848 mg,1.0 mmol) and CuI (693 mg,4.0 mmol) were dissolved in 30 mL of THF under protection in 80 mL of THF o Reaction for 12 h under C, concentrate in vacuo, extract with dichloromethane (3X 50 mL) and Na anhydrous 2 SO 4 Dried, concentrated in vacuo, purified by column chromatography (PE/EA = 2). 1 H NMR (400 MHz, CDCl 3 ) δ 7.06 (s, 4H), 6.81 (d, J = 7.8 Hz, 1H), 6.48 (d, J = 8.1 Hz, 1H), 6.23 (s, 1H), 5.05 (s, 1H), 4.79 – 4.71 (m, 1H), 4.16 (s, 4H), 2.43 (m, 18H), 1.22 (d, J = 6.0 Hz, 6H). 13 C NMR (101 MHz, CDCl 3 ) δ 190.5, 151.8, 150.9, 144.1, 136.2, 131.0, 129.1, 131.5, 128.3, 128.0, 126.8, 125.5, 123.7, 75.8, 56.4, 22.8, 22.5, 21.8, 21.2, 19.8, 18.6. MS (ESI): m/z: 608.1 [M-Cl]. Elemental analysis calcd for C 31 H 39 Cl 2 N 2 O 2 Ru: C 57.85; H 6.11; N, 4.35; found C 57.82, H 6.10, N 4.38.
Example 2:
preparation of ruthenium compound catalyst (Ru-2) having a structure represented by formula (III):
the procedure for the preparation of B was the same as in example 1;
the difference between the preparation of C-2 and the preparation of C-1 in example 1: methyl iodide is used for replacing 2-iodopropane;
the preparation of D-2 differs from the preparation of D-1 in example 1: c-2 prepared in the example is used for replacing C-1;
the preparation of E-2 differs from the preparation of E-1 in example 1: d-2 prepared in the example is used for replacing D-1;
preparation of Ru-2 (reaction scheme:
the method comprises the following specific operation steps:
at N 2 E-2 (150 mg,1.0 mmol), GII (848 mg,1.0 mmol) and CuI (693 mg,4.0 mmol) were dissolved in 30 mL THF under protection at 80 o Reaction for 12 h under C, concentrate in vacuo, extract with dichloromethane (3X 50 mL) and Na anhydrous 2 SO 4 Dried, concentrated in vacuo, purified by column chromatography (PE/EA = 2). 1 H NMR (400 MHz, CDCl 3 ) δ 7.02 (s, 4H), 6.80 (d, J = 7.8 Hz, 1H), 6.42 (d, J = 8.1 Hz, 1H), 6.21 (s, 1H), 5.02 (br, 1H), 4.13 (s, 4H), 3.92（s, 3H), 2.42 (m, 18H). 13 C NMR (101 MHz, CDCl 3 ) δ 190.0, 152.6, 150.8, 143.5, 135.6, 130.4, 128.9, 131.0, 128.6, 128.1, 127.4, 125.3, 123.2, 56.4, 51.8, 21.6, 21.4, 19.6, 18.2. MS (ESI): m/z: 580.1 [M -Cl]. Elemental analysis calcd for C 29 H 35 Cl 2 N 2 O 2 Ru: C 56.58; H 5.73; N, 4.55; found C 56.55, H 5.72, N 4.59.
Example 3:
preparation of ruthenium compound catalyst (Ru-3) having the structure represented by formula (IV):
B. the preparation procedures of C-1, D-1 and E-1 were the same as those in example 1;
preparation of Ru-3 (reaction scheme:
wherein, ipr the structure of GII is shown below:
the method comprises the following specific operation steps:
at N 2 Under protection, E-1 (178 mg,1.0 mmol), ipr GII (purchased from Sigma-Aldrich) (947 mg,1.0 mmol) and CuI (693 mg,4.0 mmol) were dissolved in 30 mL of THF at 80 o Reaction for 12 h under C, concentrate in vacuo, extract with dichloromethane (3X 50 mL) and Na anhydrous 2 SO 4 Dried, concentrated in vacuo, purified by column chromatography (PE/EA = 2). 1 H NMR (400 MHz, CDCl 3 ) δ 7.50 (t, J =7.6 Hz, 1H), 7.40 (d, J = 7.7 Hz, 1H), 7.10 (s, 1H), 6.85-6.83 (m, 1H), 6.82 (d, J = 7.8 Hz, 1H), 6.80-6.74 (m, 2H), 6.38 (d, J = 8.1 Hz, 1H), 6.20 (s, 1H), 5.04 (br, 1H), 4.80 (m, 1H), 3.56-3.52 (m, 2H), 3.14-3.10 (m, 2H), 1.40 (m 6H), 1.20 (m, 6H), 1.29 (m, 6H), 1.08 (m, 6H), 0.95 (m, 6H). 13 C NMR (101 MHz, CDCl 3 ) δ 190.5, 151.8, 148.9, 146.6, 137.8, 136.5, 131.9, 131.0, 128.9, 128.0, 127.8, 124.0, 123.3, 76.1, 51.6, 29.1, 28.4, 26.5, 26.2, 22.5, 22.0. MS (ESI): m/z: 692.3 [M -Cl]. Elemental analysis calcd for C 37 H 51 Cl 2 N 2 O 2 Ru: C 61.06; H 7.06; N, 3.85; found C 61.02, H 7.03, N 3.88.
Example 4:
preparation of ruthenium compound catalyst (Ru-4) having a structure represented by formula (V):
B. the preparation procedures of C-2, D-2 and E-2 are the same as those of example 2;
preparation of Ru-4 (reaction scheme:
the method comprises the following specific operation steps:
in N 2 Under the protection of the catalyst, adding E-2 (150 mg,1.0 mmol), ipr GII (947 mg,1.0 mmol) and CuI (693 mg,4.0 mmol) were dissolved in 30 mL THF at 80 o Reaction for 12 h under C, concentration in vacuo, extraction with dichloromethane (3X 50 mL), anhydrous Na 2 SO 4 Dried, concentrated in vacuo and purified by column chromatography (PE/EA =2 1) and spin-dried on a rotary evaporator to give Ru-4 (426 mg, 61%) as a green solid. 1 H NMR (400 MHz, CDCl 3 ) δ 7.48 (m, 1H), 7.36 (d, J = 8.0 Hz, 1H), 7.08 (s, 1H), 6.83-6.80 (m, 1H), 6.78 (d, J = 8.0 Hz, 1H), 6.82-6.76 (m, 2H), 6.38 (d, J = 8.0 Hz, 1H), 6.18 (s, 1H), 5.02 (br, 1H), 4.16 (s, 4H), 3.94（s, 3H), 3.52-3.46 (m, 2H), 3.12-3.08 (m, 2H), 1.42 (m, 6H), 1.24 (m, 6H), 1.03 (m, 6H), 0.96 (m, 6H). 13 C NMR (101 MHz, CDCl 3 ) δ 190.3, 151.6, 148.7, 146.2, 137.6, 136.0, 131.6, 131.3, 130.0, 128.2, 128.0, 124.2, 123.7, 56.1, 51.3, 29.2, 28.2, 26.9, 26.3, 22.9, 22.3. MS (ESI): m/z: 664.2 [M -Cl]. Elemental analysis calcd for C 35 H 47 Cl 2 N 2 O 2 Ru: C 60.08; H 6.77; N, 4.00; found C 60.10, H 6.78, N 3.98.
Example 5:
ruthenium compound catalyst for catalyzing ethenolysis reaction of biomass monomer
In a glove box, under the nitrogen atmosphere, adding a ruthenium compound catalyst, a biomass monomer and toluene into a reaction kettle, setting a proper temperature, adjusting ethylene to a specified pressure, reacting for 60min, stopping the reaction, opening the reaction kettle, taking a little liquid, testing nuclear magnetism, and further obtaining the conversion rate through calculation. Table 1 shows the specific experimental conditions and experimental results of the ethenolysis of biomass monomers provided by the present invention.
TABLE 1 results of ruthenium catalyzed Biomass monomer ethenolysis
And (3) annotation: the polymerization condition is that 3mL of 10 mu mol of catalyst, 3mmol of olefin monomer and toluene are reacted for 1h, and the yield is obtained by hydrogen spectrum calculation; the comparative example Ru is the Hoveyda-Grubbs second generation catalyst.
As can be seen from the analysis in Table 1, the yield of the ruthenium compound catalyst prepared by the invention for catalyzing the ethenolysis reaction of biomass monomers is at least equivalent to that of the Hoveyda-Grubbs second-generation catalyst under the same polymerization conditions, wherein the catalytic yield of Ru-1, ru-2 and Ru-3 is obviously higher than that of the Hoveyda-Grubbs second-generation catalyst, which indicates that the ruthenium compound catalyst with the novel structure synthesized by the invention has higher catalytic activity for the ethenolysis reaction of biomass monomers. Meanwhile, the catalytic activity of the ruthenium compound catalyst prepared by the invention for catalyzing the ethenolysis reaction of the biomass monomer is enhanced along with the increase of temperature or pressure; under the same polymerization condition, the catalytic yield of different reaction monomers is kept consistent, and compared with a Hoveyda-Grubbs second-generation catalyst, the catalyst has more excellent catalytic stability and wider application prospect.
Example 6:
ruthenium compound catalyst for ring-opening polymerization of cyclic olefin monomer
In a Schlenk bottle, under the nitrogen atmosphere, a cyclic olefin monomer and anhydrous dichloromethane are added, a proper temperature is set, and a dichloromethane solution of a ruthenium metal complex is injected for reaction for 0.5h. The reaction was stopped, the reaction solution was concentrated, and methanol was added to precipitate a white powdery polymer. Filtering, drying and weighing to calculate the monomer conversion rate. Table 2 shows the specific experimental conditions and experimental results of the ring-opening polymerization of the cyclic monomer provided in the present invention.
TABLE 2 ruthenium catalyzed Ring opening polymerization of Cyclic olefin monomers
And (3) annotation: polymerization conditions, namely 60mL of 30mmol of cyclic monomer and dichloromethane are reacted for 0.5h, and the yield is calculated according to the mass of the obtained polymer; comparative example Ru is the Hoveyda-Grubbs second generation catalyst.
As can be seen from the analysis in Table 2, under the same polymerization conditions, the yield of the ring-opening polymerization reaction of the cyclic olefin monomer catalyzed by the ruthenium compound catalyst prepared by the invention is at least equivalent to that of the Hoveyda-Grubbs second-generation catalyst, and the catalytic yield of Ru-1 and Ru-2 is obviously higher than that of the Hoveyda-Grubbs second-generation catalyst, which indicates that the ruthenium compound catalyst with the novel structure synthesized by the invention has better catalytic activity for the ring-opening polymerization reaction of the cyclic olefin monomer. Compared with a product catalyzed by a Hoveyda-Grubbs second-generation catalyst, the product catalyzed by the catalyst Ru-1 has higher molecular weight under the condition of the same molecular weight distribution, and the catalyst Ru-1 can improve the polymerization degree of reaction and catalyze to generate a product with higher molecular weight. Meanwhile, the catalytic activity of the Ru-1 catalyst prepared by the invention for catalyzing the ring-opening polymerization reaction of the cyclic olefin monomer is enhanced along with the increase of the dosage of the catalyst; under the same polymerization condition, the catalytic yield of different reaction monomers is kept at a higher level, not less than 80%, and the catalyst shows a wider application prospect.
Example 7:
effect of additives on the catalysis of the ethenolysis reaction of Biomass monomers by ruthenium compound catalysts
In a glove box, adding a ruthenium compound catalyst, an additive, a biomass monomer and toluene into a reaction kettle in a nitrogen atmosphere, setting a proper temperature, adjusting ethylene to a specified pressure, increasing microwave radiation (200W) to assist reaction for 60min, stopping the reaction, opening the reaction kettle, taking a little liquid to test nuclear magnetism, and further obtaining the conversion rate through calculation. Table 3 shows the specific experimental conditions and experimental results of ethenolysis of biomass monomers provided by the present invention.
TABLE 3 results of ruthenium catalyzed Biomass monomer ethenolysis under additive conditions
Note that: polymerization conditions, namely 3mL of 10 mu mol of catalyst, 3mmol of olefin monomer, additive and toluene (v/v, 1; t1 is octafluorotoluene, T2 is octafluorotoluene containing 3- (perfluorophenyl) benzo [ c ] isoxazole (w/w, 1.
From the analysis in table 3, it can be seen that under the same polymerization conditions, the yield of the ethenolysis reaction of biomass monomers catalyzed by the ruthenium compound catalyst prepared by the invention is obviously improved under the condition of additive addition. The improvement degree of the yield of the vinyl hydrolysis reaction of the ruthenium compound catalyst catalyzed biomass monomer by adding the 3- (perfluorophenyl) benzo [ c ] isoxazole as the additive is obviously higher than that of the vinyl hydrolysis reaction of the octafluorotoluene as the additive, and the 3- (perfluorophenyl) benzo [ c ] isoxazole is adopted to promote the vinyl hydrolysis reaction of the ruthenium compound catalyst with the novel structure prepared by the invention on the biomass monomer, possibly through generating stronger pi-pi and pi-ion interaction, the additive is more favorable for playing the role, and the catalytic activity of the ruthenium compound catalyst for catalyzing the vinyl hydrolysis reaction of the biomass monomer is stronger.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. The application of the ruthenium compound catalyst in catalyzing ethenolysis reaction or ring-opening polymerization reaction is characterized in that the ruthenium compound catalyst is one of compounds shown in formulas (II) - (V):
2. the use according to claim 1, wherein the ruthenium compound catalyst is prepared by a process comprising:
reacting a compound with a structure shown in a formula (VI) with a compound with a structure shown in a formula (VII) to obtain compounds with structures shown in formulas (II) - (V);
wherein R is 1 、R 2 Selected from methyl or isopropyl; r 3 Selected from methyl or isopropyl.
3. The use according to claim 1, wherein the ruthenium compound catalyst catalyzes an olefin metathesis reaction comprising:
carrying out ethylene decomposition reaction or ring-opening polymerization reaction on the olefin monomer under the action of a catalyst;
the olefin monomer is selected from one or more of nonpolar cyclic or chain monomers and polar cyclic or chain monomers; the nonpolar cyclic or chain monomer is selected from: one or more of cyclooctene, substituted cyclooctene, cyclooctadiene, norbornene, 2-hexene, 3-hexene; the polar cyclic or chain monomers are selected from: one or more of polar substituted cyclooctene, polar substituted cyclopentene, 5-norbornene-2-carboxylic acid methyl ester, 5-norbornene-2-carboxylic acid, 2-cyano-5-norbornene, 5-norbornene-2-methanol, 5-norbomen-2-yl acetate, methyl oleate, oleic acid or oleyl alcohol.
4. Use according to claim 3, wherein the ethenolysis reaction and the ring-opening polymerization reaction are carried out in the presence of an organic solvent.
5. Use according to claim 4, wherein the organic solvent is selected from one or more of dichloromethane, chloroform, benzene, toluene, chlorobenzene, ethyl acetate.
6. The use according to claim 3, wherein the reaction temperature of the ethenolysis reaction and the ring-opening polymerization is 20 to 50 ℃ and the reaction time is 0.5 to 2h.
7. Use according to claim 3, wherein additives are added during the ethenolysis reaction, said additives comprising octafluorotoluene and 3- (perfluorophenyl) benzo [ c ] isoxazole.
8. Use according to any one of claims 1 to 7 to produce an ethylene hydrolysate and an unsaturated ring-opened polymer.
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| CN105728046A (en) * | 2016-03-25 | 2016-07-06 | 上海克琴化工科技有限公司 | Ruthenium metallic olefin metathesis catalyst and preparation and application methods thereof |
| CN108299506A (en) * | 2018-01-29 | 2018-07-20 | 中国科学院成都有机化学有限公司 | N- heterocycle carbine ruthenium complexs and its preparation method and application |
| CN109126899A (en) * | 2018-09-26 | 2019-01-04 | 上海克琴科技有限公司 | A method of increasing ruthenium metal olefin metathesis catalyst stability in the solution |
| CN109134547A (en) * | 2017-06-28 | 2019-01-04 | 赞南科技(上海)有限公司 | A kind of ruthenium complex, preparation method and application |
| CN110938164A (en) * | 2019-11-12 | 2020-03-31 | 中国科学技术大学 | One-pot method for tandem catalytic copolymerization of ethylene and 1, 2-disubstituted polar internal olefin and product thereof |
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| CN109134547A (en) * | 2017-06-28 | 2019-01-04 | 赞南科技(上海)有限公司 | A kind of ruthenium complex, preparation method and application |
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| CN110938164A (en) * | 2019-11-12 | 2020-03-31 | 中国科学技术大学 | One-pot method for tandem catalytic copolymerization of ethylene and 1, 2-disubstituted polar internal olefin and product thereof |
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